1. business and industrial
2. chemicals industry
3. plastics and polymers

American Chemical Society Division of Cellulose and Renewable Materials
249th ACS National Meeting, Denver, CO, March 22-26, 2015
C. Frazier, Program Chair
SUNDAY MORNING
Cellulose in Solid State and Solution - Structure, Chemistry and Reaction Mechanisms: Anselme Payen Award Symposium in Honor of Thomas
Rosenau A. Potthast, Organizer; F. Liebner, Organizer; L. Lucia, Organizer; P. Kosma, Presiding; J. Ralph, Presiding Papers 1-8
Functional Lignocellulosics and Nanotechnology T. Nypelö, Organizer; M. S. Peresin, Organizer; I. Filpponen, Organizer; S. Spirk, Organizer; T.
Nypelö, Presiding; M. S. Peresin, Presiding Papers 9-19
Advances in Lignocellulosic Materials and Chemistry: A Tribute to W.G. Glasser G. Garnier, Organizer; T. G. Rials, Organizer; S. Kelley,
Organizer; T. G. Rials, Presiding Papers 20-26
Lignin Biosynthesis, Characterization and Modifications T. Tamminen, Organizer; C. Crestini, Organizer; C. Crestini, Presiding Papers 27-34
Application of Computational Chemistry to Biomass Chemistry and Utilization T. J. Elder, Organizer; S. C. Chmely, Organizer; P. Ramakrishnan,
Presiding Papers 35-42
SUNDAY AFTERNOON
Cellulose in Solid State and Solution - Structure, Chemistry and Reaction Mechanisms: Anselme Payen Award Symposium in Honor of Thomas
Rosenau A. Potthast, Organizer; F. Liebner, Organizer; L. Lucia, Organizer; H. Sixta, Presiding; A. Van Heiningen, Presiding Papers 43-50
Functional Lignocellulosics and Nanotechnology M. S. Peresin, Organizer; I. Filpponen, Organizer; T. Nypelö, Organizer; S. Spirk, Organizer; I.
Filpponen, Presiding; T. Tammelin, Presiding Papers 51-61
Advances in Lignocellulosic Materials and Chemistry: A Tribute to W.G. Glasser G. Garnier, Organizer; T. G. Rials, Organizer; S. Kelley,
Organizer; G. Garnier, Presiding Papers 62-69
Lignin Biosynthesis, Characterization and Modifications T. Tamminen, Organizer; C. Crestini, Organizer; T. Tamminen, Presiding Papers 70-77
Application of Computational Chemistry to Biomass Chemistry and Utilization
T. J. Elder, Organizer; S. C. Chmely, Organizer; P. Ciesielski, Presiding Papers 78-85
SUNDAY EVENING
Advances in Lignocellulosic Materials and Chemistry: A Tribute to W.G. Glasser G. Garnier, Organizer; T. G. Rials, Organizer; S. Kelley,
Organizer; Papers 86-115
General Posters C. E. Frazier, Organizer; Papers 87-153
MONDAY MORNING
Cellulose in Solid State and Solution - Structure, Chemistry and Reaction Mechanisms: Anselme Payen Award Symposium in Honor of Thomas
Rosenau A. Potthast, Organizer; F. Liebner, Organizer; L. Lucia, Organizer; M. Tenkanen, Presiding; D. O. Klemm, Presiding Papers 154-161
Functional Lignocellulosics and Nanotechnology I. Filpponen, Organizer; T. Nypelö, Organizer; M. S. Peresin, Organizer; S. Spirk, Organizer; M. S.
Peresin, Presiding; I. Filpponen, Presiding Papers 162-171
Advances in Lignocellulosic Materials and Chemistry: A Tribute to W.G. Glasser G. Garnier, Organizer; T. G. Rials, Organizer; S. Kelley,
Organizer; S. Kelley, Presiding Papers 172-179
Lignin Biosynthesis, Characterization and Modifications T. Tamminen, Organizer; C. Crestini, Organizer; R. Gosselink, Presiding Papers 180-187
Frontiers in Glycoscience K. J. Edgar, Organizer; L. Wang, Organizer; L. C. Hsieh-Wilson, Presiding Papers 188-193
MONDAY AFTERNOON
Cellulose in Solid State and Solution - Structure, Chemistry and Reaction Mechanisms: Anselme Payen Award Symposium in Honor of Thomas
Rosenau F. Liebner, Organizer; A. Potthast, Organizer; L. Lucia, Organizer; D. G. Gray, Presiding; F. Liebner, Presiding Papers 194-201
Functional Lignocellulosics and Nanotechnology T. Nypelö, Organizer; M. S. Peresin, Organizer; I. Filpponen, Organizer; S. Spirk, Organizer; T.
Nypelö, Presiding; C. A. Carrillo, Presiding Papers 202-212
Application of Computational Chemistry to Biomass Chemistry and Utilization T. J. Elder, Organizer; S. C. Chmely, Organizer; B. Knott, Presiding
Papers 213-220
Lignin Biosynthesis, Characterization and Modifications
T. Tamminen, Organizer; C. Crestini, Organizer; D. Da Silva Perez, Presiding Papers 221-228 Frontiers in Glycoscience K. J. Edgar, Organizer; L.
Wang, Organizer; K. J. Edgar, Presiding Papers 229-235
MONDAY EVENING
Sci-Mix C. E. Frazier, Organizer; Papers 87, 90, 93, 94, 95, 96, 98, 100, 103, 105, 109, 110, 111, 112, 115, 116, 119, 120, 126, 127, 130, 133, 135,
136, 145, 148, 153
TUESDAY MORNING
Cellulose in Solid State and Solution - Structure, Chemistry and Reaction Mechanisms: Anselme Payen Award Symposium in Honor of Thomas
Rosenau A. Potthast, Organizer; F. Liebner, Organizer; L. Lucia, Organizer; A. Isogai, Presiding; T. J. Heinze, Presiding Papers 236-243
Functional Lignocellulosics and Nanotechnology M. S. Peresin, Organizer; I. Filpponen, Organizer; T. Nypelö, Organizer; S. Spirk, Organizer; M. S.
Peresin, Presiding; T. Tammelin, Presiding Papers 244-254
Smart and Responsive Composites from Renewable Building Blocks L. A. Lucia, Organizer; Y. Habibi, Organizer; Q. Lin, Organizer; L. A. Lucia,
Presiding Papers 255-262
Renewable Resources for Materials and Energy: Recent Research and Developments in Ibero-America M. L. Auad, Organizer; O. J. Rojas,
Organizer; O. El Seoud, Organizer; D. Petri, Organizer; J. Campos-Teran, Organizer; O. J. Rojas, Presiding; O. El Seoud, Presiding Papers 263-270
Frontiers in Glycoscience K. J. Edgar, Organizer; L. Wang, Organizer; J. H. Prestegard, Presiding Papers 271-276
TUESDAY AFTERNOON
Cellulose in Solid State and Solution - Structure, Chemistry and Reaction Mechanisms: Anselme Payen Award Symposium in Honor of Thomas
Rosenau F. Liebner, Organizer; A. Potthast, Organizer; L. Lucia, Organizer; A. Potthast, Presiding; K. J. Edgar, Presiding Papers 277-283
Frontiers in Glycoscience K. J. Edgar, Organizer; L. Wang, Organizer; L. Wang, Presiding Papers 284-290
WEDNESDAY MORNING
Cellulose in Solid State and Solution - Structure, Chemistry and Reaction Mechanisms: Anselme Payen Award Symposium in Honor of Thomas
Rosenau A. Potthast, Organizer; F. Liebner, Organizer; L. Lucia, Organizer; L. Lucia, Presiding; T. Roeder, Presiding Papers 291-299
Functional Lignocellulosics and Nanotechnology S. Spirk, Organizer; I. Filpponen, Organizer; T. Nypelö, Organizer; M. S. Peresin, Organizer; S.
Spirk, Presiding; I. Filpponen, Presiding Papers 300-310
Smart and Responsive Composites from Renewable Building Blocks L. A. Lucia, Organizer; Y. Habibi, Organizer; Q. Lin, Organizer; Y. Habibi,
Presiding Papers 311-318
Renewable Resources for Materials and Energy: Recent Research and Developments in Ibero-America M. L. Auad, Organizer; O. J. Rojas,
Organizer; O. El Seoud, Organizer; D. Petri, Organizer; J. Campos-Teran, Organizer; M. L. Auad, Presiding; R. Christoph, Presiding; J. VegaBaudrit, Presiding Papers 319-327
Cellulose Dissolution: New Solvents and Mechanisms N. Abidi, Organizer; E. L. Quitevis, Organizer; N. Abidi, Presiding; E. L. Quitevis, Presiding
Papers 328-335
WEDNESDAY AFTERNOON
ACS Award for Affordable Green Chemistry: Symposium in Honor of John Frye, Todd Werpy, and Alan Zacher L. A. Lucia, Organizer; C. E.
Frazier, Organizer; L. A. Lucia, Presiding; C. E. Frazier, Presiding Papers 336-344
Functional Lignocellulosics and Nanotechnology I. Filpponen, Organizer; T. Nypelö, Organizer; M. S. Peresin, Organizer; S. Spirk, Organizer; T.
Nypelö, Presiding; M. S. Peresin, Presiding Papers 345-351
Smart and Responsive Composites from Renewable Building Blocks L. A. Lucia, Organizer; Y. Habibi, Organizer; Q. Lin, Organizer; L. A. Lucia,
Presiding Papers 352-357
Renewable Resources for Materials and Energy: Recent Research and Developments in Ibero-America M. L. Auad, Organizer; O. J. Rojas,
Organizer; O. El Seoud, Organizer; D. Petri, Organizer; J. Campos-Teran, Organizer; D. Petri, Presiding; S. Madrigal, Presiding Papers 358-365
Cellulose Dissolution: New Solvents and Mechanisms E. L. Quitevis, Organizer; N. Abidi, Organizer; E. L. Quitevis, Presiding; N. Abidi, Presiding
Papers 366-373
THURSDAY MORNING
Conservation Science of Cellulosic Materials - Recent Developments U. Henniges, Organizer; A. Potthast, Organizer; U. Henniges, Presiding Papers
374-381
Research on Renewable Materials: US and EU Perspectives P. E. Fardim, Organizer; P. R. Navard, Organizer; P. E. Fardim, Presiding Papers 382387
Renewable Resources for Materials and Energy: Recent Research and Developments in Ibero-America M. L. Auad, Organizer; O. J. Rojas,
Organizer; O. El Seoud, Organizer; D. Petri, Organizer; J. Campos-Teran, Organizer; J. Campos-Teran, Presiding; E. Torres, Presiding Papers 388396
Cellulose Dissolution: New Solvents and Mechanisms N. Abidi, Organizer; E. L. Quitevis, Organizer; N. Abidi, Presiding; E. L. Quitevis, Presiding
Papers 397-403
THURSDAY AFTERNOON
Conservation Science of Cellulosic Materials - Recent Developments U. Henniges, Organizer; A. Potthast, Organizer; A. Potthast, Presiding Papers
404-409
Research on Renewable Materials: US and EU Perspectives P. R. Navard, Organizer; P. E. Fardim, Organizer; P. R. Navard, Presiding Papers 410416
CELL 1
CELL 3
Thomas Rosenau, playful explorer of the mysteries of
cellulose
Fabrication
and
nanoanemone
Alfred D. French, [email protected]. Southern
Regional Research Center, U.S. Department of Agriculture,
Metairie, Louisiana, United States
Tetsuo Kondo, [email protected]. Graduate
School of Bioresource and Bioenvironmental Sciences, Kyushu
University, Fukuoka, Japan
Those who have been fortunate to spend significant time with
Rosi and his family will soon realize that they are all amazing
individuals. Even before that sinks in, you may wonder whether
Antje and Rosi’s lively young son Sebastian is the more staid,
or dare I say mature of the two males. But Rosi’s playful
character pays off in his science. Despite lack of commercial
prospects, some of their work is carried out just to see if
knowledge can be increased by synthesis of a new molecule.
Other work investigated a crystal found serendipitously in an
NMR tube. The lecture will touch on some of the findings from
crystal structures of derivatives of glucose, cellobiose and a
dimer of a ketoglucoside that add significantly to the
knowledge of cellulose and its chemistry.
The aqueous counter collision (ACC) method, which is
supposed as a nano-pulverizing method using only a pair of
water jets, also reveals the inherent nature of living things on
the individual hierarchical levels including nano-scales. When
the microbial cellulose pellicle secreted by Gluconacetobacter
xylinus was subjected to the ACC method, it was found to
deliver single nanofibers with subfibrillation as an aqueous
dispersion.More recently, an anaerobic culture using dissolved
oxygen for the bacterium provided a different type of nanofiber
to engage a pellicle. Namely, the secreted cellulose nanofiber
was thinner and richer in I-alpha crystalline phases than that
secreted in the normal culture. The engaged pellicle had a less
dense network structure than the normal one. These
morphological features indicated that the generated pellicle
under the anaerobic condition was meta-stable to physical
forces.In this study, the ACC process was, therefore, applied to
the pellicle cultured under the anaerobic condition to deliver a
different type of separate cellulose nanofibers. As the result,
the single nanofibers obtained were found uniquely fibrillated
only from the reducing end with lower collision energy. The
entire structure of the separate cellulose nanofiber resembled
sea anemone, and thus we have termed as “cellulose nanoanemone”.
CELL 2
Imperfections in higher plant cellulose: Crystal stacking
faults and structure of crystal-crystal interfaces
Carlos Driemeier, [email protected]. CTBE,
CNPEM, Campinas, São Paulo, Brazil
We report recent advances in understanding how structure of
higher plant cellulose deviates from the Iα and Iβ crystal
structures, which represent models of perfect cellulose
crystals. In the first part of this work, we consider a type of
crystallographic defect known as stacking fault [1]. This type of
defect is defined by Iα-like molecular layers existing within Iβ
crystals. We present diffraction patterns calculated from
crystals with stacking faults and show that such patterns
compare favorably with experimental data. The proposed
stacking faults bring a novel interpretation for Iα-Iβ coexistence
in higher plant cellulose. In the second part of the work, we
investigate the nature of cellulose crystal-crystal interfaces,
which are inherent to formation of cellulose crystal aggregates.
A geometric model of these interfaces is proposed with basis
on results from X-ray diffraction and moisture sorption
analyses performed across wide spectrum of celluloses
isolated from higher plants [2]. Furthermore, a novel analytical
technique - infrared spectroscopy associated with dynamics of
deuterium exchange - has been developed to selectively probe
such interface regions [3]. First results from this novel
technique are presented, bringing valuable information to
understand cellulose supramolecular structure in crystal-crystal
interface
regions.
[1] Driemeier, C.; Francisco, L. H. Cellulose 2014, 21, 3161–
3169.
[2] Driemeier, C.; Bragatto, J. J. Phys. Chem. B 2013, 117,
415–421.
[3] Driemeier et al. (in preparation).
characterization
of
cellulose
CELL 4
Cellulose nanocrystals: New preparation routes, and the
relationship to the structure of native cellulose
Eero Kontturi1,2, [email protected]. (1) Department of
Forest Products Technology, Aalto University, Aalto, Finland
(2) Department of Chemical Engineering, Imperial College
London, London, United Kingdom
Cellulose nanocrystals (CNCs) are conventionally prepared by
controlled sulphuric acid hydrolysis that is harsh enough to
cleave the disordered regions in the cellulose microfibril but still
mild enough to leave the crystallites intact. Recently, our group
has explored two alternative preparation routes to CNCs:
TEMPO-mediated oxidation of microcrystalline cellulose and
HCl vapour treatment of cotton fibres (filter paper). The first
method, TEMPO-mediated oxidation of microcrystalline
cellulose, resulted in nanocrystals of higher charge density
than in traditional CNCs, but the yield of CNCs was low (~4%).
Most of the microcrystals were converted to large, porous
particles with high charge density and – as shown by cryo TEM
– high degree of alignment between the cellulose crystallites
that they were composed of. The second route, hydrolysing
cotton fibres with HCl vapour, led to uncharged CNCs, yet their
yield was extremely high (>98%). The yield and the behaviour
of both substrates under CNC preparation conditions are
discussed from the point of view of the structure of native
cellulose. In addition, swelling of a CNC network on an ultrathin
film under increased humidity is explored and discussed.
CELL 5
Structural characteristics influencing the reactivity of
isolated cellulose I
[email protected].
(1)
Tomas
Larsson1,2,
Innventia AB, Stockholm, Sweden (2) KTH, Wallenberg Wood
Science Center, Stockholm, Sweden
Isolated cellulose I, can be considered to be a semi-crystalline
solid. Being one of the most abundant organic compounds on
the planet, its use in the production of commodities has
attracted attention for a long time. The ease by which cellulose
rich materials can be converted into chemicals or materials
with desirable properties, inevitably depend on the reactivity of
cellulose. The complex arrangements of the b-(1,4)-D-glucan
polymers in isolated cellulose creates a supramolecular
structure in the 1 nm – 100 nm range, capable of directly
influencing the reactivity and possibly also the chemistry of
cellulose I. In this paper examples will be presented illustrating
the influence of the supramolecular structure of isolated
cellulose I on its solubility, chemical reactivity and enzymatic
reactivity. Examples will also be given illustrating the
importance of well characterized samples for the purpose of
correctly interpreting results from enzymatic reactivity
measurements. A crystalline lattice of cellulose I type exists
within fibrils. In a sense fibrils are the smallest building blocks
of the supramolecular structure found in isolated cellulose I,
with fibril aggregates as building blocks at the next level. Fibrils
with widths of 3 nm to 5 nm are typically found in cellulose
isolated from wood. Due to their relatively high density and
stability, fibrils presents the phase boundaries responsible for
the maximally achievable specific surface area (SSA) of
cellulose I. Co-axial aggregation of fibrils and the presence of a
fibril aggregate network may limit the effective SSA. The
specific surface area and fibre wall average pore size are
shown to be factors influencing the reactivity of cellulose I
isolated in the form of fibres. The b-(1,4)-D-glucan polymers
present at fibril surfaces are the initial targets for any chemical
modification. Results indicate that the b-(1,4)-D-glucan
polymers present at fibril surfaces in isolated cellulose I exist in
a structurally and dynamically distinct state. Surface polymers
are significantly different from those present in the fibril interior.
Based on these findings connections between the properties of
the surface polymers and their reactivity, and connections to
the measurable degree of crystallinity of cellulose I will be
discussed.
interactions. If the state of the surface hydroxyl groups were
characterized better, it should be possible to develop a better
understanding of how to minimize the effect of water in
cellulose composites.Traditionally, deuterium (2H) NMR studies
of cellulose assessed molecular mobility by detecting the
motionally averaged 2H spectrum. Here, we demonstrate using
2H magic-angle-spinning (MAS) NMR to access different
populations of hydroxyl groups at the surface of 2H-exchanged
cellulose fibers. The cellulose fibers are initially equilibrated in
2H O atmosphere of controlled humidity and then dried in a
2
highly controlled manner so as to avoid contact with ambient
H2O. This process replaces the hydrogens of the accessible
hydroxyl groups by 2H. Different surface hydroxyl groups with
distinct molecular mobility are then observed by their response
in inversion recovery experiments with 2H MAS NMR detection.
CELL 7
High-resolution solution-State NMR of wood and pulp in
ionic liquid electrolytes
Ashley J. Holding, Valtteri Mäkelä, Kari J. Helminen, Ilkka
Kilpelainen, Alistair W. King, [email protected].
Department of Chemistry, University of Helsinki, Helsinki,
Finland
Ionic liquids are known to be highly effective solvents for
cellulose. They are mainly being investigated for cellulose
dissolution/regeneration
and
chemical
modification
applications. However, they also offer potential, as directdissolution media, for the analysis of wood and pulps, which
are rich in cellulose. In this abstract we present our results on
the 1 & 2D NMR analysis of cellulose dissolved in
tetraalkylphosphonium acetate: DMSO-d6 electrolytes. The
resolution is such that common polysaccharide resonances,
including reducing end anomers, have been identified in
several pulp samples. These can be identified in the 1H spectra
even for the highest molecular weight dissolving pulps, offering
new opportunities for analyses. Wood treated under various
conditions has also been analysed, giving more insight into the
factors which affect wood solubility in direct dissolution
solvents. Solubility was also found to be dependent on the size
of the cation in the electrolyte. At larger cation size solutions
were found to be isotropic until their saturation points. At lower
cation sizes liquid-crystalline phases were found to form at
relatively low pulp concentrations. In this regard, changes in
the NMR spectra, as a function of cellulose concentration and
temperature will also be discussed.
CELL 6
CELL 8
Identifying different hydroxyl populations in cellulose by
2H MAS NMR
Erik Lindh1,2, [email protected], Camilla Terenzi1,2, István Furó2,
Lennart Salmén1,3. (1) Wallenberg Wood Science Center, KTH
Royal Institute of Technology, Stockholm, Sweden (2) Division
of Applied Physical Chemistry, KTH Royal Institute of
Technology, Stockholm, Sweden (3) Innventia AB, Stockholm,
Sweden
Cellulose fibers have properties that make them a promising
renewable resource for creating strong composite materials. A
weakness of cellulose-based materials is, though, that their
advantageous properties are seriously affected when coming
in contact to water. One contributing reason for this effect is
the relatively high density of hydroxyl groups on the fiber
surface through which water can modulate fiber-fiber
NMR analysis of periodate-oxidation products of 5-Nacetylneuraminic acid methyl glycosides and 2,8polysialic acid (PSA)
Paul Kosma, [email protected]. Chemistry, University
of Natural Resources Life Sciences, Vienna, Austria
Periodate oxidation of α-(2→8)-linked polysialic acid PSA has
frequently been used to generate an aldehyde group at C7 of
the distal end unit of the polysaccharide chain to be used in
subsequent conjugation to protein carriers [1,2]. In-depth
analysis of reaction products ranging from Neu5Ac mono- to
tetramers, 4 kDa and 20 kDa polymers and their respective
periodate-oxidized products by high-field NMR spectroscopy
allowed for a detailed analysis of non-degenerate signals at
both reducing and non-reducing termini, respectively.
Moreover, the presence of a free 7-aldehyde group could be
excluded. Instead, oxidation of both anomeric Me glycosides
gave the 7-hydrated aldehyde products, whereas oxidation of
the oligomeric and polymeric substrates led to interresidue
hemiacetal formation extending from C7 of the terminal end
group to O-9 of the neighboring Neu5Ac residue [3].
Acknowledgment
The oxidized 4 kDa polysialic acid material was kindly provided
by Serum Institute of India Ltd.
Refs:
[1] M. Mühlenhoff et al., Curr. Opinion Struct. Biol. 1998 (8)
558. [2] L.M. Krug et al., Clin. Cancer Res. 2004 (10) 916. [3]
G.J. Ray, N. Ravenscroft, J. Siekmann, Z. Zhang, P. Sanders,
U. Shaligram, C. M. Szabo, P. Kosma, Bioconj. Chem. 2014
(25) 665.
CELL 9
Pickering foams from cellulose nanofibrils
Lars Wagberg1, [email protected], Nicholas Tchang Cervin2.
(1) Fibre Polymer Technology and Wallenberg Wood Science
Centre, KTH Royal Institute of Technology, Stockholm,
Sweden (2) Wallenberg Wood Science Center, Stockholm,
Sweden
During the last decade there has been a huge interest in new
materials from nanocellulosic either in the form of cellulose
nano crystals (CNC) or cellulose nanofibrils (CNF)1. The
interest is partly based on our urgent need for renewable raw
materials in today’s society and partly on new efficient
production methods both for CNC and CNF. However, both the
CNC and the CNF are prepared at very low solids
concentration and their handling and conversion to final
materials poses significant challenges. We have shown that it
is possible to prepare strong, low density CNF foams using
solids concentration between 1 and 10 g/l. To do this we have
used a pickering foam technique where surface modified CNFs
are used to stabilize air bubbles which become so stable that
they can be dried with a maintained structure. By using
fluorescently labelled CNF and high speed photography it was
shown that the fibrils do concentrate at the air/water interface
and that they are able to stabilize two air bubbles forced
together. On a more fundamental level our results also show
that the accumulation of the CNFs at the air/water interface
both increases the complex viscoelastic modulus of the
interfaces and decreases the interfacial tension. It is also
demonstrated that the aspect ratio of the particles is important
since CNF is much more efficient in increasing the foam
stability compared with CNC with a similar chemical
composition and the efficient gel-forming ability of the CNF at
the interface is suggested to be a major explanation to the
excellent foam stability during dewatering and drying of the
foam.
Klemm, D., Kramer, F., Moritz, S., Lindström, T., Ankerfors, M.,
Gray, D. and Dorris, A. (2011) Nanocelluloses : A new Family
of Nature – Based Materials. Angewandte Chemie
(International Ed. in English), 200, 5438–5466.
CELL 10
Inhibition of alphavirus infection with tyrosine sulfate
mimetic cellulose nanocrystals
Justin O. Zoppe1, [email protected], Ville Ruottinen2,
Seppo
Rönkkö2,
Leena-Sisko
Janne
Ruotsalainen2,
3,
2
Ari Hinkkanen , Kristiina Järvinen2, Jukka
Johansson
Seppälä3. (1) Institute of Materials, Polymers Laboratory,
EPFL, Lausanne, Switzerland (2) University of Eastern
Finland, Kuopio, Finland (3) Aalto University, Espoo, Finland
The spread of diseases caused by arthropod-borne viruses
calls for the development of novel inhibitors that can be used
for topical treatment and prevention in endemic areas.
Tyrosine sulfate-mediated interactions, and often sulfated
polysaccharides, play a crucial role in viral infections and are a
potential target for biomimetic nanostructures. We believe
cellulose nanocrystals (CNCs) offer a natural nanotechnologybased alternative to other classes of polyanionic inhibitors. By
the nature of sulfuric acid hydrolysis, CNCs carry a multivalent
display of anionic sulfate groups on their surfaces. We
developed multiple approaches for introducing multivalent
displays of tyrosine sulfate mimetic ligands on the surface of
CNCs. Subsequently, we used CNCs to inhibit fluorescent
marker expressing Semliki Forest virus vector (VA7-EGFP)
infection in primate cells in vitro. Furthermore, when tyrosine
sulfate mimetic CNCs were applied to VA7-EGFP, improved
viral inhibition was observed. Additionally, functionalized CNCs
did not cause observable toxicity to multiple cell lines. We
propose that conjugation of target-specific functionalities to
CNC surfaces provides a means to control their antiviral
activity and could be potentially employed against a broad
range of viruses, including HIV and Herpes simplexes.
CELL 11
Modification of nanocellulose with natural molecules: A
green perspective for cellulose based materials with active
properties
[email protected],
Araceli
Garcia1,2,
Alessandro Gandini1, Naceur Belgacem1, Julien Bras1. (1)
Laboratoire de Génie des Procédés Papetiers (LGP2),
Grenoble INP-Pagora, Grenoble, France (2) Department of
Chemical and Environmental Engineering, University of the
Basque Country UPV/EHU, Donostia-San Sebastián, Spain
Because its availability and renewability, the use of cellulose
fibers and crystals for the development of renewable and bionano-based composites is gaining great interest in last
decades. Moreover, the replacement of synthetic additives by
naturally obtained active compounds (antioxidants, antifungals,
toxins and radical scavengers) results a very important issue
from social, health and economic points of view.
In the present work, cellulose nanowhiskers and nanofibers
were grafted with different compounds containing functional
groups naturally available (aromatics, furanics) and for which
bioactive activity has already been reported. In this regard, the
bioactive groups grafted nanocelluloses were used together
with different renewable matrices for the in the formulation of
bio-nano-inspired composites and the development of smart
and active materials.
CELL 12
Size exclusion nanocellulose based paper filter for virus
removal
Albert
Mihranyan,
[email protected].
Nanotechnology and Functional Materials, Dep of Engineering
Sciences, Uppsala University, Uppsala, Sweden
Viral contamination of biotechnological products is a serious
challenge for production of therapeutic proteins and vaccines.
Because of the small size, virus removal is a non-trivial task,
and, therefore, inexpensive and robust virus removal filters are
highly demanded. Synthetic polymer based virus removal
filters are expensive because they are produced through
tedious multistep phase-inversion processing involving
hazardous solvents and rigorous pore annealing processing.
Cermaic based virus removal filters are heavy, hard to
regenerate (or to dispose), and thus impractical. Cellulose is
one of the most common materials to produce various types of
filters because it is inexpensive, disposable, inert, non-toxic,
mechanically strong, hydrophyllic, stable in a wide range of pH,
and withstanding sterilization e.g. by autoclaving. Normal
paper filter, used for chemistry, has too large pores to remove
viruses. A nanocellulose based paper filter is designed which is
capable of removing virus particles with the efficiency matching
that of the best industrial virus filters[1]. The reported paper
filter, which is manufactured according to the traditional paper
making processes, consists of 100% high purity cellulose
nanofibers directly derived from nature. The main mechanism
of virus removal is size exclusion rather than interception of
viruses via electrostatic interactions, which are sensitive to pH
and salt concentrations. The filtration properties of the
membrane have been verified using controlled size polystyrene
latex beads tagged with fluorophore groups (Figure 1) and
swine influenza virus (SIV) particles.
[1]. Metreveli, G., Wågberg, L., Emmoth, E., Belak, S.,
Strømme, M., Mihranyan, A. (2014). Size-exclusion
nanocellulose filter paper for virus removal, Advanced
Healthcare Materials, 3(10): 1546-1550
Figure 1. Polystyrene latex beads (100 nm) retained on a
nanocellulose based paper filter as studied by scanning electron
microscopy.
CELL 13
Antibacterial
materials
surface
modification
of
nanocellulosic
Jonatan Henschen, [email protected], Josefin Illergård, Per
Larsson, Monica Ek, Lars Wågberg. Department of Fibre and
Polymer Technology, KTH Royal Institute of Technology,
Stockholm, Sweden
Nanocellulose is a family of high-performance biomaterials
characterized by high stiffness, strength and biocompatibility,
and is proposed as a component in many applications, ranging
from barrier products to absorbency and medical products. For
many of these applications it can be desirable to incorporate
antibacterial properties to protect the product and/or the user.
Antibacterial modification of nanocellulose is commonly done
through incorporation of inorganic antimicrobial agents such as
colloidal silver. The use of silver is controversial and can lead
to environmental problems as the silver leaches out and is
even thought to lead to antibiotic resistance. It is therefore
desirable to find safer and sustainable alternatives. It has been
shown that cellulosic fibers can be made antibacterial by
adsorption of polyelectrolyte multilayers (PEMs) consisting of
polyvinylamine and polyacrylic acid (Illergård, J.; et al.
Cellulose 2012, 19, 1731-1741). The adsorption takes place in
water and is performed at room temperature using low-toxicity
compounds. On the fibers, the PEMs works via a contactactive antibacterial mechanism, i.e. the bacteria are
immobilized upon contact, and do not leach toxic compounds.
The same technique is possible to adapt to nanocellulose and
to thereby obtain a sustainable and environmentally-friendly
antibacterial nanocellulose material. In the present work,
materials produced from cellulose nanofibrils were modified
with the above-mentioned polyelectrolytes. The two tested
materials consisted of low-density aerogels with high specific
areas and high water absorbance capacity as well as films with
good oxygen barrier properties suitable for packaging
applications. The results showed that it is possible to adsorb
PEMs on both nanocellulose aerogels and films. The modified
aerogels efficiently removed bacteria from solutions while
maintaining its structure and ability to absorb water. The films
showed lower antibacterial effect compared to both the
aerogels and the previously tested cellulosic fibers and is still
under evaluation. Still, the results on the aerogels demonstrate
the feasibility of using the PEM technique on nanocellulose
materials. By introducing an environmentally friendly
antibacterial
modification
on
materials
made
from
nanocellulose, we are able to further improve on the
advantages of nanocellulose materials in technically
demanding areas such as the food, medical and hygiene area.
CELL 14
Tuning the properties and yield of cellulose nanocrystals
in the production space
Junyong Zhu, [email protected].
Madison, Wisconsin, United States
USDA
Forest
Service,
Cellulose nanocrystals (CNCs) are commonly produced using
strong acid hydrolysis of cellulosic fibers. The reduction of
cellulose degree of polymerization (DP), sulfation of cellulose,
and production of CNC under strong acid concentrations
occurred abruptly and simultaneously. As a result, process
control and optimization are very difficult. For over 60 years,
sulfuric acid concentration of approximately 64wt% has been
used as the standard condition for producing CNCs with good
dispersion properties due to the formation of sulfate groups
that imparts electrostatic stability, important for aqueous
processing. Low CNC yield of approximately 30-50% has been
the main drawback of this standard production acid
concentration despite several optimization studies were carried
out in the last several decades. Furthermore, the properties of
the resultant CNCs are not much affected by varying other
hydrolysis conditions at standard acid concentration of 64 wt%.
Here we present the first kinetic study of strong acid hydrolysis
reaction of cellulosic fibers. We were able to identify a
transition acid concentration of 58% below which low CNC
yield is due to insufficient cellulose deploymerization, while
above which low CNC yield was caused by CNC dissolution by
acid. This finding provides a mechanism for controlling CNC
yield by simply controlling acid concentration. Laboratory
bench scale experiments verified that CNC yield of over 70%
can be achieved when a bleach hardwood pulp was used. We
also found that acid concentration can be used to produce
desired CNC properties, such as CNC morphology, crystal
length, crystallinity, and surface charge. The importance of this
study is that the production of CNCs can now be tailored to a
specific application, for example, CNCs with large aspect ratio
(or long crystal length) may be most desirable for polymer
reinforcement in composite, while low aspect ratio CNCs with
uniform crystal length and high crystallinity may be more
suitable for smart windows or LED displays.
nanoparticles.
At the LS Institute of Wod Chemistry
thermocatalytic method is developed and later improved by
chemical oxidation pre-treatment. Also method of regeneration
of NSC from ionic liquids (IL) and traditional acid hydrolysis
were applied. Thermocatalytic method: materials are
impregnated with a weak acid (HCl) solution and thermally
treated, then dispersed in water medium in a ball mill. To
improve thermocatalytic method TEMPO (employing 2,2,6,6tetramethyl-piperidinyl-1-oxyl radical) catalysed oxidation pretreatmen was used. When using another oxidizer from
traditional ones like periodate, perchlorate or persulphate for
chemical pre-treatment destructed pulp sample is mixed with
oxidizer that has been dissolved in HCl and heated. Cellulose
sample is washed with deionized water and afterwards treated
by mixing and heating with NaOH and following washing. To
obtain nanoparticle gel the grinding in a ball mill is required.
Many problems for thermocatalytic method are solved by using
oxidizer – the energy consumption is decreased by 80% during
the grinding, obtained homogeneous nanoparticles with certain
shape. Crystallinity degree increase from 60% to 80-90%.
Ionic liquids (IL) are new eco-friendly solventsfor cellulose
dissolution. IL’s have abbility to modificate cellulose, both physically and chemically, even to nanoparticles in case of
specific IL and sonification. Regeneration method was
performed with 1-butyl-methylimidazolium hydrogen sulfate
(Bmim HSO4) IL. Acid hydrolysis was carried out in the
traditional way with 64% H2SO4 , followed by dialysis .
Particles
obtained
were
analyzed
with
Malvern
“ZetaNanosizer”, atomic force microscopy (AFM), electron
scanning microscopy (ESM) and x-ray diffraction (XRD).
Table 1. Cristallinity degree of cellulose samples by XRD
CELL 15
CELL 16
Properties of nanocellulose from wood pulp and bacterial
cellulose obtained by different methods
Nanocrystalline cellulose from agricultural waste for
optical devices
Laura Vikele1,2, [email protected], Inese Sable1, Linda
Rozenberga1,2, Rita Treimane2,1, Arnis Treimanis1,2, Pavels
Semjonovs2. (1) Latvian State Institute of Wood Chemistry,
Riga, Latvia (2) Institute of Microbiology and Biotechnology,
Riga, Latvia
Lisa Maria Steiner1, [email protected], Ahu G. Dumanli1,2,
David Reid1, Melinda Duer1, Silvia Vignolini1. (1) Department of
Chemistry, University of Cambridge, Cambridge, United
Kingdom (2) Soft Matter Physics, Adolphe Merkle Institute,
Fribourg, Switzerland
Nanostructured cellulose (NSC) serves as a promising
candidate for composite products. The aim of the study was to
develop nanostructurated cellulose (NSC) preparation methods
from bleached birch pulp and bacterial cellulose (BC). BC has
ribbon-shaped fibrils, high crystallinity degree, higher water
holding capacity and higher degree of polymerization. BC
creates interest as a new raw material for obtaining
Grape pomace is a cellulose-rich agricultural waste product in
the wine industry. In natural form cellulose is constituted of
amorphous and crystalline parts assembled into fibrillar form. It
is possible to extract the cellulose nanocrystals (CNCs) from
pomace through a multistep chemical purification and
hydrolysis process. In this work we demonstrate the extraction
of CNCs from the skin of white grapes [1]. XRD, NMR and FT-
IR were used to characterise the starting material, the
extraction process and the extracted cellulose micro-fibrils.
Then, these cellulose micro-fibrils were hydrolysed into
cellulose nanocrystals via acid hydrolysis, and AFM and SEM
were used to understand their morphological parameters such
as
dimensions
and
particle
size
distribution.
At a critical concentration, water based suspensions of CNCs
are shown to assemble into a chiral nematic phase that can be
maintained in the dry state, giving rise to strong iridescent
colourations [2,3]. These chiral nematic solid films have very
interesting optical properties such as only reflecting left handed
circularly polarised light. As the second stage of this study we
tested the self-assembly behaviour of the grape skin based
CNCs by evaporating from an aqueous suspension in a
controlled environment. Optical characterisation of the
obtained films was performed with optical microscopy and
optical goniometry [4].
[1] Lu P., Hsieh Y.; Carbohyd. Polym.; 87; 2546-2553; (2012)
[2] A. G. Dumanli, G. Kamita, J. Landman, H. van der Kooij, B.
J. Glover, J. J. Baumberg, U. Steiner, S. Vignolini; Adv. Opt.
Mat. 2; 646-650; (2014)
[3] A. G. Dumanli, H. van der Kooij, G. Kamita, E. Reisner, J. J.
Baumberg, U. Steiner, S. Vignolini; ACS Appl. Mater.
Interfaces 6 (15); 12302–12306; (2014)
[4] Vignolini S., Moyroud E., Glover B.J., Steiner U.; J R Soc
Interface; 10; (2013)
Cellulose NanoCrystals (CNC) can significantly improve the
mechanical performances of polymers at low loading levels
offering opportunities for new high value-added nanocomposite
materials. But to achieve an improvement of these properties,
good interfacial interactions must be obtained and the CNC
must be homogeneously dispersed in the polymeric matrix,
which is not trivial. Because of their high surface area and their
hydrophilic nature, the CNC cannot be easily dispersed in low
polarity mediums rendering it difficult to efficiently reinforce
most of the classical polymer matrices. The dispersability of
the CNC in such media can however be improved by surface
functionalization: chemical functions can be grafted at the CNC
surface to decrease the interfacial energy and increase their
interaction with the matrix (physical and/or chemical
interactions). In this context, we envisaged tailoring the CNC
surface by two original esterification methods performed in
water. The first one is based on the transesterification of vinyl
esters and the second one on carboxylic acid reactions
activated by water-soluble carbodiimide (EDCI). The CNC
surface after reaction was characterized by Fourier transform
infrared spectroscopy (FT-IR) and X-ray photoelectron
spectroscopy (XPS). The supramolecular structure of the
nanoparticles was examined by X-ray diffraction (XRD) and
atomic force microscopy (AFM). The reinforcing properties of
esterified CNC were subsequently investigated using naturel
rubber as a model matrix. The impact of the esterification
treatment on the properties of the nanocomposites will be
particularly discussed through various microscopic, thermal
and mechanical characterizations (SEM, TEM, DMA…).
CELL 18
Control of the surface properties of cellulose nanocystals
by transesterification of vinyl esters
Jérémie Brand, [email protected], Gilles Sèbe.
Laboratoire de Chimie des Polymères Organiques, University
of Bordeaux, Bordeaux, Aquitaine, France
AFM image of cellulose nanocrystals obtained from grape skin as
shown in the inset.
CELL 17
Characterisation and reinforcing properties of cellulose
nanocrystals esterified in water
Benjamin Dhuiege, [email protected], Gilles Sèbe.
Laboratoire de Chimie des Polymères Organiques, University
of Bordeaux, Pessac, France
In the current context of sustainability, there is a growing
interest in developing novel functional materials based on
sustainable bioresources. In particular, cellulose nanocrystals
(CNC) are nanometer-sized particles, which can be easily
recovered
from
cellulosic
substrates
(wood
pulp,
microcrystalline cellulose…) by sulfuric acid treatment.
Because of their high specific strength, modulus and aspect
ratio, CNC can significantly improve the mechanical
performances of polymers, at low loading levels. They can also
serve as stabilizing agents in Pickering emulsions, as matrix
for the preparation of aerogels or foams, or as templating
agents. But to realize the full potential of these applications,
the CNC surface must be tuned by appropriate functions to
control its dispersive, interfacial and self-assembling
properties. In this context, a novel and straightforward method
for the surface esterification of CNC by transesterification of
vinyl esters is proposed. The reaction of vinyl esters with the
CNC hydroxyl groups was examined in different solvents, with
potassium carbonate as catalyst. Reactions were performed
under microwave activation and monitored by Fourier
transform infrared spectroscopy (FT-IR) and Nuclear Magnetic
Resonance (NMR) spectroscopy. The supramolecular
structure of the CNC before and after modification was
characterized by X-ray diffraction (XRD) and atomic force
microscopy (AFM). The thermal stability was evaluated by
thermogravimetric analysis (TGA). The dispersibility of the
acetylated nanoparticles was examined in various solvents of
different polarities, using dynamic light scattering (DLS). The
impact of solvent and reaction time on the efficiency of the
reaction and
discussed.
nanoparticles
integrity
will be particularly
University, Sapporo, Japan (3) Department of Biomaterial
Sciences, Graduate School of Agricultural and Life Sciences,
The University of Tokyo, Tokyo, Japan
CELL 19
One step polymer grafting of poly(methyl methacrylate)
from cellulose nanocrystals for composite applications
Stephanie Kedzior, [email protected], Lexa Graham,
Emily D. Cranston. Chemical Engineering, McMaster
University, Hamilton, Ontario, Canada
Cellulose nanocrystals (CNCs) are desirable in composite
materials due to their low cost, bioavailability, light weight and
renewability. CNCs form stable colloidal suspensions in water,
however their hydrophilic nature often limits their applications,
since dispersing CNCs in hydrophobic polymer matrices and
organic solvents poses many challenges. In this work, we have
used a “grafting-from” method to graft short chain poly(methyl
methacrylate) (PMMA) polymers from the surface of cellulose
nanocrystals using ceric ammonium nitrate as the initiator in a
one step, water-based polymerization. PMMA-grafted-CNCs
were characterized using NanoSight nanoparticle tracking
analysis, atomic force microscopy, zeta potential, X-ray
photoelectron spectroscopy, contact angle, and nuclear
magnetic resonance. PMMA-grafted-CNCs were incorporated
into bulk PMMA composites using melt mixing and wet ball
milling methods and the mechanical, rheological and
morphological properties of CNC composites were assessed.
CELL 20
Mechanisms of biogenic formaldehyde generation in wood
Charles E. Frazier, [email protected], Guigui Wan, Mohammad
Tasooji, Heather Wise. Sustainable Biomaterials, Virginia Tech
, Blacksburg, Virginia, United States
We seek to understand the formation of natural biogenic
formaldehyde in solid wood, and how biogenic formaldehyde
impacts compliance with emissions regulations for nonstructural wood composites. Upon heat treatment, P. virgininia
wood generates substantial quantities of formaldehyde with no
detectable change in sugar composition, and with a large
reduction in lignin thioacidolysis yield. This suggestion of
lignin’s role was predicted in past studies of beta-O-4 models,
and that the gama methylol group is activated for formaldehyde
generation. Our attempts to test this mechanism verify some
but not all predictions from the lignin literature. Furthermore it
appears that extractives in P. virginiana also play a large role.
Our attempts to identify mechanisms of formaldehyde
generation will be described. The presentation will demonstrate
that current regulations require a thorough accounting of both
synthetic and biogenic formaldehyde sources.
CELL 21
Amphipathic
lignin
derivatives
for
enzymatic
saccharification and fermentation of lignocellulosics
Yoko
Yamamoto1,
[email protected], Ningning Cheng1,
Kiyohiko Igarashi3, Keiichi Koda2, Yasumitsu Uraki2. (1)
Graduate School of Agriculture, Hokkaido University, Sapporo,
Hokkaido, Japan (2) Research Faculty of Agricuture, Hokkaido
An enzymatic saccharification of lignocellulosics using
cellulase is considered as an environmentally benign, first
process for bioethanol production. However, the enzyme cost
is a main obstacle to its widespread application. Enzymatic
saccharification also faces difficulty in the repeated use of
cellulase. Several additives, such as non-ionic surfactant and
polyethylene glycol (PEG) with the molecular mass of more
than 4000 Da, have been reported to overcome the problems.
We also developed amphipathic lignin derivatives as the
additives, which were prepared from isolated lignins by the
reaction with epoxylated PEG analogues. When the lignin
derivatives were added to enzymatic saccharification media,
the sugar yield was significantly increased, and the cellulase
used could be recovered with remarkably high enzyme activity
from the media. In this study, we investigated the effect of the
amphipathic lignin derivatives on simultaneous saccharification
and fermentation process (SSF) of unbleached pulp, and the
mechanism to explain their contribution to enzymatic
saccharification. In a fed-batch SSF, bioethanol concentration
was significantly increased from 37.8 % to 49.4 % by the
addition of amphipathic lignin derivatives. This possitive effect
was assumed to be attributed to their high sacchrification
efficiency with the cellulase activity maintained during the
process. Hence, the interaction of cellulase with amphipathic
lignin derivatives and PEG 4000 was examined by Biocore, an
analyzer to monitor weight gain resulting from the association
between biological molecules based on surface plasmon
resonance. As a result, amphipathic lignin derivatives were
strongly adsorbed onto cellobiohydrases (CBH) I and II that are
the major components of cellulase derived from Trichoderma
reesei, while they were not adsorbed on endoglucanase (EG).
These different affinities are considered to be caused by the
difference
in
the
structures
of
CBH
and
EG.
On the other hand, PEG 4000 was not adsorbed on any
enzyme. This result suggests that the positive effect of PEG on
enzymatic saccharification is not attributed to its association
with cellulase. Thus, the mechanisms of our amphipathic lignin
derivatives and PEGs on the improved enzymatic
saccharification are quite different.
CELL 22
Homogeneous tosylation of agarose as an approach
towards functional bio-based materials
Martin Gericke, [email protected], Thomas J.
Heinze. Friedrich Schiller University of Jena, Jena, Germany
With respect to the limitations of fossil-based materials,
exploration and innovative use of bioresources become
increasingly important. Agarose, an abundant seaweed
polysaccharide (PS) that is renowned for its thermoreversible
gelation, has considerable potential in this context for the
preparation of functional biomaterials, e.g., hydrogels and
tissue-scaffolds. It is non-ionic and provides a large density of
OH-groups, i.e., agarose is well suited for polymer analogues
chemical modification. Tosylated polysaccharides are keyintermediates that can be converted with a vast variety of
nucleophiles to yield functional derivatives with specific
features. Based on knowledge on the preparation of ‘classical’
PS-derivatives, e.g., derived from cellulose or starch, tosylation
of agarose was studied with respect to the effects of the
reaction parameters (type of PS-solvent, time, amount of
tosylation reagent) on the molecular structure of the products.
Tosyl agaroses (TOSA) with high DStosyl ≤ 1.81 were obtained
in completely homogeneous reactions and characterized by
FT-IR and 1D-/2D-NMR spectroscopy. Despite the structural
resemblance of agarose and cellulose, TOSA showed a unique
substitution pattern that could be triggered from nonpreferential to regioselective tosylation by performing the
reaction with or without LiCl. Finally, the nucleophilic
displacement reaction of TOSA was studied using azide and
ethylendiamine with the aim to yield products (i) for “clickchemistry” approaches, (ii) with specific surface affinity/selfassembling properties. The novel deoxy-agarose derivatives
obtained partly showed thermoreversible gelation and will be
used for creating functional bio-based materials.
CELL 23
From sustainable chemical blocks to fuel: Synthesis of
hydrocarbons from isoprene and acrolein
Zhaohui Tong, [email protected], Fei Wang. University of
Florida, Gainesville, Florida, United States
The conversion of biomass to biofuels and value-added
chemicals has attracted numerous attention in terms of less
dependence on fossil fuel and increasing concerns on
environmental problems. Hydrocarbon fuels such as diesel and
jet fuel (C8-C21) have an advantage because of compatibility
with the current infrastructure and a higher energy density
suitable for truck and jet engines. Many routes have
extensively studied to produce hydrocarbon fuels using
furfural-based chemicals as the starting materials. Herein, we
reported new approach for the synthesis of hydrocarbon fuels
(C8 and C16) using abundant biomass-derived chemicals
isoprene and acrolein as the starting materials. C8 hydrocarbon
can be prepared directly by two-step reaction including a DielsAlder reaction between isoprene and acrolein to form 4-methylcyclohex-3-enecarbaldehyde
followed
by
a
hydrodeoxygenation reaction with up to 57% total yield. The
transition metal catalysts such as Pt/C, Pd/C, Fe/SiO2 and
Ni/SiO2 were screened to optimize the product yield.
Furthermore, a long chain C16 hydrocarbon was also
synthesized by a sequence of Diels-Alder reaction, reductive
coupling, and hydrodeoxygenation from isoprene and acrolein
as well.
CELL 24
Development of an efficient polymer analogous reaction in
ionic liquids and its application to chemical modification
of lignocellulose
Ryohei Kakuchi, [email protected], Yoshiki
Shibata, Makoto Yamaguchi, Kenji Takahashi. Institute of
Science and Engineering, Kanazawa University, Kanazawa,
Japan
As driven by a growing demand on alternative resources,
chemists have initiated researches on utilization of raw
biomass to produce chemicals, which targets chemical industry
without employing fossil resources. Biomass, in other words
the ligunocellulose, is known to be composed of three main
components, namely the lignin, the hemicellulose, and the
cellulose with highly sophisticated architectures. Usually,
biomass
utilization
has
been
depending
on
the
depolymerization processes of either lignin or polysaccharides.
Hence, reported biomass utilization approaches were
thermodynamically and economically disadvantageous.
Because of the limited solubility and reactivity of lignocellulose,
chemical modification of lignocellulose has been extremely
difficult for long years. A pioneering work in the field of biomass
utilization was reported in 2002 by Rogers and co-workers, in
which they have experimentally demonstrated that ionic liquids
(ILs) could dissolve cellulose under mild conditions. Triggered
by this report, other bio renewable materials including lignin
and even a raw biomass itself have been discovered to be
dissolved in ILs under mild conditions. Along with a fruitful
properties of ILs as solvent for biomass components, ILs have
been recently found to catalyze organic transformation
reactions in ILs with ILs as a catalyst. These findings
encouraged us to target chemical modification of biomass in
ILs with an organo-catalytic ability of ILs. Herein, we now
develop a conceptually new biomass utilization approach,
which is essentially based on a polymer analogous reactions of
the polysaccharide and lignin of the biomass. We paid our
attention to the common character of lignocelluloses. To be
precise, the hydroxyl groups exist in any components of
biomass. Therefore, the biomass modification was defined as
the polymer analogous reaction of polymers featuring hydroxyl
groups, namely the cellulose, the hemicellulose, and the lignin.
In this presentation, we describe 1) an efficient polymer
analogous reaction of cellulose in ILs with ILs as a catalyst to
afford modified cellulose and 2) polymer analogous reaction of
biomass in ILs to afford polysaccharide and lignin derivatives.
CELL 25
Fundamental approaches to multiscale,
phenomena in cellulose pyrolysis chemistry
multiphase
Christoph Krumm, [email protected], Alex Paulsen, Paul
J. Dauenhauer. Chemical Engineering & Materials Science,
University of Minnesota, Twin Cities, Minneapolis, Minnesota,
United States
Biomass pyrolysis is a promising thermochemical method for
producing renewable fuels and chemicals from biomass.
Development of a fundamental understanding of biomass
pyrolysis chemistry is difficult due to the multi-scale and multiphase nature of the process; biomass length scales span 11
orders of magnitude and pyrolysis phenomena include solid,
liquid, and gas phase chemistry in addition to heat and mass
transfer [1]. These complexities have a significant effect on
chemical product distributions [2]. Fundamental understanding
of cellulose pyrolysis chemistry in the absence of heat/mass
transfer limitations will allow for detailed chemical input-output
models used to scale up and optimize biomass pyrolysis
reactors. In this work, we describe the design of a new high
temperature reactor used to study cellulose pyrolysis
chemistry. The mechanisms and pathways of the primary
reactions of cellulose pyrolysis, including solid-liquid-vapor
transformations, are experimentally characterized. Our findings
highlight the importance of mass transfer on cellulose pyrolysis
chemistry and provide insight for the rational design of fullscale pyrolysis reactors.
[1] Mettler, M. S., Vlachos, D., and Dauenhauer, P. J., Energy
&
Envrinmental
Science,
2012,
5(7),
7797-7809
[2] Paulsen, A. D., Mettler, M. S., and Dauenhauer, P. J.,
Energy
&
Fuels,
2013,
27(4),
2126-2134
[3] Di Blasi, C., Prog. Energy Combust. Sci., 2008, 34, 47–90
CELL 26
Valorization of lignin to renewable fuels and chemicals
through biological funneling and chemical catalysis
Derek Vardon1,2, [email protected], Mary Ann Franden2,
Christopher Johnson2, Eric Karp2, Michael Guarnieri2, Jeffrey
Linger2, Philip Pienkos2, Timothy J. Strathmann1, Gregg
Beckham2. (1) University of Illinois at Urbana Champaign,
Lakewood, Colorado, United States (2) National Renewable
Energy Laboratory, Golden, Colorado, United States
observed with quinone methides containing syringyl structures.
It was also found that the stereochemistry in the addition of
water to QM’s at pH3 was closer to that found in native lignins
than at pH6. These findings suggest that lignin biosynthesis
may take place at lower pH than commonly suggested or the
QM reaction are otherwise catalysed by Lewis acids. In the
alkaline degradation of the arylglycerol β-O-4 structures, on the
other hand, the effect of sulphidity on the course of reactions
was followed. In addition to the experiments with dimeric QM’s
the reactivity of a large variety of oligomeric β-O-4 type lignin
models (trimers, tetramers, pentamers) and DHP was followed
by model cookings. The results were then compared with the
structural information obtained from isolated lignins of different
types of alkaline cooks (conv. Kraft, Soda-AQ, PolysulphideAQ, Flow-trough Kraft). The results demonstrate some
interesting differences in the behavior of quinone methides in
kraft and soda cooks
CELL 28
Lignin is an alkyl-aromatic polymer present in plant cell walls
for defense, structure, and water transport. Despite exhibiting a
high-energy content, lignin is typically slated for combustion in
modern biorefineries due to its inherent heterogeneity and
recalcitrance; however, it is critical for the economic success of
third-generation biorefineries to valorize lignin alongside
polysaccharides. This talk presents an integrated strategy that
employs biological conversion, separations, and catalysis to
convert lignin-derived species into renewable plastics, fuels,
and polymer precursors. Native and engineered strains of
Pseudomonas putida were utilized to produce (1) intracellular
medium chain length polyhydroxyalkanoic acids (mcl-PHAs) for
direct use as renewable plastics or for subsequent catalytic
conversion to hydrocarbon fuels, and (2) extracellular cis,cismuconic acid for subsequent catalytic conversion to adipic
acid, a nylon 6-6 precursor. Shake flask and fed-batch
biological conversion studies were conducted with model lignin
monomers, as well as with a depolymerized lignin stream
derived from alkaline pretreatment of corn stover. Downstream
processing strategies were examined to selectively recover
target metabolites, and subsequent catalytic processing was
demonstrated with a wide range of chemical catalysts.
Collectively, this effort provides a path forward towards
valorizing lignin to renewable fuels and chemicals through an
integrated scheme of biological funneling and chemical
catalysis.
CELL 27
β-O-4 -type quinone methides in lignin biosynthesis and in
pulping
Jussi Sipila1, [email protected], Anssi Haikarainen4,
Paula Nousiainen2, Mikko Muuronen3. (1) University of
Helsinki, Helsinki, Finland (2) Organic chemistry, University of
Helsinki, Helsinki, Finland (3) Department of Chemistry,
University of Helsinki, 00014 Helsingin yliopisto, Finland (4)
Medicinal chemistry, Orion Corporation, Espoo, Finland
p-Quinone methides constitute one of the most important class
of reactive intermediates in chemistry of plant biomass. In our
laboratory we have specifically investigated the reactivity of
different types of β-O-4 p-quinone methides, precursors of
arylglycerol-b-aryl ether structures. The results give new
aspects on the role of quinone methides in lignin chemistry.
While in aqueous solution at low pH (pH3) quinone methides
react quatitatively with water, at pH 6 significant amounts of
products formed via homolytical degradation pathway were
Molecular models of milled-wood lignin
Peter Schiffels1, [email protected], Heiko
Lange2, Claudia Crestini2. (1) Fraunhofer IFAM, Bremen,
Germany (2) Università degli Studi di Roma Tor Vergata,
Rome, Italy
Lignin is the second most abundant bio-polymer which
accounts for approximately 30% of the organically bound
carbon. Lignin exhibits a heterogeneous composition and
according to present knowledge lacks a defined primary
structure, its composition generally characterized by the
relative abundance of H/G/S units and by the distribution of
interunit bonding motifs. Various methods exist to reveal the
molecular details of lignin structure and most notably, there
have been significant advances in the interpretation of
quantitative HSQC-data and 31P-NMR spectra including endgroup titration. For Norway-Spruce Milled Wood Lignin (NSMWL), the currently available data provide sufficient
information for the construction of detailed molecular models.
In this talk, we demonstrate that the experimentally determined
relations between structural moieties or groups of structural
moieties can be used to formulate a well-defined set of linear
independent equations for the lignin structure. Standard
numerical techniques are used to solve the algebraic equations
for the most relevant structural motifs, which now enables us to
actually construct molecular models for individual oligomeric
lignin chains which in sum are representative of the whole
lignin sample. Starting from chain terminations, oligomeric
lignin chains are assembled as 2-D SMILES representations
by randomly connecting the motifs according their respective
abundance. Using present day computers, it is feasible to
generate thousands of SMILES-strings in reasonable times
and we show that this ensemble of 2-D molecular models not
only reproduces the known experimental data, but can also be
utilized to predict the effect of functionalizations such as the
change in molecular weight distribution as the sample is
subjected to AcBr treatment.
CELL 29
Mechanical properties of bamboo nanofibers: An atomistic
simulation study
Sina Youssefian2, Nima Rahbar1,2, [email protected]. (1) Civil
Engineering, Worcester Polytechnic Institute, Worcester,
Massachusetts, United States (2) Mechanical Engineering,
Worcester Polytechninc Institute, Worcester, Massachusetts,
United States
fibrils in plant cell walls and provide evidence as to the nature
of the lignin-cellulose interactions.
Bamboo, a fast-growing grass, has a higher strength-to-weight
ratio than steel and concrete. The unique properties of bamboo
come from the natural composite structure that comprises
mainly of cellulose nanofibers in a matrix of intertwined
hemicellulose and lignin called lignin-carbohydrate complex
(LCC). Here, we have utilized atomistic simulation to
investigate the mechanisms of interaction between these
materials present in the nanostructure of bamboo. With this
aim, we have developed a molecular model of LCC from lignin
and hemicellulose structures to study the elastic moduli, glass
transition temperatures and their adhesion energies to
cellulose nanobril faces. Good agreements are observed
between the simulation results and experimental data,
indicating the validity of the models. Studying the
Nanostructural
properties of these materials suggests that the abundance of
hydrogen bonds in hemicellulose chains is responsible for the
mechanical behavior of LCC. The strong van der Waals forces
between lignin molecules and cellulose nanobril cause
relatively large adhesion energy between LCC and cellulose
nanofibrils.
CELL 31
CELL 30
Impact of changes in the lignin synthetic pathway on cell
wall architecture
Jiliang Liu2, [email protected], Joanne C. Cusumano3,
Jeong Im Kim3, Clint chapple3, Lee Makowski1. (1)
Northeastern University, Boston, Massachusetts, United States
(2) electrical and computer engineering, northeastern
university, Malden, Massachusetts, United States (3)
Department of Biochemistry, purdue univeristy, West
Lafayette, Indiana, United States
We used scanning x-ray microdiffraction to the study of the
impact of mutations in the lignin biosynthetic pathway on the
architecture
of
the
plant
cell
wall.
Microdiffraction from the plant cell wall was separated into
oriented and disoriented components using custom software.
The oriented component exhibits significant cellulosic
reflections indicating that the oriented material in the plant cell
wall
is
mainly
composed
of
cellulose
fibrils.
Although the disoriented component shows considerable
cellulosic scattering, distinct non-cellulosic diffraction observed
is suggestive of amorphous formation of non-cellulosic
material. Lignin induced mutants introduce a modulation of the
observed intensity in the small angle region. This modulation
may rise from interference due to enhanced ordering of
cellulose fibrils. Inter-fibril distance was estimated on the basis
of a two-cylinder model. The interference calculation indicates
that the distance between cellulose fibrils in plant cell wall is
increased in plants with enhanced lignin content.
The (2 0 0) cellulosic reflections exhibited double orientation in
most tissues. The angle between the split reflections is referred
to as the microfibril angle. The increase in microfibril angle
from xylem to pith indicates that variation in lignin content
affects the ordering of cellulose fibril in a tissue specific
fashion. Although the rate of variation in microfibril angle
among lignin mutants and wild type were different the
maximum and minimum in microfibril angle was essentially
unchanged. These studies indicate that lignin content is tightly
correlated with the degree of order and orientation of cellulose
Diastereoselective fungal ligninolysis
Daniel J. Yelle2, [email protected], Alexander N. Kapich3,4,
Carl Houtman2, Fachuang Lu1, Vitaliy Tymokhin1, Raymond C.
Fort5, John Ralph1, Kenneth Hammel2,3. (1) Department of
Biochemistry, University of Wisconsin, Wisconsin Energy
Institute, Madison, Wisconsin, United States (2) Forest
Products Laboratory, U.S. Forest Service, Madison, Wisconsin,
United States (3) Department of Bacteriology, University of
Wisconsin, Madison, Wisconsin, United States (4) Institute of
Microbiology, National Academy of Sciences of Belarus, Minsk,
Belarus (5) Department of Chemistry, University of Maine,
Orono, Maine, United States
The white rot basidiomycete Ceriporiopsis subvermispora
delignifies wood selectively and has potential biotechnological
applications. Its ability to remove lignin before the substrate
porosity has increased enough to admit enzymes suggests that
small diffusible oxidants contribute to delignification. A key
question is whether these unidentified oxidants attack lignin via
single electron transfer (SET), in which case they are expected
to cleave its propyl sidechains between Cα and Cβ and to
oxidize the threo-diastereomer of its predominating β-O-4linked structures more extensively than the corresponding
erythro-diastereomer. We used two-dimensional solution-state
NMR techniques to look for changes in partially biodegraded
lignin extracted from spruce wood after white rot by C.
subvermispora. The results showed that (a) benzoic acid
residues indicative of Cα–Cβ cleavage were the major
identifiable truncated structures in the lignin after decay, and
(b) depletion of β-O-4-linked units was markedly
diastereoselective with a threo preference. The less selective
delignifier Phanerochaete chrysosporium also exhibited this
diastereoselectivity on spruce, and a P. chrysosporium lignin
peroxidase operating in conjunction with the P. chrysosporium
metabolite veratryl alcohol did likewise when cleaving synthetic
lignin in vitro. However, C. subvermispora was significantly
more diastereoselective than P. chrysosporium or lignin
peroxidase/veratryl alcohol. Our results show that the
ligninolytic oxidants of C. subvermispora are collectively more
diastereoselective than currently known fungal ligninolytic
oxidants, and suggest that SET oxidation is one of the
chemical mechanisms involved.
Chemical reactions occurring during: (a) Cleavage of lignin structure
A via fungal SET oxidation, followed by autooxidation of the
resulting lignin benzaldehydes; (b) Formation of structure A in the
lignifying plant cell wall via free radical coupling and nucleophilic
addition of water, showing routes for production of the erythro- and
threo-diastereomers.
exposure, showing oxidation at the surface (left and top) but not in
the interior of the wood.
CELL 32
CELL 33
Exquisite sensitivity of Acridine Orange to lignocellulosic
oxidation and mechanistic investigation
Lipoxygenase:
biorefinery
Peter Kitin1,2, Joe Worple2, Jon Houtman3, Kenneth E.
Hammel1,2, Christopher G. Hunt1, [email protected], Carl J.
Houtman1. (1) US Forest Service, Forest Products Laboratory,
Madison, Wisconsin, United States (2) Bacteriology, University
of WIsconsin - Madison, Madison, Wisconsin, United States (3)
Microbiology, University of Iowa, Iowa City, Iowa, United States
Claudia Crestini, [email protected], Heiko Lange, Paola
Giannì, Elisavet Bartzoka. Department of Chemical Sciences
and Technologies, University of Rome 'Tor Vergata', Rome,
Italy
Surface oxidation precedes depolymerization of lignocellulosic
biopolymers during fungal decay. We have observed that the
metachromic fluorescent dye acridine orange (AO) indicates
the oxidation state of wood surfaces. Fresh wood adsorbs AO
in a manner that results in green emission. In the first three
panels of the figure, thin sections exposed to a white-rot
fungus, Phanerochaete chrysosporium exhibit fluorescence
that begins as green and progresses to red by seven days.
Acid-chlorite treatment and UV exposure also result in red
emission (panels 4,5). AO has found wide application as a
microscopy stain, due to its metachromic behavior. The
association of poly nucleic acids with AO appears to have two
mechanisms. With double-stranded DNA and RNA, AO is
electronically isolated and emits green. In contrast, charged
interactions dominate interactions with single strands, which
favors stacking of AO molecules. Stacking results in a
combined electronic state between two AO molecules giving a
red fluorescent emission and fluorescent energy transfer
(FRET) quenching of any isolated AO molecules within the
Förster distance. We wish to understand the chemical
modifications that are responsible for the shift in AO-wood
interaction. Apparently, unmodified wood adsorbs AO as
isolated molecules. Microcrystalline cellulose, Sigmacell, and
milled wood enzyme lignin fluoresce green. Carboxy
methylated agarose beads, however, fluoresce red. These
observations lead to the hypothesis that carboxylic acid sites
are important for associations leading to red fluorescence,
which may be produced during oxidation. This is consistent
with isothermal titration calorimetry data, which indicate strong
binding sites and elimination of red fluorescence by
competitive adsorption by calcium. Fluorescence lifetime
measurements also indicate FRET between the green and red
fluorescent species on wood.
Acknoledgement: Supported by DE-SC0006929 from the U.S.
DOE, BER
Fluorescence of AO-stained white spruce wood after: (A) 0 days, (B)
3 days, (C) 7 days colonization by P. chyrsoporium, and after (D)
acid chlorite oxidation. (E) Cross section of a pine specimen after UV
A
new
oxidative
enzyme
for
lignin
The biotechnological conversion of lignocellulosic biomass is
widely used within the development and refinement of
biorefinery processes. Rather than functionalising lignin,
however, enzymatic treatments are used during the initial pretreatment of biomass for easing separation of components, or
for funnelling purposes during the production of different fuel
classes out of initial degradation products. Numerous studies
exist that describe the use lignocellulosic enzymes of laccases,
peroxidases, cellulases in biorefinery processes (e.g., Van Dyk
et al. 2012). We report here for the first time the use of
lipoxygenase for the valorisation of lignin. Based on detailed
mechanistic insight (Zoia et al. 2011), we used commercially
available lipoxygenase (EC 1.13.11.x) for structurally modifying
lignins. Control of reaction conditions allow the generation of
different structural features within oligomeric lignin chains, and
to covalently link functional moieties naturally not present in
lignin to the lignins via non-hydrolysable covalent bonds.
VanDyk, J.S., Pletschke, B.I. (2012). A review of lignocellulose
bioconversion using enzymatic hydrolysis and synergistic
cooperation between enzymes—Factors affecting enzymes,
conversion and synergy. Biotechnology Advances, 30(6),
1458-1480.
Zoia, L., Perazzini, R., Crestini, C., Argyropoulos, D.S. (2011).
Understanding the radical mechanism of lipoxygenases using
31P NMR spin trapping. Bioorganic & Medicinal Chemistry,
19(9), 3022-3028.
CELL 34
Quantitation of S/G ratio in woods using 1064 nm FTRaman spectroscopy
Umesh P. Agarwal, [email protected], Sally Ralph. Forest
Products Lab, Madison, Wisconsin, United States
A simple and accurate method based on 370 cm-1 Raman
band intensity was developed for quantification of syringyl-toguaiacyl ratio in woods. One of the major advantages of the
method is that woods (and probably other lignocelluloses) can
be directly analyzed and no prior isolation of lignin is required.
Therefore, the S/G ratio is representative of the whole cell wall
lignin and not just the isolated part or the portion of lignin that
gets cleaved during certain S/G chemical analyses. Besides,
additional problems associated with the traditional approaches
are avoided. The Raman analysis is quick, is free of use of
harmful chemicals, carried out nondestructively, and is
insensitive to the wet or dry state of the sample. The only
limitation is that a wood sample be not significantly fluorescent.
Although in the case of the latter, in some cases, methods
exist to rectify the situation. To test the accuracy of the Raman
method, the obtained S/G ratios were calibrated against the
values generated by the DFRC and 2D-13C NMR methods. The
former being an S/G method that takes into account only the
cleaved β-O-4 lignin units whereas NMR reports S/G ratio on
the whole cell wall lignin. Reliability of the Raman approach
was further supported by the quantitative analysis of several
syringyl lignin models.
CELL 35
Synthesizing cellulose
Brandon C. Knott1, [email protected], Michael F.
Crowley1, Michael Himmel1, Jochen Zimmer2, Gregg
Beckham1. (1) National Renewable Energy Laboratory,
Golden, Colorado, United States (2) University of Virginia,
Charlottesville, Virginia, United States
Cellulose is the most abundant biomaterial on Earth, yet the
mechanism of its synthesis has only begun to be revealed.
Understanding cellulose biosynthesis is a significant problem
with direct relevance to both glycopolymer sciences and the
design of new energy feedstocks with reduced recalcitrance.
After decades of research by groups worldwide, an
unprecedented discovery was reported in 2013 when the first
crystal structure of a bacterial cellulose synthase (Bcs) protein
complex was solved.1 Intriguingly, this multi-domain,
membrane-bound Bcs was captured with an intact cellulose
chain of 18 glucose units threaded through the binding tunnel
in an activated state. From this crystal structure, it is clear that
Bcs adds one glucose molecule at a time to the growing
cellulose chain from a UDP-glucose donor substrate. After
each glucose residue is added to the growing chain, the entire
chain must move forward one glucose unit before further
elongation. Further details of this processive cycle are
unknown. We investigate various scenarios of both the
chemical reaction and translocation with advanced molecular
simulation methods. The former of these utilizes transition path
sampling of hybrid QM/MM (quantum mechanical/molecular
mechanical) simulations. These simulations enable the
computation of free energy barriers, reveal detailed
mechanistic information regarding the glycosyl transfer
chemical reaction and cellulose translocation, and aid in
elucidating the nature and order of the discrete steps of the
synthase processive cycle. This work constitutes the first
dynamical look at the method by which the majority of Earth’s
organic carbon is produced.
1J.L.
Morgan, J. Strumillo, J. Zimmer, Nature 493, 181 (2013).
CELL 36
QM/MM and MD study on catalytic mechanism of bacterial
CESA
Hui Yang2, [email protected], Jung-Goo Lee1, Jochen
Zimmer3, Yaroslava G. Yingling1, James D. Kubicki2. (1)
Materials Science and Engineering, North Carolina State
University, Raleigh, North Carolina, United States (2)
Geosciences, The Pennsylvania State University, State
College, Pennsylvania, United States (3) Molecular Physiology
and Biological Physics, University of Virginia, Charlottesville,
Virginia, United States
Cellulose is a linear polymer of glucose molecules and
represents the most abundant renewable hydrocarbon source
in the world. Cellulose synthesis in plants is mediated by
cellulose
synthase
(CESA),
a
membrane-bound
glycosyltranferase family 2 enzyme, polymerizing glucose
molecules via glycosidic bonds between the C1 and C4
carbons. CESA utilizes activated glucose, UDP-α-D-Glucose
(the donor), as substrate and inverts the configuration of the
newly added glucosyl residue from α to β. Cellulose is also
produced by some bacteria, especially Gram-negative species,
where its biosynthesis is often concomitant with the formation
of biofilms. Bacterial biofilms are of particular concern to
human health due to their increased tolerance to antibiotics
and disinfectant chemicals. Due to difficulties in expressing
and manipulating catalytically active CESA enzymes, the
molecular mechanism of plant cellulose biosynthesis is still
elusive. The catalytic mechanism of bacterial cellulose
synthase was investigated by using a hybrid quantum
mechanics and molecular mechanics (QM/MM) approach. The
Michaelis complex model was built based on the X-ray crystal
structure of the cellulose synthase subunits BcsA and BcsB
containing a uridine diphosphate molecule and a translocating
glucan. A SN-2-type transition structure corresponding to the
nucleophilic attack of the non-reducing end O4 on the anomeric
carbon C1, the breaking of the glycosidic bond C1-O1, and the
transfer of proton from the non-reducing end O4 to the general
base Asp343 has been identified via the QM/MM simulation.
The activation barrier found for this SN-2-type transition state is
68 kJ/mol. The rate constant of polymerization is estimated to
be ~8.0 s-1 via transition state theory. Another Michaelis
complex model was built based on the X-ray crystal structure
relaxed with 200ns MD simulations at 300 K. The catalytic
mechanism obtained from MD relaxed structure has been
compared to the one obtained from X-ray crystal structure.
CELL 37
Molecular dynamics simulation study of the AxCeSD
octamer compelxed with cellulose chains
Toshifumi Yui1, [email protected], Takuya Uto1,5, Yuki
Ikeda3, Kenji Tajima2, Min Yao4. (1) Faculty of Engineering,
University of Miyazaki, Miyazaki, Japan (2) Graduate School of
Engineering, Hokkaido University, Sapporo, Japan (3)
Graduate School of Engineering University of Miyazaki, Japan,
Miyazaki, Japan (4) Faculty of Advanced Life Science,
Hokkaido University, Sapporo, Japan (5) Research Fellow of
Japan Society for the Promotion of Science, Miyazaki, Japan
The cellulose syntheses subunit D octamer in Acetobacter
xylinum (AxCeSD) is one of the four (A to D) subunits
composing the cellulose synthesizing terminal complex.
AxCeSD, coupled with AxCeSC, is suggested to play roles in
glucan chain extrusion and crystallization. The 3D structure of
the AxCeSD exhibits an exquisite cylinder shape of octamer
assembly.1 It also was suggested that a cellulose chain passed
through each of the dimer-dimer interfaces as an inner
pathways. The present study reports the computer docking and
molecular dynamics (MD) studies of the AxCeSD-cellulose
complex model to evaluate interactions between surfaces of
the
pathways
and
cellulose
chains.
Cellulose chains with DP = 24 were manually docked in the
pathways to form the complex model (Fig. 1). The 50 ns NTP
MD calculation (300 K and 1 bar) was carried out for the
complex model in solution state. The average binding energy
<ΔGbind> values based on the final 20 ns trajectories were
evaluated for each pathway and then decomposed by a
residue. Inside the pathways, water molecules diffused around
the equatorial sides of the cellulose chains where polar
functional groups were arrayed and the hydrophobic pyranose
faces tended to interact with amino acid residues.
Hydroxylmethyl groups were allowed to rotate frequently in the
pathways. The largest negative <ΔGbind> value, ranging about 7 to -4 kcal/mol pre residue, was found in the interior glucose
residues. Hu et al reported that cellulose production was
greatly depressed in the mutant cell with the AxCeSD gene of
N-terminus truncation up to Lys6.1 The present MD
calculations indicated that interactions with the cellulose chains
were detected from Ile3 and the following amino acid residues.
1. Hu S-Q, et al. Proc. Natl. Acad. Sci. USA 2010, 107, 1795717961.
CELL 39
DFT calculations on the
component interactions
thermodynamics
of
PCW
James D. Kubicki1, [email protected], Virgil Gibilterra1, Thomas
Weiss1, Heath Watts2, Loukas Petridis3, Paul Langan4, Linghao
Zhong5. (1) Geosciences, The Pennsylvania State University,
State College, Pennsylvania, United States (2) Space
Telescope Science Institute, University Park, Pennsylvania,
United States (3) Center for Molecular Biophysics, Oak Ridge
National LAboratory, Oak Ridge, Tennessee, United States (4)
MS 6475, Oak Ridge National Lab, Oak Ridge, Tennessee,
United States (5) Chemistry, Penn State Mont Alto, Mont Alto,
Pennsylvania, United States
A major goal in plant science is to construct an accurate,
detailed model of the plant cell wall (PCW - both primary and
secondary). Models have been proposed and improved over
the past few decades as information from biological
experiments, microscopy, mechanical tests, and spectroscopy
have added to our understanding of plant cell wall component
interactions. Although the assembly of plant cell walls is not
expected to be an equilibrium process, we hypothesize that
plant
cell
wall
architecture
takes
advantage
of
thermodynamically favorable interactions in order to optimize
the strength of the cell wall. Consequently, in this work, we
estimate the interaction energies of cellulose, hemicellulose,
lignin and pectin with one another using density functional
theory (DFT) calculations. Tetramer models are used with and
with explicit solvation via H2O molecules in order to examine
the effect water may have on PCW interactions. We also
compare the DFT energies and structures to those obtained
with the classical force fields CHARMM and COMPASSII.
Discussion of the various modeling approaches, comparison to
experimental observations and the implications for the
chemical strength of PCW component interactions will be
included.
Fig. 1 The structure of the AxCeSD and cellulose complex model.
CELL 38
Molecular basis for cellulose twist
Michael F. Crowley, [email protected], Lintao Bu,
Michael Himmel. National Renewable Energy Lab, Lakewood,
Colorado, United States
The observation of twisted microfibrils in cellulose I both in
imaging and in molecular simulations has been reported and
studied for years. Other crystalline forms of cellulose do not
show evidence of twisting at the microfibril scale. This article
reports a computational modeling study of cellulose I twist
showing its strong dependence on fibril diameter and no
dependence on fibril length or DP. We report the major cause
of the twist in the model empirically and analytically as the
hydrogen bonding that spans the glycosidic linkage. The lack
of twist in other forms of cellulose is strengthened by the need
for the TG orientation of primary alcohols, which only cellulose
I has, to form the twist-causing hydrogen bonds.
CELL 40
Can crystal structure conformations help
conformational analyses of isolated molecules?
validate
Alfred D. French, [email protected]. Southern
Regional Research Center, U.S. Department of Agriculture,
Metairie, Louisiana, United States
Some time ago, we tested a proposal that molecules in crystals
could be considered to be randomly deformed, compared to
their minimum-energy shapes in isolation. (French et al., J Mol
Graph Model 18 (2000) 95–107; Carbohydr Res 326 (2000)
305–322.) Recent work for a review article (French, DOI
10.1007/978-3-319-03751-6_33-1) expanded the range of
analyses to include geometries for furanose rings, as well as
new disaccharide linkage geometries. Given an energy
hypersurface for a given molecule such as a Ramachandran
f,y map for a disaccharide, the corresponding energies for the
geometries in various related crystal structures can be
obtained. For example, sufficiently related molecules might
include methyl lactoside when f and y of cellobiose are being
studied. According to the hypothesis of Bürgi and Dunitz (Acta
Crystallogr Sect B 44 (1988) 445–448) the distribution of these
energies should resemble a Boltzmann distribution, and a
“temperature” of the distribution can be derived by fitting an
exponential equation to the curve. Several apparently
successful fittings suggest that a “temperature” of about 500K
is appropriate to mimic the geometric variations observed in
crystals. It is also necessary to consider the overall distribution
to learn whether all of the low-energy areas are occupied by
observed conformations. Typically, some concession to the
condensed phase is needed in the modeling study.
CELL 41
Hydration control of the mechanical and dynamical
properties of cellulose
Loukas Petridis1, [email protected], Hugh M. ONeill2, Mariah
Johnsen7, Bingxin Fan3, Eugene Mamontov6, Janna K.
Maranas4, Roland Schulz1, Paul Langan5, Jeremy C. Smith1.
(1) Center for Molecular Biophysics, Oak Ridge National
LAboratory, Oak Ridge, Tennessee, United States (2) Biology
and Soft Matter Division, Oak Ridge Natl Lab, Oak Ridge,
Tennessee, United States (3) The Pennsylvania State
University, University Park, Pennsylvania, United States (4)
Penn State University, University Park, Pennsylvania, United
States (5) MS 6475, Oak Ridge National Lab, Oak Ridge,
Tennessee, United States (6) Oak Ridge National Laboratory,
Oak Ridge, Tennessee, United States (7) Ripon College,
Ripon, Wisconsin, United States
The mechanical and dynamical properties of cellulose are
essential for its function in plant cell walls and advanced
biomaterials. Cellulose is almost always found in a hydrated
state, and it is therefore important to understand how hydration
influences its dynamics and mechanics. Here, the
nanosecond-timescale dynamics of cellulose is characterized
using dynamic neutron scattering experiments and molecular
dynamics (MD) simulation. The experiments reveal that
hydrated samples exhibit a higher average mean-square
displacement above ~240 K. The MD simulation reveals that
the fluctuations of the surface hydroxymethyl atoms determine
the experimental temperature and hydration dependence. The
increase in the conformational disorder of the surface
hydroxymethyl groups with temperature follows the cellulose
persistence length, suggesting a coupling between structural
and mechanical properties of the biopolymer. In the MD
simulation 20% hydrated cellulose is more rigid than the dry
form, due to more closely-packed cellulose chains and water
molecules bridging cellulose monomers with hydrogen bonds.
This finding may have implications for the use of cellulose in
composite materials as well as understanding the origin of
strength and rigidity of secondary plant cell walls. The detailed
characterization obtained here provides a clear link between
structural, dynamical and mechanical properties of this
important biomolecule.
CELL 42
Modeling graphene-cellulose-water interactions
Stephen J. Eichhorn2, [email protected], Richard A.
Bryce1, Rasha Alqus1. (1) University of Manchester, School of
Pharmacy and Pharmaceutical Sci, Manchester, United
Kingdom (2) Physics, University of Exeter, Exeter, United
Kingdom
Molecular dynamics simulations have been applied to study
the interactions between hydrophobic and hydrophilic faces of
model cellulose crystals and a single layer of graphene in
explicit aqueous solvent. The hydrophobic face of the cellulose
crystal is predicted to form a stable complex with graphene.
The interface remains solvent-excluded over the course of the
simulation, with preservation of cellulose intra- and inter-chain
hydrogen bonds and a vacuum-like tg orientation of its
hydroxymethyl groups. Greater flexibility is observed in the
more solvent-exposed cellulose chains of the complex. By
contrast, over the course of 300 ns molecular dynamics
simulation, the hydrophilic face of cellulose exhibits
progressive rearrangement as it seeks to present its
hydrophobic face, with disrupted intra- and inter-chain
hydrogen bonding, sequential residue twisting to form CH-p
interactions with graphene and expulsion of interstitial water.
This transition is also reflected by an increasing cellulosegraphene adhesion energy as predicted at the PM6-DH2 level
of theory. The stability of cellulose’s hydrophobic face at the
graphene surface exemplifies the amphilicity of cellulose and
provides insight into favored interactions within this flexible,
conductive and mechanically strong nanocomposite material.
CELL 43
Recent progress on oxygen delignification of softwood
Kraft pulp
Adriaan Van Heiningen, [email protected].
Forest Bioproducts Res Inst, University of Maine, Orono,
Maine, United States
It has been identified that p-hydroxyphenyl structures in lignin
and condensed phenolic structures such as 5,5 biphenyls and
diphenyl methane are relatively inert during oxygen
delignification1,2,3. Therefore these structures accumulate in
residual lignin during oxygen delignification just as has been
found for glucomannan-lignin LCCs which are more stable than
xylan based LCC4. As a result very low oxygen delignification
rates and poor delignification/carbohydrate degradation
selectivities are obtained at high delignification degrees. This
explains that commercial softwood oxygen delignification is
halted at about 60% (based on kappa number) to avoid
excessive cellulose degradation and pulp yield loss. The
delignification rate at high lignin removal may be increased by
raising the temperature from a conventional level of about
90°C to 110-115°C, and by using a flow-through mode of
operation of oxygen delignification to achieve a low but
relatively constant alkali concentration similar as is practiced in
modern pulping. Unfortunately the increased temperature also
leads to increased cellulose degradation. Based on recent
analysis of the kinetics of delignification and cellulose
degradation during oxygen delignification we have proposed
that the increased cellulose degradation at high temperature is
caused by initial alkaline attack of labile groups on cellulose,
most likely carbonyls, which have survived Kraft pulping. After
the initial alkaline attack leading to cellulose cleavage by β
elimination, subsequent cellulose DP loss during oxygen
delignification is caused by oxygen-based radicals generated
as part of the phenolic delignification mechanism. Fortunately
the delignification/carbohydrate selectivity of phenolic
delignification is not affected by temperature. More recently we
have shown that the initial high temperature cellulose DP loss
may be reduced by high temperature treatment of softwood
kraft pulp in a through-flow oxygen delignification set-up where
the oxygenated alkaline solution is reinforced with NaBH4 at
the ppm level. Based on the present state of knowledge of
oxygen delignification the present talk will attempt to propose
how a higher pulp yield at lower final oxygen delignification
kappa number may be obtained by selecting the appropriate
operating conditions and integration of Kraft pulping and
oxygen delignification.
CELL 44
BLN hot water extraction process — taking forest biomass
fractionation to a totally new level
Stefan Willför1, [email protected], Lari Vähäsalo1,2, Sebastian
von Schoultz2. (1) Process Chemistry Centre, Åbo Akademi
University, Åbo, Finland (2) BLN-Woods Ltd, Pargas, Finland
This paper will discuss the novel BLN process, which provides
a significantly improved way of obtaining pure cellulose from
wood biomass, at the same time producing pure
hemicelluloses (WO2014009604 (A1), Method for extracting
biomass, pat. appl.) and sulfur- and carbohydrate-free lignin
(pat. pending). The process utilize vacuum and a design that
minimizes oxidation and degradation of the biomass and also
keeps the water consumption low. This enables water-soluble
and polymeric hemicelluloses, containing only a minimum of
lignin and other impurities, to be extracted at almost
quantitative yield from commercial wood chips and at lower
temperature (<150°C) than conventional extractions or
autohydrolysis processes. The fiber fraction can go on to a
normal pulping stage or then a fast and mild alkaline stage
(mild soda pulping) can recover the lignin, leaving a pulp with
an alpha-cellulose content >98% (41-43% total yield of the
wood for birch) at much lower energy input and chemical
consumption compared to traditional pulping.
CELL 45
Full utilization of wood in the future pulp mill bio-refinery
Peter Axegård, [email protected]. Business Area
Biorefining, Innventia AB, Stockholm, Sweden
Wood bio-refining is here defined as full utilization of wood into
a wide range of products. The kraft pulp process is here one
unique possibility. It is well-developed, industrially implemented
and minor modifications are needed to convert a kraft pulp mill
into an advanced bio-refinery producing technically pure wood
polymers and other products by the following approaches:
· Co-processing other bio-based feed-stocks as forestry
residues, sugar cane bagasse and by-products from
agriculture into lignin, cellulose (glucose) and C5/C6
hemicellulose.
· Extracting lignin and xylan from the black liquor.
· Extracting C5/C6 hemicellulose prior to kraft cooking.
· Utilizing internal pulp mill process streams such as solid byproducts and black liquor evaporation condensate.
Cellulose with high purity and high reactivity can by produced
from wood by pre-hydrolysis followed by kraft pulping. This is
interesting for environmentally benign processes for
regenerated cellulose. A major break-through (activation in the
pulp mill) has recently been made making it possible to
produce regenerated cellulose without carbon disulfide.
Glucose from side-streams is an attractive intermediate for
lactic
acid,
acetic
acid
and
ethanol.
Hemicelluloses it can be separated from hydrolysis stage of
wood prior the kraft cooking, from pulp fibers and from black
liquor. Hemicelluloses are interesting as raw material in
applications such as paper chemicals, composites and gas
barriers.
Lignin removal from kraft black liquors can be produced with
the LignoBoost process and similar processes. The first
commercial LignoBoost plant started production 2013 in the
US. The next installation starts production Q1 2015 in Finland.
Besides fuel applications promising results have been obtained
with carbon fibers from kraft lignin. Due to the high aromatic
content lignin shows promise as feed-stock for phenols, other
aromatics and transportation fuel.
CELL 46
Influence of pectinase treatments on the dissolution
abilities of cellulose pulps in NaOH-water
Patrick R. Navard1, [email protected], nuno
Dos Santos1,2, Jürgen Puls2, Bodo Saake2. (1) Mines
ParisTech, Sophia Antipolis, France (2) University Hamburg,
Hamburg, Germany
This paper is describing the effect of pectinase as a
pretreatment of several dissolving pulps and one paper grade
pulp prior to dissolution in NaOH. Two main studies were
performed, first with a pure pectinase, then with a mixture of
pectinase and endoglucanase. Despite the amount or
presence of pectin on the starting pulps was too low to be
determined, the incubation of different pulps with pectinase
preparations lead to an increase of the accessibility of the
fibers, reaching dissolution yields increase higher than 150%.
The enzymatic treatments were not affecting all the studied
pulps on the same manner, showing that the pretreatments
history of the dissolving pulps have an influence on the
enzymatic efficiency. Using a mixture of endopectinase and
endoglucanase showed that the synergistic effect of these two
enzymes is more effective than each enzyme taken alone on
cellulose activation. Endopectinase treatments show a great
improvement on cellulose accessibility to NaOH without any
significant changes of the chemical composition or
macrostructure and without material losses. The increase on
the dissolution yield in NaOH is directly proportional to the
enzyme concentration and to the time of the enzymatic
incubation. For the range of concentration and time
investigated, the enzymes have shown to be stable and, when
keeping constant the total endopectinase activity, the
enzymatic performance is independent of the time or enzyme
concentration. This allowed the definition of a new parameter
that is useful on the interpretation of results, the “total activity
units”, defined by the product of the initial activity units (units
per gram of pulp) by the incubation time (in hours). Although it
is clear that endopectinase treatments are improving the
chemical accessibility of the cellulose fibers, the mechanisms
behind this effect has not been fully understood. Some
hypothesis about this effect will be given.
CELL 47
Nanoporous cellulose: A new form of cellulose with novel
properties
Rajai H. Atalla1,2, [email protected], Rowan S. Atalla1. (1)
Cellulose Sciences International, Madison, Wisconsin, United
States (2) University of Wisconsin, Madison, Madison,
Wisconsin, United States
We report a novel form of cellulose formed by a treatment that
is a variation on the mercerization process. By using NaOH in
a co-solvent system that includes water and an alcohol rather
than pure water, it is possible to arrest the transition state
between celluloses I and II. It has a more open structure that
appears to have properties that are significantly different from
other celluloses. The key to its stability is that the removal of
the NaOH must be under conditions that prevent
mercerization. It is much more accessible to modifying
reagents whether chemical or enzymatic. Its porosity is
illustrated by its accessibility to the large polyiodide anions
responsible for the blue color obtained with starch. Its
accessibility to enzymes is such that the enzyme dosage
necessary for hydrolysis is an order of magnitude lower than
the dose required for the cellulose from which it is prepared.
Investigation of the structure of nanoporous state by x-ray
diffraction, together with Raman and solid State 13C NMR
spectroscopy suggests that it is a partially disordered state
wherein the cellulose chains remain parallel while the spacing
between them is expanded. However, it appears that the
anhydroglucose units within individual chains are partially
disordered. The disorder appears to occur at the nanoscale
only. The microscale and macroscale organization of pulp
fibers treated by the preparative process seem unaltered. The
primary difference in macroscopic properties is that pulp fibers
become quite elastic and can develop some curvature.
CELL 48
New model of plant cell wall cellulose elementary fibril
Umesh P. Agarwal, [email protected]. Forest Products Lab,
Madison, Wisconsin, United States
Traditionally, it has been accepted that the cell walls are made
up of elementary fibrils which are crystalline. However, based
on the recently obtained Raman evidence that showed that the
interior of a fibril was less than perfectly ordered a new model
is proposed. In this model, the molecular chains of cellulose
are still organized along the fibril direction but, at the local
level, the molecules retain significant degrees of freedom. This
results in some interior fibril-regions being water accessible.
The new fibril model has implications for not only formation of
inter-chain H-bonds and therefore, cellulose ultrastructure but
also, a number of areas of practical applications where
cellulose fibers are used. Various research and development
areas are likely to be impacted. A few implications will be
explored.
CELL 49
Effect of cellulose polymorphism on the TEMPO-based
oxidation and further grafting by amidation
Denilson Da Silva Perez3, [email protected],
[email protected],
Audrey
Youssef
Habibi2,
Guillemain3, Jean-Luc Puteaux1, Laurent Heux1. (1) CERMAVCNRS, Grenoble Cedex09, France (2) Advanced Materials and
Structures, CRP Henri Tudor, Hautcharage, Luxembourg (3)
New Materials DIvision, FCBA, Grenoble, France
The selective oxidation of primary hydroxyl groups of
polysaccharides
by
2,2,6,6-tetramethyl-piperidine-1-oxil
(TEMPO) has been demonstrated by different authors. From
the COOH group formed at C6 position, further grafting can be
achieved by amidation of different moieities in aqueous
medium. However, the success of using the TEMPO-oxidation
method for cellulose to produce water-soluble polyglucuronic
acid is highly dependent on the cellulose polymorphs. In the
case of native cellulose (cellulose I), although a significant
increase of water-soluble polyglucoronic acid is observed,
water-insoluble material always remains in all preparations.
This concept has been exploited to produce carboxylated
cellulose nanocrystals or nanofibres. Cellulose II is obtained by
fully dissolution of cellulose in appropriate solvents and
recrystallization. In this case, the reorganization of cellulose
chains in an anti-parallel arragement seems to liberate the
CH2OH group at C6 position for the TEMPO-mediated
oxidation reaction. Thus, contrarily to the native cellulose,
Cellulose II allomorph can be fully oxidized to yield pure
polyglucuronic acid. The swelling of cellulose in ammonia or
other higher amines is a simple and classical way to yield the
cellulose III allomorphs (IIII from cellulose I and IIIII from
cellulose II). This essentially solid-state process improves the
reactivity of crystalline cellulose for the preparation of
derivatives that keeps the integrity of the cellulose microfibrils
while achieving a substantial decrystallization and a
reorganization of the intracrystalline hydrogen bond pattern of
cellulose. We have demonstrated that a pretreatment of
cellulose sample with ammonia aiming at conversion of
cellulose I into III greatly improves its reactivity upon TEMPOmediated oxidation system. Finally, amorphous cellulose must
also be considered as it is rapidly and fully oxidized yielding
polyglucuronan. In this presentation, the effects of
polymorphism obtained from different cellulose sources for
TEMPO-oxidation and further grafting using different moieties
will be presented. Different aspects of the reactivity of the
different allomorphs will be addressed: the kinetics and
topochemistry of carboxylation and the consequent
solubilisation of the polyglucoronic acids, the impact on the
degree of polymerization of cellulose and/or polyglucoronic
acids and the reactivity of the oxidized cellulose and/or
polyglucoronic acids derivatives by amidation.
CELL 50
Porosity development of dissolving
mechanical and enzymatic processing
pulp
during
Stina Grönqvist1, Terhi Hakala1, Taina Kamppuri3, Marianna
Vehviläinen3, Tiina Liitiä1, Thad Maloney2, Anna Suurnäkki1,
[email protected]. (1) Technical research centre of Finland
VTT, Espoo, Finland (2) Aalto University, Espoo, Finland (3)
Tampere University of Technology, Tampere, Finland
Dissolving pulps, i.e. pulps consisting mainly of cellulose and
only of traces of hemicellulose and lignin, are used as raw
material for regenerated cellulose fibres. The intense chemical
treatments of wood carried out to produce the dissolving grade
pulps, result in removal of most hemicellulose and lignin from
the wood fibres and consequently increase the fibre porosity
[1,2]. However, the cell wall pores only exists in the water
swollen state and collapse to non-porous solid when dried
[1,3]. The fibre pore structure is relevant to almost all aspects
of cellulosic fibre processing. Mechanical forces cause internal
bonds in the fibre cell wall to break, allowing the cell wall to
expand, increasing its accessibility, flexibility and shrinkage
potential in drying. The fibre cell wall pore structure also affects
the action of cellulolytic enzymes having size similar to the
pores in the cell wall of chemical pulp fibers. Any changes in
the cell wall pore structure through e.g. mechanical processing
of fibers can thus influence the surface area that is accessible
to enzymes. Only basic aspects of the cell wall pore size
distribution, swelling and, most recently, fibril level swelling
have been described so far in connection to enzymatic
hydrolysis of cellulosic fibres. In this presentation the effects of
the mechanical and enzymatic pre-treatments on the pore
structure and alkaline solubility of dissolving grade pulp are
discussed based on recent findings. Formation of micro- and
macropores in the pulp fibres during mechanical shredding
was found to correlate with the susceptibility of the fibres to
enzymatic hydrolysis [4]. The fibre porosity development during
the processing was studied by a modified solute exclusion
approach, which revealed differences between the effect of
mild enzyme or acid hydrolysis on the pore structure of fibres.
The dissolution of the modified fibres in NaOH/ZnO was
evaluated and found to correlate with overall pore volume and
accessible surface area analysed by the modified solute
exclusion method.
values used to generate the experimental plan were the
following: Reaction time; NaBr, NaOCl; TEMPO. The
responses studied for the system were: Mean area-weighted
length (µm; Fines content, millions/g of puls; Reaction yield
(%); Carboxyl groups (mmol/g). Based on the results obtained
with the DoE CCD models, the following conditions were used
for the each scaling-up trial: 20 kg pulp (Domsjö); 400 L water
(5 % of consistency); 40 g TEMPO; 2.8 kg NaBr; 40 L NaOCl
(150 g/l); reaction time : 2 h. Five masterbatchs were produced
and the COOH content groups varied between 1.13 to 1.24
mmol/g, demonstrating very good repeatability of the trials
even at such scale.
1. Pönni R et al. 2013. Carbohydrate polymers 93:424-429.
2. Sixta H. 2006. Pulp Properties and Applications in
Handbook of Pulp. Sixta H (ed), Wiley-VHC GmbH &Co KGaA,
Weinheim
1009-1067.
3. Oksanen T. et al. 1997. Holzforschung 51:355-360.
4. Grönqvist, S. et al. 2014. Cellulose, article in press.
Figure 1 - TEMPO-oxidation M/NFC functionnalisation strategies
CELL 51
CELL 52
Functionalising micro/nanofibrillated cellulose with
TEMPO-based approaches: From laboratory to pilot scale
Structurally colored films using nanocellulose fiber
Denilson Da Silva Perez1, [email protected],
Audrey Guillemain1, Sandra Tapin-Lingua 1, Valerie Meyer2,
Benjamin Fabry2, Patrick Huber2. (1) New Materials DIvision,
FCBA, Grenoble, France (2) CTP, Centre Technique du
Papier, Grenoble, France
Stephen J. Eichhorn3, [email protected], Peter
Vukusic3, Daniel Hewson3, Jaime C. Grunlan1, Ping Tzeng2. (1)
Texas A M Univ, College Station, Texas, United States (2)
Dept Chem Eng, Texas A M Univ, College Station, Texas,
United States (3) Physics, University of Exeter, Exeter, United
Kingdom
One of the major drawbacks for using NFC is the high water
content of the final gel-like product (solid content between 24% ) . This extremely high viscosity is a major obstacle for any
application of NFC suspension in industrial processes.
TEMPO-mediated oxidation seems an interesting way of
increasing the solids content of the NFC suspension. TEMPO
oxidation allows selective oxidation of cellulose in C6 position.
Further functionalisation can be achieved by amidation of the
carboxyl
groups
introduced
by
TEMPO
oxidation.
In the frame of a European collaboration project (SUNPAP),
we were interested in an innovative approach consisting in
reducing NFC surface energy to control viscosity of NFC
suspension.
Three different strategies (1A, 1B and 1C) were studied for the
TEMPO-oxidation, according to the scheme of Figure 1. For
the strategy 1A, the oxidation is carried out on NFC while for
the other two strategies, it is performed on fibers prior NFC
production. Based on the results obtained, the strategy 1C was
chosen
for
scaling-up
the
process.
Then the TEMPO-oxidation conditions were optimized using a
Design of Experiment methodology by means of a Composite
Central Design (CCD). The following factors and the extreme
This talk will present some recent work on the assembly and
optical characterisation of structurally coloured films
comprising cellulose nanocrystals and other materials. The two
basic fabrication approaches used are layer-by-layer
deposition (LbL) of anionically charged cellulose nanocrystals
(CNCs), produced by sulphuric acid hydrolysis, and cationically
charged clay and the controlled drying of water/CNC droplets.
To form structurally coloured films using LbL, systems
comprising several sets of two different layers, of low and high
refractive index, are formed. For the low refractive index layers
a combination of colloidal silica and CNCs were combined. To
form a high refractive index layer, polyethyleneimie (PEI) was
combined with Vermiculite (VMT). Sequential dipping in each
of these solutions led to the formation of multilayered films,
also known as Bragg stacks. Alternatively we also investigated
the drying of concentrated droplets of CNCs in water on a
range of different substrates. A range of colored appearances
is reported across each dried droplet, with different structural
colors observed in different regions. This is thought to be due
to the presence of both multilayers and chiral nematically
arranged CNCs. In both cases (LbL and droplets) these CNC
structures have been characterised optically. Multilayer
modelling is also used to try understand the structures in more
detail.
CELL 53
Architecture and properties of hybrid cellulose
nanocrystals/Gibbsite nanoplatelets multilayered films
Clélia Martin1,3, [email protected], Robert Barker3,
Emily D. Cranston2, Laurent Heux1, Bruno Jean1. (1)
CERMAV-CNRS, Grenoble Cedex 9, France (2) Chemical
Engineering, McMaster University, Hamilton, Ontario, Canada
(3) Institut Laue-Langevin, Grenoble, France
This project aims at designing new hybrid organic/inorganic
functional thin films associating cellulose nanocrystals (CNCs)
and Gibbsite nanoplatelets (GNs) and at establishing the
relationships between the tunable film architecture and its
mechanical or optical properties. NCCs are biobased nanorods
that are attracting increasing attention from both the academic
and industrial communities due to their numerous properties
such as renewability, high specific surface area, excellent
mechanical properties, light weight, or non-toxicity. CNCs are
thus considered as highly promising building blocks for the
production of high performance biobased composites. In the
last ten years, negatively charged CNCs have been associated
with natural or synthetic polycations or neutral biopolymers
within thin multilayered films built by the layer-by-layer
assembly technique [1]. In the present study, polymer chains
have been replaced by positively charged inorganic Gibbsite
platelets to form innovative hybrid nanoparticles based thin
films. We have shown that the architecture of (CNC/GN) films
can be tuned over a wide range by adjusting the physicochemical parameters such as the aspect ratio of the CNCs, the
ionic strength, or by applying an intermediate drying step
between the layers deposition. For example, thin, dense and
very well-defined films or very thick and more porous
multilayers can be obtained in a controllable manner. The
detailed internal structure of the multilayered films has been
elucidated by the complementary use of AFM and neutron
reflectivity. The mechanical properties of films of various
architectures (Young’s modulus) have been measured using
the strain induced elastic buckling instability for mechanical
measurements technique and tentatively related to the films’
structure. The tunable properties of such hybrid multilayers
pave the way to the design of thin films and coatings for
separation membranes or supports for flexible electronics.
[1] C. Martin and B. Jean Nordic Pulp & Paper Research
Journal, 2014, 29, 19-30.
CELL 54
Functional cellulose nanocrystals for ATRP and click
chemistry-preparation and characterization
Anna Carlmark, [email protected], Assya Boujemaoui, Surinthra
Mongkhontreerat, Eva E. Malmstrom. KTH Royal Institute of
Technology, Stockholm, Sweden
The interest in cellulose nanocrystals (CNCs) have increased
rapidly1 and it is foreseen that the application potential of CNCs
can be significantly enhanced by surface modification.2
However, the functionalization of the CNCs by chemical
methods is very challenging. Typically, unmodified CNCs are
prepared by acid hydrolysis of cellulose fibers, followed by
liquid exchange into organic solvents or freeze drying and re-
dispersion, and subsequent post-functionalization. Herein,
functional CNCs (F-CNCs) have been produced employing
simultaneous acid hydrolysis and esterification, utilizing
functional organic acids in the preparation step,3 thus omitting
extra functionalization steps and tedious liquid exchange. In a
facile manner, functionalities such as double and triple bonds,
thiol groups and initiators for Atom Transfer Radical
Polymerization (ATRP)4 has been incorporated simultaneously
to the production of the CNCs, by the addition of 4-pentenoic
acid, 2-propynoic acid, 3-mercaptopropionic acid and 2bromopropionic acid, respectively. The F-CNCs were
investigated by FTIR, XPS, elemental analysis, XRD and AFM.
The thiol functionalized CNCs were reacted with Ellman´s
reagent and the thiol content was estimated to be 766 μmol g-1.
The alkyne functionalized CNCs were reacted with azidefunctionalized disperse red 13 via azide-alkyne Huisgen
cycloaddition5 and the content of triple bonds was estimated to
be 335 μmol g-1. The ATRP-initiator functionalized CNCs were
grafted with MMA by ATRP. We believe this study to be of
outmost importance for the chemical modification of CNCs and
hence
for
the
production
of
functional
CNCs.
1A. Dufresne, Nanocellulose:From Nature to High Performance
Tailored Materials, Berlin,Walter de Gruyter, 2012
2Y. Habibi, Chem. Soc. Rev. 2014, 43(5), 1519-1542
3B. Braun and J. R. Dorgan, Biomacromolecules, 2009, 10(2),
334-341
4W. A. Braunecker, K. Matyjaszewski, Prog. Pol. Sci. 2007, 32,
93-146
5H. C. Kolb, M. G. Finn, K. Barry Sharpless, Angew. Chem. Int.
Ed. 2001, 40, 2004-2021
CELL 55
Surfactant and polymer-enhanced
emulsions, gels, and oil powders
CNC
Pickering
Zhen Hu, Robert H. Pelton, Emily D. Cranston,
[email protected]. Chemical Engineering, McMaster
University, Hamilton, Ontario, Canada
By learning from nature and using biological components, we
can engineer sustainable high-performance materials with
improved functionality. This works presents emulsions
stabilized by cellulose nanocrystals (CNCs) combined with
either
cationic
surfactants
or
cellulose-adsorbing
polysaccharides. The resulting emulsions are extremely stable
over long time periods (> 1 year) and can be tailored to be oilin-water or water-in-oil. Surfactant and polymer adsorption to
CNCs modifies their surface/interfacial tension reducing
abilities and wettability which is directly linked to emulsion
droplet size and stability to coalescence. Polymer-enhanced
CNC Pickering emulsions can be transitioned to emulsion gels
at high temperatures by using thermally responsive polymers
and can be freeze-dried to give CNC-stabilized oil powders.
This work may extend the potential of CNCs to new liquid
formulations as well as extruded/spray-dried materials that are
low-cost, green and potentially edible.
CELL 56
Cellulose nanocrystals with CO2-switchable aggregation
and redispersion properties
Hai-Dong Wang2, Jean Bouchard1, Philip G. Jessop3, Pascale
Champagne4,
Michael
F.
Cunningham2,
[email protected]. (1) FPInnovations,
Pointe-Claire, Quebec, Canada (2) Dept Chem Eng, Queens
Univ, Kingston, Ontario, Canada (3) Dept of Chemistry,
Queens Univ, Kingston, Ontario, Canada (4) Civil
Engineering/Chemical Engineering, Queens University,
Kingston, Ontario, Canada
Cellulose nanocrystals (CNCs) were modified through a onestep 1,1′-carbonyldiimidazole (CDI)-mediated coupling with 1(3-aminopropyl)imidazole (APIm). The CNC-APIm prepared
could be readily dispersed into carbonated water. Subsequent
sparging of N2 into the dispersion gave rise to the formation of
aggregates.
This
dispersion/aggregation
cycle
was
reproducible by alternatively sparging CO2/N2 into the CNCAPIm aqueous dispersion, indicating that the chemically
bonded imidazole groups on the CNC surface were stable and
could respond to the CO2 stimulus in an effective and
repeatable manner. Moreover, above certain concentrations
(around 5.5~10 mg/ml) the CNC-APIm dispersion could be
gelled in the presence of N2 while subsequent sparging CO2
could break the gel and regenerate CNC-APIm dispersion.
This dispersion-gelation conversion was reversible by
alternatively switching between sparging CO2 and N2. To our
knowledge, the present work is the first report of CO2switchable CNCs.
CELL 57
Nanocellulose composites for electronic paper displays
Ahu G. Dumanli1,2, [email protected], Hua-Kang Yuan1,
Ullrich Steiner2. (1) Physics, Cavendish Laboratories,
Cambridge, United Kingdom (2) Soft Matter Physics, Adolphe
Merkle Institute, Fribourg , Switzerland
Cellulose is a renewable and highly abundant material with
excellent mechanical properties. Because of this, its
applications are wide-ranging and ubiquitous. Its use in
electronic devices provides an exciting alternative to current
implementations of plastic substrates (1). Using knowledge of
the nanostructure of cellulose, the present study demonstrates
fabrications of an electronic paper using nanocellulose (nanofibrillated bacterial cellulose -NFC) and multi-walled carbon
nanotubes (MWCNTs) and graphene, see Figure 1.
Our study shows that the quality of the films showed varying
degrees of macroscopic quality. Surface inhomogeneities are
suggested to be the result of polydispersity in NFC
suspensions. Scanning electron microscopy of successful films
showed that MWCNTs were embedded within the matrix
structure of NFC. Raman spectra of composites confirmed the
blend of materials and provided an indication of composite
dispersion. 4-point probe measurements revealed a range of
conductivities, from 1.06x10-6 Scm-1 to 0.0034 Scm-1. Finally,
graphene composites (Gr-NFC) were made by exfoliating
graphene flakes directly in NFC, as suggested by literature (2).
1. Shah J, Malcolm Brown R, Jr. Towards electronic paper
displays made from microbial cellulose. Appl Microbiol
Biotechnol.
2005
2005/01/01;66(4):352-5.
English.
2. Paton KR, Varrla E, Backes C, Smith RJ, Khan U, O’Neill A,
et al. Scalable production of large quantities of defect-free fewlayer graphene by shear exfoliation in liquids. Nat Mater. 2014
06//print;13(6):624-30.
Figure 1. A. Mechanical mixing of nanocellulose and Graphene
produce electroconductive nanocellulose composite thin films. B.
Cellulose papers produced with changed CNT content.
CELL 58
Manufacturing of cellulose nanofiber and applications
Yuichi Noguchi, [email protected]. Oji Holdings
Corporation, Koto Ward, Tokyo, Japan
Cellulose Nano Fiber (CNF) is nano size cellulose fiber with
high aspect ratio, which is produced by fibrillation of pulp. In
order to facilitate fibrillation of pulp efficiently, we investigated
new chemical pretreatments (e.g. Oxidation but not by
TEMPO, Esterification, and Etherification). We mainly use
highly concentrated pulp（30～100%）in these reactions
which means that the productivity is very high. Using these
techniques, we can control its size (short or long, coarse or
fine), surface charge (anionic, cationic or neutral) and
pKa(specifically with anionic CNF).We can also introduce
reactive or hydrophobic substituent group on surface of CNF.
We try to apply these unique CNFs to various applications. For
example, using high transparency CNF, we have been
successful in manufacturing continuous CNF transparent
sheet. The CNF transparent sheet has high transmittance
(>90%), low haze (<1%), high mechanical properties,
tolerability to organic solvent and flexibility. This sheet will be
useful as a material for organic light emitting display, foldable
solar cell and flexible TFT substrate.
CELL 60
Structure and properties of carboxylated nanocellulose
with various counter-ions
Michiko Shimizu1, [email protected], Tsuguyuki
Saito1, Akira Isogai2. (1) Department of Biomaterials Science,
The University of Tokyo, Tokyo, Japan (2) Univ Tokyo, Tokyo,
Japan
Figure 1. CNF transparent sheet roll
Table 1. Properties of CNF transparent sheet
CELL 59
Composite fibers from cellulose nanofibril emulsions
Tiina Nypelö1,2, [email protected], Carlos A. Carrillo2,
Orlando J. Rojas3,2. (1) Department für Chemie/ NAWARO,
Universität für Bodenkultur Wien, Tulln, Austria (2) Forest
Biomaterials, North Carolina State University, Raleigh, North
Carolina, United States (3) Department of Forest Products
Technology, Aalto University School of Chemical Technology,
Espoo, Finland
Cellulosic fillers and nanocelluloses have been of interest as
fillers and reinforcing agents in composites. Incorporation of
cellulose nanofibrils (CNFs) into a polymer matrix is not trivial
due to challenges in combining hydrophilic and hydrophobic
domains. CNF incorporation into a hydrophobic matrix has
typically been addressed by chemical modifications and
commonly requires processing steps such as drying or solvent
exchange. Contact between the filler and the matrix is
essential to avoid formation of weak interfaces that can impair
the performance of the composite. Here, we used a mixture of
lipophilic and hydrophilic amphiphiles to prepare CNF
emulsions with polystyrene and an organic solvent. The
favorable interactions between the nanocellulose and polymer
phase enabled the production of micro and nanofibers by
electrospinning. The surfactant system enabled a high
interfacial area between the organic and water phases, which
eliminated the need for solvent-exchange or drying of CNF to
prepare the spinning dope. Utilization of the surfactant system
together with CNFs enables preparation of a precursor system
leading to a new, efficient and scalable platform for the
preparation of CNF-reinforced polymer composites.
Nanofibrillated natural cellulose structures, or so-called
“nanocellulose”, have attracted increasing attention as highperformance sustainable materials with high elastic modulus,
high strength and low coefficient of linear thermal expansion.
Nanocellulose can form various types of stiff structured
materials. For example, nanocellulose films show high stiffness
and low oxygen permeability, and are promising as packaging
films and substrates for flexible electronics devices. However,
these nanocellulose materials have hydrophilic nature, which
often impairs such excellent properties. Here, we report
hydrophobic and ductile transparent nanocellulose films using
TEMPO
(2,2,6,6-tetramethylpiperidine-1-oxyl)-oxidized
cellulose nanofibrils (TOCNs). When native celluloses are
oxidized using TEMPO as a catalyst, sodium carboxylate
groups are formed in high density on the nanofibril surfaces.
We found that TOCNs with bulky quaternary alkylammonium
carboxylates (TOCN-QAs) can be dispersed into various
solvents including not only water but also alcohol and acetone.
In the present study, material properties of TOCN-QAs films
were characterized. All the TOCN-QA films showed high
optical transparency. As the alkyl chain lengths of the QAs
were increased, densities and moisture contents of the TOCNQA films decreased, and the pore diameters increased.
Mechanical properties of the TOCN-QA films were changed by
introducing QAs with different alkyl chain lengths. The ductility
of TOCN-QA films was likely brought about by the short and
dense alkyl chains of the QAs at the interfaces between the
TOCNs. Water contact angles of the TOCN-QA films increased
with the alkyl chain lengths of the QAs. The gas permeability of
the TOCN film was mainly explained by pore diameters of the
TOCN films and interactions between TOCNs. The present
study demonstrates that structural and material properties of
the TOCN films can be largely tunable through a simple
counterion-exchanging process.
CELL 61
Thermoresponsive TOCN films: Influence of PNIPAm on
film properties
Nathalie Lavoine1, [email protected], Julien Bras2,
Tsuguyuki Saito1, Akira Isogai1. (1) Biomaterial Sciences,
University of Tokyo, Tokyo, Japan (2) Laboratory of Pulp and
Paper Sciences and Graphic Arts (LGP2), Grenoble Institute of
Technology, Grenoble, France
Stimuli-responsive drug delivery systems are a promising
approach to control drug delivery according to the physiological
needs of the patient. They allow delivery of the drug at the right
time and concentration, by only releasing the drug in response
to an external stimulus. This study suggests a new kind of
responsive polymeric delivery system based on TEMPOoxidized
cellulose
nanofibers
(TOCN)
and
N(isopropylacrylamide),
PNIPAm,
a
commonly
used
thermoresponsive polymer for biomedical applications (Lower
Critical Solution Temperature of around 32 °C, closed to the
body temperature (37 °C)). Using an amide coupling reaction,
PNIPAm was grafted in aqueous medium and at different
molar ratio to TOCN dispersions with different carboxylate
contents. The influence of PNIPAm grafting was studied on the
films obtained from the grafted TOCN dispersions. Properties
such as tensile strength, water affinity, or porosity were
measured to attest the ability of such a new material to be
used as drug delivery system.
CELL 62
Contributions
of
computational
understanding cellulose
chemistry
to
Alfred D. French, [email protected]. Southern
Regional Research Center, U.S. Department of Agriculture,
Metairie, Louisiana, United States
In his role as Editor-in-Chief of Cellulose, Professor Glasser
has strongly supported computational approaches to
understanding cellulose, including our work. He has also been
a major enthusiast of vigorous debate, perhaps especially
appropriate for the applications of computational chemistry.
Participation in some of these debates has certainly expanded
both effort and focus on the issues that may be holding back
the increased use of the most prevalent biological
macromolecule. In particular, we were able to add knowledge
regarding molecular symmetry and crystal shape, hydroxyl
orientation and the “glue” that holds cellulose together. The
lecture will summarize our views and the evidence that
supports them.
CELL 63
Pros and cons of various cellulose crystallinity estimation
methods: 380-Raman, 13C NMR, and Segal-WAXS
Umesh P. Agarwal, [email protected]. Forest Products Lab,
Madison, Wisconsin, United States
Cellulose crystallinity is an important structural parameter of
cellulose materials and therefore, it needs to be measured
accurately. Considering that three methods, 380-Raman, 13C
NMR, and Segal-WAXS are frequently used to estimate
crystallinity, the methods are compared with respect to their
strengths and limitations. To evaluate the effectiveness of each
method, a number of criteria were selected. The latter included
effect of moisture, presence of amorphous components,
existence of mixed phases of cellulose, microfibril
coalescence, and presence of sample-fluorescence. In
addition, presenter’s observations on use of Scherrer formula
will be offered.
CELL 64
Interactions between rod-shaped nanoparticles
polymer chains in aqueous solutions
and
Hale Oguzlu, [email protected], Zahra Khalili, Yaman
Boluk. Department of Civil and Environmental, University of
Alberta, Edmonton, Alberta, Canada
Cellulose nanocrystals (CNC) are rod-shaped nanoparticles
with a typical particle length of 100-200 nm and width of 5-15
nm is produced by isolation of crystalline chains by applying
acid hydrolysis techniques. Mesoscopic scale properties
between CNC suspensions in dilute and semi-dilute water
soluble polymer solutions are leading certain rheological
properties that are interesting for personal care, coatings, and
other thickened industrial fluids. When CNCs present in
aqueous polymer solutions, polymer chains can either deplete
CNC or be adsorbed onto CNC. To investigate these
interactions, Nuclear Magnetic Resonance (NMR), Polarized
Optical Microscopy (POM) and rheological measurements of
carboxyl methyl solutions (CMC) with CNC nanoparticles were
performed. 1H NMR solvent relaxation technique has been
used to investigate adsorption and depletion interaction
between polymers and CNC. Unexpected maxima in spin-spin
(T2) relaxation with respect to polymer concentration graph
show depletion interaction due to depletion layer in solutions.
The steady-state shear and linear viscoelastic properties of
dilute and semi-dilute solutions of CNC in CMC solutions were
investigated. Steady state low shear viscosities of CMC
solutions increased 2-500 with respect to CNC concentration.
Gelation point of CNC-CMC solutions were observed with
frequency sweep analyses. The formation of depletion layer
which lead to an increase in the bulk polymer concentration is
resulted in an increase in shear viscosity and gelation. Phase
behavior of aqueous mixture of CMC and CNC, was
investigated by means of POM and birefringent gel-like
structures were observed in CMC solutions with the increase of
CNC concentration.
CELL 65
Synthesis and properties of fatty acid esters of technical
lignins for biorefinery applications
Klaus Koivu3, Hasan Sadeghifar2, Paula Nousiainen4, Dimitris
Argyropoulos1, Jussi Sipila3, [email protected]. (1) North
Carolina State Univ, Raleigh, North Carolina, United States (2)
North Carolina State University, Raleigh, North Carolina,
United States (3) University of Helsinki, Helsinki, Finland (4)
Organic chemistry, University of Helsinki, Helsinki, Finland
The utilization of the second most abundant plant biopolymer
lignin as a source for thermoplastics additives in polymeric
materials has challenged material chemists over several
decades. Only limited success have been achieved despite
broad variety of formulations studied so far, partly due to great
variances of lignins obtained from technical processes in terms
of structure, chemical reactivity and molecular size.
In the study new convenient methods for the preparation of
long chain fatty acid derivatives of lignins have been
developed. E.g. softwood LignoBoost kraft lignin was esterified
with ethanoyl (C2), octanoyl (C8), dodecanoyl (C12) and
hexadecanoyl (C16) chloride with various molar ratios with
respect to the total OH of lignin and analyzed with quantitative
31P-NMR
spectroscopy, FTIR- ATR, molecular weight
distribution and Differential Scanning Calorimetry (DSC). Their
structure and polymer properties (MW, Tg, rheological
properties) were examined with comparison to variety of
conventional Kraft lignins and new non-sulfur technical lignins.
The partially acylated technical lignins were further methylated
to obtain fully substituted lignins and studied on viscometer,
extruder and DSC to understand the effect of long chain fatty
acids on material properties. Oligomeric lignin model
compounds were applied to study the behavior of the so-called
“reactive groups” of lignins in the derivatization procedures and
to assist the selection of the particular type of technical lignins
for special application. The esterified lignins, in particular,
showed interesting properties as fiberboard barrier materials1
and possess promising properties also for thermoplastic
additives.
CELL 66
Single step functionalization of cellulose to produce
bacterial cellulose-reinforced derivatised all-cellulose
nanocomposites
Koon-Yang
Lee2,
Alexander
Bismarck1,
[email protected]. (1) Department of Chemical
Engineering, Imperial College London, London, United
Kingdom (2) Department of Chemical Engineering, University
College London, London, United Kingdom
Recent interests in green nanocomposites and public demands
for more environmental friendly materials have sparked the
development of nanocomposites derived from renewable
sources. One of the most studied materials in the field of green
nanocomposites is cellulose. Cellulose is the most abundant
organic material in the world. It can be produced by plant or
bacteria from the Acetobacter species. However, cellulose is
extremely hydrophilic in nature due to the presence of hydroxyl
groups. This will result in poor interfacial adhesion between
cellulose and hydrophobic biodegradable polymer matrices.
Therefore, novel methods are required to improve the
compatibility between the cellulose and the matrix. In this work,
a novel method of manufacturing bacterial cellulose (BC)reinforced derivatised all-cellulose nanocomposites in a single
step is presented. This concept is based on the co-modification
of two different celluloses and with different reactivity in the
same reaction medium. Never-dried BC was co-esterified in
the presence of microcrystalline cellulose (MCC) with hexanoic
acid. It was found that MCC could be severely modified with
hexanoic
acid,
producing
derivatised
all-cellulose
nanocomposites (C6-MCC) with degree of substitution of 0.78.
Introducing 5 wt.-% BC led to a slight decrease in the DS to
0.70 of the resulting BC-reinforced derivatised all-cellulose
nanocomposite (5 wt.-% BC-C6-MCC). Whilst BC is highly
crystalline, X-ray diffraction showed that the neat MCC used in
this study possess both a cellulose-I and -II structures.
Hydrogen-deuterium exchange experiments showed that the
cellulose-II structure of neat MCC led to more accessible
hydroxyl groups in neat MCC and therefore more susceptible
to esterification reaction compared to BC. Both C6-MCC and 5
wt.-% BC-C6-MCC were also found to be highly soluble in
toluene. The tensile modulus and strength of the solution
casted C6-MCC were found to be 0.99 GPa and 23.1 MPa,
respectively. The presence of 5 wt.-% BC in C6-MCC led to an
increase in tensile modulus and strength of the resulting
nanocomposites to 1.42 GPa and 28.4 MPa, respectively.
hydrophobic polymer block, easily prepared employing ATRP
in combination with Ring Opening-Polymerization (ROP), can
be adsorbed onto cellulose surface under aqueous
conditions.2,3 Herein, covalent grafting and physical adsorption
have been compared for the first time, with respect to the
material properties of nanocomposites. The nanocomposites
were prepared using PCL as matrix and cellulose nanofibrils
(CNF) as reinforcing element. The CNF had previously been
modified with PCL either through grafting-from by surfaceinitiated ROP of ε-CL or by physically adsorbing a polymer of
quaternized PDMAEMA-block-PCL. Evaluation of the final
bionanocomposites revealed that modification by physical
adsorption resulted in a strong but brittle material, while
modification by covalent grafting resulted in a tougher material.
E. Malmström, A. Carlmark, Polymer Chemistry, 2012, 3 (7),
1702 – 1713.
S. Utsel, L. Wågberg el al. ACS Appl. Mater. Inter. 2012, 4,
6796.
A. Carlmark, Macromol. Chem. Phys. 2013, 214(14), 15391544.
S. Hansson, et al. Biomacromolecules 2013, 14(1), 64-74
CELL 67
Polymer-grafting or adsorption of amphiphilic block
copolymers - different approaches to compatibilization in
CNF-based nanocomposites
Eva E. Malmström, [email protected], Carl Bruce, Linda
Fogelström, Mats K. Johansson, Anna Carlmark. Fiber and
polymer technology, KTH Royal Institute of Technology,
Stockholm, Sweden
The modification of cellulose through polymer grafting has
been of interest for many years. Typically, chains are grafted,
either via grafting-to of preformed polymer chains, or via
grafting-from, where the polymerization is initiated from the
surface.1 Another approach to cellulose modification is to
physically adsorb polymers onto the fiber surface. Amphiphilic
block copolymers, composed of a cationic polyelectrolyte and a
Cellulose nanofibrils are surface modified either by grafting from (G)
or by adsorption of amphiphilic block copolymers (A). The modified
CNFs are compounded in a PCL matrix. The materials properties are
evaluated and compared.
CELL 68
Cellulose surfaces modified by latex particles prepared via
RAFT-mediated emulsion polymerization
Anna Carlmark2, [email protected], Linn K. Carlsson2, Eva E.
Malmstrom2, Lars Wagberg2, Joakim Engström2, Fiona
Hatton2, Markus Jawerth2, Carmen Freire1, Frank D'Agosto3,
Muriel Lansalot3. (1) University of Aveiro, Aveiro, Portugal (2)
KTH Royal Institute of Technology, Stockholm, Sweden (3)
Université de Lyon, Lyon, France
The pulp and paper industry has modified cellulose by
polyelectrolyte adsorption for centuries, in order to improve
properties such as wet-strength and de-watering. This
approach is especially advantageous for the modification of
nanocelluloses, such as cellulose nanofibrils (CNF), as these
are produced in dilute water suspension and can easily be
anionically charged through TEMPO-oxidation. By utilizing
controlled polymerization techniques, more advanced
polyelectrolytes can be obtained, allowing the possibility to
fine-tune the properties of the surfaces of cellulose fibers and
fibrils.1 Herein, cationic polymer latexes have been prepared
and physically adsorbed to cellulose model surfaces and
cellulose nanofibrils (NFC). Charged polymer nanoparticles
composed of amphiphilic block copolymers based on
poly(dimethylaminoethyl methacrylate) (PDMAEMA) and a
hydrophobic block composed either of a high Tg polymer,
poly(methyl methacrylate) (PMMA), or a low Tg polymer,
poly(butyl acrylate) (PMA), were synthesized by RAFTmediated2 surfactant-free emulsion polymerization. During the
synthesis, the amphiphilic block copolymers self-assembled
into spherical cationic latex nanoparticles by polymerizationinduced self-assembly (PISA).3 The length of the hydrophilic
block. i.e. the macro-RAFT, was kept constant and latexes with
varying lenght of the hydrophobic block were prepared. These
cationic latexes were subsequently physically adsorbed onto
cellulose model surfaces and CNF. From adsorption
measurements in the QCM-D, it was shown that large amounts
of latex-particles were adsorbed to the cellulose model
surfaces, something which was also confirmed by AFM
measurements. The surfaces were fairly hydrophobic after the
adsorption and upon heat treatment of the surfaces, which
collapsed the latex particles and exposed the hydrophobic
core, the hydrophobicity increased. Furthermore, the latex
particles were adsorbed onto NFC in solution and the modified
NFC were incorporated into a PCL matrix. Results showed that
the adsorption of latex particle-modified NFC improved the
mechanical properties of the composites.
1A.
Carlmark, Macromol. Chem. Phys., 2013, 214(14), 15391544
2C. Barner-Kowollik, Handbook of RAFT-polymerization. 2008,
Wiley-VCH
3B. Charleux, G. Delaittre, J. Rieger, and F. D'Agosto,
Macromolecules, 2012, 45, 6753-6765
CELL 69
Model cellulose surfaces to characterize (bio)polymer
interaction: Designing the interphase
[email protected],
jielong
Su1,
Gil
Garnier1,
Christopher Garvey3, Warren Batchelor1, Warwick Raverty2. (1)
Chemical Engineering, Monash University, Clayton, Victoria,
Australia (2) Circa, Melbourne, Victoria, Australia (3) ANSTO,
Sydney, New South Wales, Australia
Cellulose offers unique opportunities of interphase formation
with polymers and biopolymers. As a high molecular weight
polysaccharide, cellulose can adopt a completely crystalline or
and amorphous structure, while its three hydroxyl per
monomer offer strong hydrogen bonding ability, hydrophilicity
and easy chemical functionalization. Here, we analyse how
cellulose can be engineered to develop unique interphases
with (bio)polymers, and how those enable novel applications
such as bioactive paper and nanocellulose composites. Model
cellulose surfaces were built to optimize polymer-cellulose
interphase characterization using specular neutron/X-ray
reflectometry, AFM and synchrotron x-ray scattering. Thin and
smooth amorphous and crystalline cellulose films were spin
coated on silicone blocks and quartz slides for analysis by
reflectometry and SAXS, respectively. Amorphous cellulose
films were achieved by spin coating a cellulose
acetate/acetone solution and regeneration by sodium
methoxide; crystalline films were made by spin coating a 6.5%
nanocellulose crystals suspension. In a first series of
experiments, Cationic polyacrylamide (CPAM) of very high
molecular weight (13MW) but varying charge density (5-50%)
were adsorbed from solution at the cellulose/D2O interphase
and the polymer thickness measured by neutron-reflectometry.
In water, amorphous cellulose becomes a hydrogel and swells
by adsorbing around 70 % water. While the high molecular
weight CPAM studied were secluded to the surface, this opens
new opportunities of polymer/cellulose interface. In a second
series of experiments, deuterated cellulose films were
prepared for contrast optimization of adsorbed biomolecules by
neutron reflectometry. Polymer-cellulose interphases are
characterized in terms of morphology and composition and
related to application. CPAM and PEI are used to retain
nanoparticles and biomolecules (cells, antibody, enzyme) on
paper. The effect of the cellulose surface on antibody
stabilization is also analyzed.
CELL 70
Why "laboratory standard" is not good enough in GPCanalyses of lignins
Heiko Lange, [email protected], Federica Rulli,
Claudia Crestini. Department of Chemical Sciences and
Technologies, University of Rome 'Tor Vergata', Rome, Italy
One crucial component within the efforts aiming at the
valorization of lignin is a rather precise knowledge regarding its
structural features in terms of the amounts of aliphatic and
phenolic hydroxyl groups, the amount of non-phenolic end
groups, and the nature of interunit bonding motifs including
their abundances. For achieving a complete characterization,
these data are best to be interpreted in connection with the
molecular mass key data describing the oligomeric lignin
chains, namely the number average molecular weight Mn, the
weight average molecular weight Mw, and the polydispersity
PD. Especially the latter one is often referred to when the
discussion comes to the quality of polymeric or oligomeric
sample: the smaller the PD, the better the polymer with respect
to subsequent (chemical) modifications. Within the GPC-based
determination of the above-mentioned key data like the PD for
a given lignin sample, a meaningful calibration of the
instrumentation, as well as the use of suitable detectors, are of
paramount importance: a misled estimation of the “expected”
molecular weight of a lignin sample might lead to a poor choice
of the range of molecular weights of the standards used for
calibration; the wrong detector-type lacks sensitivity. The range
of the molecular weights covered in the calibration, however,
does affect significantly the results obtained in the
measurements of the lignin samples especially with respect to
the polydispersity, and a non-suitable detector neglects the
extremes. We have developed a transparent and robust
protocol for the gel-permeation chromatography-based
characterization of plant-derived polyphenols in general, and
lignins in particular. After systematically evaluating i) the
influence of the calibration of the analytical set-up, ii) the
influence of the flow-rate, and iii) the influence of the detector
used for recording, we propose a generally applicable method
and set-up for GPC analyses of lignins, that delivers molecular
weight data that can be verified via NMR spectroscopy-based
methods.[1,2]
[1] Crestini, C., Melone, F., Sette, M., Saladino, R. (2011).
Milled wood lignin: A linear oligomer. Biomacromolecules
12(11), 3928-3935.
[2] Sette, M., Wechselberger, R., Crestini, C. (2011).
Elucidation of lignin structure by quantitative 2D NMR.
Chemistry – A European Journal 17(34), 9529-9535.
CELL 71
Enzyme surface hydrophobicity
adsorption to lignin films
predicts
enzyme
Deanne Sammond1, [email protected], John
Yarbrough2, Elisabeth Mansfield3, Yannick J. Bomble1, Michael
Resch4, Joseph J. Bozell6, Michael E. Himmel1, Michael F.
Crowley5. (1) Biosciences Division, National Renewable
Energy Laboratory, Golden, Colorado, United States (2)
Biosciences, National Renewable Energy Laboratory,
Lakewood, Colorado, United States (3) Materials Reliability
Division-853, NIST, Boulder, Colorado, United States (4)
National Bioenergy Center, National Renewable Energy Lab,
Golden, Colorado, United States (5) National Renewable
Energy Lab, Lakewood, Colorado, United States (6) Center for
Renewable Carbon, Center for the Catalytic Conversion of
Biomass (C3Bio), University of Tennessee, Knoxville,
Tennessee, United States
Lignin is a plant cell wall polymer that inhibits enzymatic
saccharification of polysaccharides for the production of
biofuel. Here we evaluate the role of hydrophobic interactions
in enzyme-lignin binding. The hydrophobicity of the enzyme
surface was quantified using an estimation of the clustering of
nonpolar atoms, identifying potential interaction sites. The
adsorption of enzymes to lignin surfaces, measured using the
quartz crystal microbalance, correlates to the hydrophobic
cluster scores. Further, these results suggest a minimum
hydrophobic cluster size for a protein to preferentially adsorb to
lignin. This method could be used to design improved cellulase
cocktails to lower the cost of biofuel production.
The Family 1 Carbohydrate Binding Module (CBM1, PDB 1cbh)
from Trichoderma reesei Cel7A (GH7) is shown in (A) sphere
representation and (B) cartoon and surface representation, with the
identified
hydrophobic
cluster
highlighted
in
orange.
CELL 72
Comparing different approaches to measure molar mass
of lignin: SEC, DOSY and AsFlFFF
Irina Sulaeva1,2, [email protected], Ivan Sumerskii1,
Markus Bacher1, Grigory Zinovyev1, Ute Henniges1, Thomas
Rosenau1, Antje Potthast1. (1) Chemistry / renewable
resources, BOKU Vienna, Vienna, Austria (2) Christian
Doppler Laboratory “Advanced Cellulose Chemistry and
Analytics”, Tulln an der Donau, Austria
Lignins are complex irregular polyphenolic compounds,
obtained in massive quantities as by-products during chemical
wood pulping processes. The search of novel lignin
applications in addition to those coming from the pulp industry
arouses the heightened interest to the amplification of a rapid
and effective way of lignin characterization. Sample
fractionation with gel permeation chromatography (GPC) or
asymmetrical flow field-flow fractionation (AsFlFFF) may
provide
comprehensive
information
about
primary
characteristics of technical lignins, such as molar mass
distribution and polydispersity index. Diffusion-ordered NMR
spectroscopy (DOSY) may be applied as an alternative source
of information about molar weight characteristics of the
samples. Lignin analysis is hindered due to inconstancy of the
structural and chemical characteristics of lignin fractions.
Chemical treatment during sulphite or kraft pulping processes
affects the solubility of analytes due to the cleavage of alkyl
aryl ether inter-unit linkages and formation of hydrophilic HSO3or OH- / HS- groups. Additionally, the tendency to aggregate in
the solution may obstruct the analysis. The hindering effects
may be minimized through the selection of proper mobile
phase and sample preparation steps for each individual
fraction. Aqueous and organic-based GPC systems were
adjusted for characterization of technical lignin samples: milled
wood lignins, lignosulfonates and kraft lignins. Mobile phase
parameters were optimized by adjusting ionic strength and pH
of the solution. Molar mass determination was performed
based on the calibration with narrow polystyrene sulfonate
standards. AsFlFFF fractionation was performed for water
soluble samples. A variety of critical AsFlFFF parameters
including laminar and cross-flow rates, sample concentration,
injection and focusing time were adjusted towards an
appropriate set of parameters for optimal sample separation
and recovery. Self-diffusion coefficients obtained by DOSY
measurements were related to molar mass values by
performing the calibration with polystyrene and dextrane
standards. The results obtained for different lignin samples will
be discussed; and a critical overview on the fractionation
techniques in comparison to DOSY analysis, and calibration
parameters are presented.
CELL 73
Exploring the use of pulsed field gradient (PFG) NMR to
extract molecular weight distributions of lignin
James
O.
Thomas2,3,
Catherine
F.
Clewett2,
1
[email protected], Todd M. Alam . (1) MS 0886, Org.
1816, Sandia National Labs, Albuquerque, New Mexico, United
States (2) Dept of Math, Chemistry Physics, WTAMU, Canyon,
Texas, United States (3) Depart. of Physics and Astronomy,
Texas A & M University -- Commerce, Commerce, Texas,
United States
Lignins are biologically based polymers with very non-linear
structures. These complex polymers are found in the
secondary cell walls in plants and, with subsequent treatment,
can be used as a starting material for many industrially
relevant chemicals. Pulsed-field gradient nuclear magnetic
resonance (PFG-NMR) was used to collect experimental
molecular diffusion data on solutions for a variety of different
lignins, both commercially available and processed from nontraditional sources. The PFG-NMR signal attenuation during
the diffusion experiments were then mathematically analyzed
assuming a gamma distribution of diffusion constants, or
through an inverse Laplace transform (ILT). As a final step, the
distribution of the measured diffusion constants was mapped to
a molecular weight domain. The PFG-NMR method of
ascertaining molecular weights has the benefit of being quick
compared to the more traditional column fractionation.
Therefore, using PFG-NMR should be the preferred method for
obtaining molecular weights of lignin samples in many
experimental situations.
CELL 75
Characterization of alkaline lignin by thermal desorption
and pyrolysis methods
Keith Voeller, [email protected], Alena Kubatova,
Evguenii I. Kozliak. Chemistry Department, University of North
Dakota, Grand Forks, North Dakota, United States
CELL 74
At present, methods addressing lignin and its decomposition
products characterization are limited; liquid-liquid extraction
followed by gas chromatography with mass spectrometry (GCMS) targets only volatile compounds while liquid
chromatography methods are not ideal for unknown products
due to limited availability of oligomeric products as
identification standards. Previously, pyrolysis (pyr) coupled
with GC-MS was used for characterization of lignin. However,
this method is not applicable to degradation products as it does
not differentiate between the occurrences of evaporating
monomeric and thermally decomposing large molecular weight
compounds. In this study, thermal methods such as thermal
gravimetric analysis, pyrolysis-GC-MS (Pyr-GC-MS), and total
carbon analysis (TCA) are used for characterization of lignin
and lignin products of hydrothermal degradation. Thermal
desorption (TD) coupled with pyr-GC-MS allowed for the
differentiation of monomeric species evolving at low
temperature steps (200, 300 °C) from large molecular weight
species pyrolyzed at 400 – 850 °C. It is essential to note the
pyrolytic portion of carbon (i.e., coke) cannot be observed with
pyr-GC-MS instruments. To achieve analysis including mass
balance closure, TCA was used obtaining a quantitative
thermal evolution profile through TD and pyrolytic temperatures
with/without oxygen. During analysis of raw lignin with TCA, up
to 55% evolved under aerobic conditions as elemental carbon
(i.e., coke). By contrast, products of lignin hydrothermal
treatments at 200 °C and 300 °C showed only 19% and 28%
pyrolyzed carbon respectively. Lignin hydrothermally treated at
300 °C evolved significantly more species at lower
temperatures during TCA than that of hydrothermal treated
samples at 200 °C which indicated the formation of monomers
at higher temperatures. TCA has thus shown that relatively low
temperature (200 – 300 °C) hydrotreatment of lignin produced
noteworthy amounts of monomers and small oligomers without
significant re-polymerization of lignin fragments.
Analysis of lignin hydroxyl groups by NMR spectroscopy
CELL 76
Ewellyn A. Capanema, [email protected]. Wood
and Paper Science, North Carolina State University, Apex,
North Carolina, United States
Low-field NMR study of interactions between lignin and
cellulase
Gamma distribution (left) and Inverse Laplace Transform (right) of
diffusion constants for multiple lignin samples.
Different types of hydroxyl groups are among important lignin
functionalities affecting lignin reactivity in lignocellulosic
processing and commercial utilization. This paper compares
the most popular quantitative NMR techniques in functional
lignin analysis (13C, 31P and 1H NMR methods). The
inaccuracies of currently used protocols have been
demonstrated and appropriate modifications in the analytical
procedures are suggested. The modified methods have been
comprehensively compared using a large number of different
native and technical lignins, including widely used lignin
standard preparations. Good correlation has been found
between the modified protocols in the quantification of various
types of phenolic and aliphatic OH groups. However, the
difference in the quantification of lignin carboxyl groups is still
significant. Advantages and limitations of each method are
discussed and an optimal approach is suggested.
Mi Li2, Jing Yang4, Maobing Tu3, Thomas J. Elder1,
[email protected]. (1) USDA Forest Service, Pineville,
Louisiana, United States (2) Auburn University, Auburn,
Alabama, United States
The efficiency of enzymatic hydrolysis of cellulose for the
production of chemicals and energy from biomass can be
impacted by the presence of lignin, and its adsorption to
proteins. Using low-field, time-domain nuclear magnetic
resonance spectroscopy the current study evaluates
interactions between lignin, water, enzymes and surfactants by
the determination of relaxation times and their distribution. In
addition, the effect of differing lignin preparations and the
presence of polysaccharides is evaluated.
CELL 77
Facile quantification of biomass lignin using acidic lithium
bromide (ALB) method
Ning Li, [email protected], Jane Alexander, Xuejun Pan.
Biological Systems Engineering, University of WisconsinMadison, Madison, Wisconsin, United States
Lignin quantification is routinely performed in the analysis of
biomass composition and in the evaluation of lignocellulosic
feedstock. Traditionally, two-stage sulfuric acid method (Klason
method) is used for the lignin quantification, but the method
suffers from the labor-intensive and tedious procedure and the
rigid dependence on analyst’s experience. In this work, a facile
quantification of biomass lignin was reported using acidic
lithium bromide (ALB) method. Under relatively mild conditions,
cellulose and hemicellulose of the biomass were dissolved and
further hydrolyzed to monomeric sugars in acidic lithium
bromide for quantification, leaving lignin fraction isolated as
insoluble residue and then quantified gravimetrically.
Compared to Klason method, ALB method shortens the
analysis time and avoids the autoclaving (or similar) operation.
Results indicated that lignin contents of varying biomass
(Douglas fir, eucalyptus, aspen, corn stover, and switchgrass)
determined by the ALB method are comparable and consistent
with those by NREL standard procedure (Klason method).
CELL 78
Solvation dynamics and energetics of hydride transfer
reactions in cellulosic biomass conversion
Samir Hemant Mushrif, [email protected], Chethana
BK, Jithin J. Varghese. Chemical and Biomolecular
Engineering, Nanyang Technological University, Singapore,
Singapore, Singapore
Cellulose and its sugar derivatives need to be dissolved in a
solvent for their catalytic conversion to chemicals and fuels
intermediates. Experimental studies have shown that the
addition of a co–solvent to water or replacing water with an
alternate solvent can significantly alter conversion and
selectivities in these reactions. [1] It is believed that solvents
can play dual role in biomass reactions. (i) A solvent can either
preferentially solvate an “active” functional group of a biomass
molecule or its derivative and protect it from taking part into the
reaction [2], or (ii) on the other hand, solvent can also directly
participate in the reaction.[3] Hydride transfer is a commonly
observed, and usually the rate limiting step in some of the key
biomass reactions like isomerization and dehydration.[4]
Solvent dynamics and non–equilibrium solvation can play a
major role in altering the energetics of charge transfer steps
like hydride transfer.[5] In the present paper, we perform Car–
Parrinello molecular dynamics-metadynamics simulations of
intramolecular hydride transfer in a glucose molecule, as a
model system, in the presence of explicit, quantum
mechanically treated solvent molecules. Free energy change
and activation free energy barrier for the hydride transfer step
are computed as a function of solvent composition. It is
observed that hydride transfer can be either exergonic or
endergonic in different solvents. Similarly the free energy
barrier for hydride transfer is a strong function of the solvent
environment. Analyses of changes in the electronic structure of
the reacting system and in solvent orientation along the
trajectory suggest that changes in the charge structure of the
sugar molecule polarizes the solvent and that hydride shift
takes place in a non–equilibrium solvation environment.
Orientational relaxation of the solvent, after the hydride
transfer, is observed to be a significantly slower process. The
free energy barrier is a result of non–equilibrium solvation and
the exergonicity or endergonicity of the hydride transfer step
depends on the relaxation dynamics of the solvent.
1. Y. Román-Leshkov et al., Science, 2006, 312, 1933-1937.
2. S. H. Mushrif et al., Phys Chem Chem Phys, 2012, 14,
2637-2644.
3. G. Li et al., Catalysis Science & Technology, 2014, 4, 22412250.
4. R. Bermejo-Deval et al., P Natl Acad Sci USA, 2012, 109,
9727-9732
5. S. H. Mushrif et al., Chem. Eng. Sci. 2014, In press
CELL 79
Frequency filtration to obtain realistic thermal vibrations
in crystal from molecular dynamics
Yu Ogawa, [email protected], Yoshiharu Nishiyama, karim
Mazeau. Cermav-CNRS, Grenoble, France
Molecular dynamics (MD) simulation using force fields is widely
used to investigate structure and properties of materials at
atomistic level. However, since atomic motions are controlled
by classical mechanics, some thermodynamic properties that
are governed by quantum effects are unrealistic (cf. the
calculated molar heat capacity is always close to 3R, where R
is the gas constant). Thermal vibration is essentially a quantum
mechanical phenomenon, and the high frequency vibrations
such as O-H stretching cannot be excited at room temperature.
In this study we showed that realistic vibrations at given
temperatures can be estimated by frequency filtration from the
Bose-Einstein distribution. Based on this new approach, the
molecular origin of the thermal expansion behaviour of the
crystals of cellulose and chitin was reinterpreted.
CELL 80
Mechanism of alkyl and alkaline earth chloride-enhanced
hydrolysis of cellulose in acid solutions
Pan Chen1, [email protected], Brooks Rabideau1,
Ahmed E. Ismail2. (1) AICES & AVT, RWTH Aachen
University, Aachen, Germany (2) Dept of Mechanical
Engineering, RWTH Aachen University, Aachen, Germany
Alkyl and alkaline earth chlorides such as sodium chloride,
lithium chloride, and calcium chloride, have been found to
promote the hydrolysis of cellulose catalyzed by dilute acid.
We have explored this phenomenon using molecular dynamics
simulations. Experimentally, the increase in the hydrolysis rate
has been found to be proportional to the salt concentration.
Our simulations suggest that the promoting effect is driven by
direct ion-cellulose interactions, which mainly occur in
concentrated salt solutions and less frequently in dilute salt
solutions. The variation in cellulose-ion interactions with
different cellulose surfaces, including (110), (1-10), (200) and
(010), as well as the quantitative analysis of the spatial
distribution of ions around the glucose ring, will also be
discussed.
CELL 81
Computational targets for reaction pathways and
energetics of cellulose conversion to fuels and chemicals
Paul J. Dauenhauer, [email protected]. Chemical
Engineering and Materials Science, University of Minnesota,
Minneapolis, Minnesota, United States
Conversion of renewable lignocellulosic biomass to fuels and
chemicals addresses the grand challenge of achieving
sustainable energy and products for the 21st century [1].
However, renewable feedstocks such as woody biomass
introduce new research challenges due to the complexity of the
solid mixture of biopolymers [2]. Reactions of cellulose to
produce either clean sugars or low-cost crude mixtures such
as pyrolysis oils (i.e. bio-oils) undergo reactions difficult to
elucidate due to extreme functionality, multi-step reaction
mechanisms, or the influence of surrounding molecules (i.e.
solvents). In this work, we present methods for connecting first
principles calculations with the reaction mechanisms of
cellulose decomposition. Chemical surrogates for cellulose
provide low-cost, rapid evaluation of chemical reaction
pathways via Car-Parrinello Molecular Dynamics simulation [3].
Multi-step reaction networks of cellulose conversion are
directly fit to detailed chemical distributions, allowing for
molecular-level model development [4]. Finally, chemical
transformation of cellulose is utilized within continuum models
of woody biomass, providing the potential for detailed chemical
prediction in real, lignocellulosic materials [5].
[1] P.J. Dauenhauer, G.W. Huber, “Biomass at the Shale Gas
Crossroads,” Green Chemistry 2014, 16, 382-383.
[2] M.S. Mettler, D.G. Vlachos, P.J. Dauenhauer, “Top ten
fundamental challenges of biomass pyrolysis for biofuels,”
Energy & Environmental Science 2012, 5(7), 7797-7809.
[3] M.S. Mettler, S.H. Mushrif, A.D. Paulsen, A.D. Javadekar,
D.G. Vlachos, “Revealing pyrolysis chemistry for biofuels
production: Conversion of cellulose to furans and small
oxygenates,” Energy & Environmental Science 2012, 5(1),
5414-5424.
[4] A.D. Paulsen, M.S. Mettler, P.J. Dauenhauer, “The role of
sample dimension and temperature in cellulose pyrolysis,”
Energy
&
Fuels
2013,
27(4),
2126-2134.
[5] A.D. Paulsen, B.R. Hough, C.L. Williams, A.R. Teixeira,
D.T. Schwartz, J. Pfaendtner, P.J. Dauenhauer, “Fast pyrolysis
of wood for biofuels: Spatiotemporally resolved diffuse
reflectance in situ spectroscopy of particles,” ChemSusChem
2014, 7(3), 765-776.
CELL 82
Interference trinity: Lignins' role in biomass recalcitrance
explored through petascale simulation
Josh V. Vermaas1,2, [email protected], Xianghong Qi2,3,
Roland Schulz2,3, Loukas Petridis2, Jeremy C. Smith2,3. (1)
Center for Biophysics and Computational Biology, University of
Illinois at Urbana Champaign, Urbana, Illinois, United States
(2) UT/ORNL Center for Molecular Biophysics, Oak Ridge
National Laboratory, Oak Ridge, Tennessee, United States (3)
Department of Biochemistry and Cellular and Molecular
Biology, University of Tennessee, Knoxville, Tennessee,
United States
Lignin that remains after the pretreatment of lignocellulosic
biomass inhibits cellulase action, and raises the cost of
biologically-derived fuels. Many mechanisms for cellulase
inhibition have been proposed, which we explore through
analysis of a 1.3 μs trajectory for an atomic model system
containing cellulose, lignin and cellulases. Through this study,
we have gained insight into the mechanisms by which lignin
inhibits cellulose degredation. We find that lignin interferes with
cellulase action in three ways. Lignin reduces the accessible
surface area of cellulose to enzymatic degradation, and does
so preferentially on the hydrophobic faces of crystalline
cellulose. Lignin also binds to specific residues on the CBM,
interfering with its ability to bind to cellulose. Through the
formation of large-scale networks between fibrils, lignin
increases the effective particle size of a single enzyme copy
and decreases the rate at which enzymes sample the cellulose
surface.
Lignin (blue) forms networks by interacting with both cellulose (red)
and cellulases (green), interfering with cellulase action in three
distinct ways.
CELL 83
Unmasking the mystery base employed by the T. reesei
Cel6A cellulase
Heather Mayes4,1, [email protected], Brandon
Knott1, Michael F. Crowley1, Andreas W. Goetz2, Jerry
Ståhlberg3, Linda J. Broadbelt4, Gregg Beckham1. (1) National
Renewable Energy Lab, Lakewood, Colorado, United States
(2) San Diego Supercomputer Center, MC0505, University of
California San Diego, La Jolla, California, United States (3)
Swedish University of Agricultural Sciences, Uppsala, Sweden
(4) Northwestern University, Evanston, Illinois, United States
Trichoderma reesei Cel6A is an industrially-important enzyme
for converting cellulose to renewable fuels and chemicals. Still,
many questions remain for the understanding of its catalytic
mechanism despite many structural and kinetic studies with
both wild-type and mutant enzymes. Cel6A is a
cellobiohydrolase (CBH) that binds the cellulose chain in a
tunnel enclosed by extended loops, which enables processive
action where multiple cellobiose units are cleaved off from the
non-reducing end of the chain before enzyme detachment. The
glycosidic bond is hydrolyzed by a single-step inverting
reaction mechanism, i.e. single displacement nucleophilic
substitution at the anomeric carbon by an activated water
molecule. However, the identity of the Cel6A catalytic base that
abstracts a proton to activate the water molecule has remained
a mystery. Path-sampling offers the tools for uncovering the
reactive potential energy surface of the catalytic event, thus
providing a molecular-level understanding of the roles of each
residue in the cleaving of the strong glycosidic bond. Our
combined quantum mechanics and molecular mechanics
(QM/MM) simulations reveal the key role of a water wire in the
shuttling of a proton away from the active site to the putative
base, as well as providing a means for catalytic rescue upon
mutation of the putative base. In addition to providing an
atomistic understanding of enzyme action, this model provides
a tool for the rational design of more efficient enzymes for use
in producing renewable chemicals and fuels from non-food
biomass.
Conversion and GVL yield in % for Ru, Pd, Pt in THF and in water
solvent. No conversion was observed for Ru and Pd in THF solvent
CELL 84
Role of water on metal catalyst performance for ketone
hydrogenation: A joint experimental and theoretical study
on levulinic acid conversion into gamma-valerolactone
Carine Michel1, [email protected], Jérémie Zaffran1,
Agnieszka M. Ruppert2, Joanna Matras-Michalska2, Marcin
Jedrzejczyk2, Jacek Grams2, Philippe Sautet1. (1) Ecole
Normale Superieure Lyon, Lyon, France (2) Faculty of
Chemistry, University of Technology, Institute of General and
Ecological Chemistry, Lodz, Poland
Most of the time, the reactions with reactants extracted from
biomass are conducted in water to efficiently solubilize reaction
intermediates and products. We will show here that water can
also play an essential role in the catalytic activity, focusing on
the conversion of levulinic acid (LA) into γ-valerolactone (GVL).
While Ru is a poor hydrogenation catalyst compared to Pt or
Pd in gas phase, it is efficient in aqueous phase conditions to
hydrogenate ketones such as the conversion of levulinic acid
into GVL. Comparing experiments in THF and water, we
showed that the activity of Ru/TiO2 catalyst is highly sensitive
to its environment while Pt/TiO2 is not (see Figure 1). Better
insight is provided by periodic DFT calculations at the GGA
level. The presence of a H-bonded water molecule can affect
the adsorption of the reactant, intermediate or product. For
instance, the obtained alcohol is not directly chemisorbed on
the surface: it is strongly h-bonded to the chemisorbed water
molecule (see Figure 2). This water molecule dramatically
reduces the energetic of the reaction pathway on Ru, hence
enhancing the catalytic activity. Conversely, the presence of
such a H-bonded water molecule doesn’t not affect the
energetic of the reaction pathway on Pt. Finally, we predict
also that this activation can be generalized to other oxophilic
metals such as Co or Ni. This study demonstrates that the
knowledge accumulated over the years for gas phase
reactions at metallic surfaces is not systematically transferable
to aqueous phase conditions.
Co-adsorption structures of acetone and water (left) and isopropanol
and water (right) on Ru(0001)
CELL 85
Multiscale modeling of the interfacial
xylan/cellulose nanocomposites
structure
in
karim Mazeau1, [email protected], Patrick
Perre2, liang Li3, Xavier Frank4. (1) CERMAV, CNRS, Grenoble
Cedex 9, France (2) LGPM, Ecole Centale Paris, Paris, France
(3) LERFoB, IN, Nancy, France (4) IATE-CIRAD, INRA,
Montpellier, France
Bio-sourced materials made of xylan reinforced by cellulose
whiskers do not generally express optimal mechanical
performance; because of poor interfacial stress transfer.
Molecular modeling is in principle a choice technique to study
the interfacial organization. Unfortunately, with present
computing, the time and space scales accessible in full-atoms
simulations are not sufficient. To overcome this difficulty, we
have developed a coarse grain force field able to describe
xylan and its interaction with crystalline cellulose. We then
have generated atomistic and coarse grain models of cellulose
xylan nanocomposites. In the interface, which was 1.5 nm
thick, the xylan chains in the immediate vicinity of the cellulose
were oriented parallel to the surface, adopting a mixture of twofold (dominant) and three-fold (minor) helical conformations
interrupted by kinks, they were mainly aligned to each other
and inclined with respect to the fiber axis. The models correctly
reproduce the experimental data from various sources. The
coarse grain approach holds great promises, it may be used
not only to estimate the behavior of the interface under various
stresses but also to study transport phenomenon in such
bionanocomposites.
CELL 86
Macroalgae as filler in thermoplastic
Opportunities and weaknesses
composites:
Mindaugas Bulota2, [email protected], Tatiana Budtova1.
(1) CEMEF/Mines ParisTech, Sophia Antipolis, France (2)
CEMEF, Mines Paris Tech., Sophia Antipolis, France
Macroalgae are cumulated in significant volumes every year on
the coasts and as waste after the extraction of polysaccharides
used in beauty and food industries. Herein, a study on the
utilization of this biosource in thermoplastic composites is
presented. Virgin and waste algae were used. The morphology
and size distribution of algae particles were investigated using
optical microscopy and SEM prior and after processing. Fully
bio-based composites, using melt compounding and injection
moulding processes, were prepared. Poly(lactic) acid was used
as matrix and algae weight fractions varied from 20 to 60 %.
The mechanical performance of composites has been
addressed with respect to the algae type, particle size and
weight fraction. Surface composition of algae was analysed
using XPS and EDS. The structure and composition of algae
was investigated using X-ray diffraction and FT-IR
spectroscopy. Additional algae treatments were carried out in
order to alter filler-matrix interactions. Finally, the changes in
crystallization behaviour of the polymer matrix have been
scrutinized.Opportunities and weaknesses of macroalgae as
filler in biocomposites will be discussed with respect to a
number of observed effects on the behaviour of PLA
composites. The analysis shows that algae particles have
flake-like structure with residues of various salts on the
surface. Although toughness of composites decreased upon
the addition of algae flakes, the Young’s modulus exhibits a
small decrease thus composites having up to 40 wt% of algae
loads can be prepared. This is of high importance as industrial
wastes can be effectively utilized as filler in thermoplastic
composites.
Acknowledgements
The work is performed within the frame of the Industrial Chair
in Bioplastics, organised by CEMEF/Mines ParisTech and
supported by Arkema, L’Oreal, Nestlé, PSA and Schneider
Electric. We thank Agrimer, Cargill and Prof. Deslandes
(Université de Bretagne Occidentale, Brest) for providing
algae.
CELL 87
Use of micro-structured cellulose from soybean hulls as
coating additives for paper
Ana Ferrer1, [email protected], Carlos L. Salas2, Thomas W.
Theyson3, Orlando J. Rojas1,4. (1) Forest Biomaterials, North
Carolina State University, Raleigh, North Carolina, United
States (2) Forest Biomaterials, NC State University, Raleigh,
North Carolina, United States (3) Tenstech Inc., Matthews,
North Carolina, United States (4) Forest Products Technology,
Aalto University, Espoo, Finland
In this work, two types of paper (uncoated paper and a highly
porous air filter paper) were used in order to test microstructured cellulose from soy hulls as coating additives. These
samples were isolated from soybean hulls by combining
chemical and mechanical treatments. Measurements of
porosity, roughness, and air permeability, among others, were
used in order to evaluate the coating process. The results
indicate a significant reduction on the air permeability of the
paper samples after coating with given formulations of the soy
hulls cellulose, and indication that these low costs material
from widely available residual bioresource can be used for high
performance applications such as paper coating processes.
CELL 88
Where are the gauche-gauche-CH2OH groups in cellulose I
materials?
Umesh P. Agarwal, [email protected]. Forest Products Lab,
Madison, Wisconsin, United States
Recent analysis of cellulose I materials using 1064 nm FTRaman spectroscopy has indicated that in addition to the tg
hydroxymethyl groups the gg conformers are present. Further
investigation on this topic revealed that the concentration of
such conformers depended upon the source of cellulose.
However, it was not clear if the units existed in the interior of
the fibrils or on cellulose surface. Evidence will be presented
that seems to suggest that these groups are mostly present in
the interior of the fibrils. The implications of this finding for the
ultrastructures of cellulose will be considered.
CELL 89
Bioinspired xyloglucan-containing films as responsive
smart materials
Ana Villares, [email protected], Céline
Moreau, Bernard Cathala, [email protected].
UR1268 Biopolymères Interactions Assemblages, , INRA,
Nantes, France
Xyloglucan is the major hemicellulose occurring in plants. Its
structure consists of a β-(1-4)-D-glucan backbone decorated
with α-D-xylosyl and β-D-galactosyl units. In nature, xyloglucan
coats cellulose forming a network that regulates structural
rigidity and strength of cell wall. Inspired in these biosystems,
we took advantage of the interaction between cellulose and
xyloglucan to fabricate stimuli responsive films containing
cellulosic polysaccharides.Cellulose nanocrystals (CNC) and
chitin nanocrystals (ChiNC) were isolated by acid hydrolysis of
cellulose cotton linters and chitin flakes from crab shells,
respectively. (CNC-XG) and (ChiNC-XG) multilayer films were
fabricated by spin-coating assisted layer-by-layer technique.
Films were prepared from CNC (3 g L-1), ChiNC (1 g L-1) and
XG (0.5 g L-1) to obtain similar thickness. The swelling behavior
of films was evaluated by the H2O/D2O solvent exchange
method monitored by quartz crystal microbalance with
dissipation (QCM-D). Increase of thickness during swelling was
determined by the coupling of QCM-D and ellipsometry.
For four-bilayer films, results showed lower water uptake (93%)
for (CNC-XG)4 compared to 135% of (ChiNC-XG)4. Thickness
increased from 32 to 133 nm for (CNC-XG)4, and from 40 to
294 nm for (ChiNC-XG)4 when films were exposed to water.
The difference suggests that XG adsorbs onto CNC via a
specific coupling, in which flexible XG chains adopt a flat
conformation to fit the surface morphology such that swelling is
low. Differently, XG deposition onto ChiNC seems less specific
and the steric hindrance caused by the acetyl groups may
result in the formation of loops and tails stretched out along the
surface,
which
favor
water
uptake
by
XG.
This work demonstrates that the swelling behavior of
xyloglucan-containing films can be easily modulated by
xyloglucan arrangement onto nanocrystal surface so that
responsive materials can be fabricated from polysaccharide
building blocks.
CELL 91
Cellulose nanoparticles from new sources – agricultural
wastes: Apple tree (Malus domestica) pruning residues
and pea (Pisum sativum) stalks
Araceli
Garcia1,2,
[email protected],
Alessandro Gandini1, Jalel Labidi2, Naceur Belgacem1, Julien
Bras1. (1) Laboratoire de Génie des Procédés Papetiers
(LGP2), Grenoble INP-Pagora, Saint-Martin-d’Hères, France
(2) Department of Chemical and Environmental Engineering,
University of the Basque Country UPV/EHU, Donostia-San
Sebastián, Spain
CELL 90
Study of nitrogen fixation by condensation of urea on
hydrothermally treated corncob
Jhon
Alexander
A.
Cordoba
Arias2,
[email protected], Eduardo Salcedo Pérez3, Ricardo
Manriquez Gonzalez1, Ezequiel Delgado4. (1) CUCEI,
Universidad de Guadalajara, Guadalajara, Mexico (2)
Posgrado, Universidad de Guadalajara, Guadalajara Jalisco,
Mexico (3) CUCEI, Universidad de Guadalajara, Guadalajara
Jalisco, Mexico
Corn cob was treated hydrothermally in water at 160° C, 7 bars
and 60 min. The product was condensed with urea-15N (14%
respect to corn cob dry basis). The solid matrix was analysed
using TKN (Total Nitrogen Kjeldahl), elemental analysis, FTIR
and 13C and 15N- NMR. The TKN indicated that 7% was fixed
which corresponded to 49.5% of the total 15N. The C/N ratio
ranged from 19.5 to 20.8. FTIR spectra showed the presence
of 15N in different forms such as amides, carbamates and
amines. The signal most evident after the treatment with urea
was observed at 55 ppm, which was assigned to the carbon C2 or C-3 of polymer cellulose linked to 15N compounds, such as
amines. The presence of other nitrogen species in cellulose
was also observed at 147 and 155 ppm in the 13C-NMR,
which can be attributed to carbamates or urethanes. Finally, a
signal at 177 ppm was indicative of carbonyl groups formed
during the condensation process. These nitrogen species were
also corroborated by 15N-NMR. It was also observed a wide
signal (70-140 ppm) due to amides, carbamates or urethanes,
and amine groups at 18 ppm. Those species represented
83.9% and 16.1%, respectively of the total 7% of nitrogen in
the sample. This study demonstrated the feasibility of enriching
hydrothermally treated corn cob with urea, in which nitrogen
was fixed through several forms. Such a product would
improve the physical, chemical, and biological aspects of soil
when used as an organic fertilizer.
In the present work, the use of two agricultural residues (apple
tree pruning and pea stalks) as source of nanocellulose was
studied. Different pretreatments were applied to these
lignocellulosic feedstocks: autohydrolysis, organosolv and
alkaline pretreatment. After a conventional bleaching step
(using a sodium chlorite – acetic acid mixture), the resulting
cellulosic fractions were submitted to nanocellulose crystals
NCC production, (using conventional acid hydrolysis) and to
nanofibers production: refining, two different non-mechanical
processes (enzymatic hydrolysis, EH and TEMPO-mediated
oxidation, TMO) and finally treated by using an ultra-fine
friction grinder.In this sense, the yield and performance of the
NCC production process were quantitatively and qualitatively
assessed, considering the effect that the use of cellulose from
different raw materials and different pretreatments has on
them. The resulting NCC’s were submitted to different
analytical techniques in order to evaluate their morphology
(EDS, AFM, FEG-SEM) and physicochemical properties (XRD,
conductimetry, TGA). Regarding NFC production, the different
cellulosic fractions obtained from the two raw materials and
after several treatment steps, were analyzed in order to
evaluate morphological changes (MorFi analysis and optical
microscopy).
CELL 92
Hybrid composites with microcrystalline cellulose, lignin,
and polyethylene
Arnis Treimanis2, [email protected], Marianna Laka2,
Johannes Ganster1, Jens Erdmann1, Lars Ziegler3. (1)
Fraunhofer IAP, Potsdam, Germany (2) Latv Inst of Wood
Chemistry, Riga, Latvia (3) Tecnaro GmbH, Ilsfeld-Auenstein,
Germany
Microcrystalline cellulose (MCC) fillers and sulphate lignin were
obtained for hybrid composites with high-density polyethylene
and lignin. Cellulose fillers were obtained from wood bleached
kraft pulp and cotton fibres. The pulp fibres were treated by the
thermocatalytic destruction method and then ground in a ball
mill. Treatment conditions were developed for each raw
material. MCC powder samples were prepared which
contained microparticles of different shape and size. The
majority of particles obtained from hardwood and softwood
pulps had the size in longitudinal direction of 20-40
micrometers. Cotton MCC revealed fiber fragments with
greater length and aspect ratio. Composite samples,which
contained polyethylene, 50% of lignin, 20% of MCC and a
coupling agent, were produced. At 20% filler content, tensile
strength, modulus of elasticity, notched Charpy impact strength
and Charpy impact strength of composites with MCC filler from
cotton linters increased by 30, 64, 50 and 15%, respectively.
Earlier it was found that the rayon filler enhanced the
mechanical properties of such composites, especially the
impact strength, much more as compared with MCC powder
fillers. However, since the high quality rayon fiber fillers are not
economically attractive, in many cases the MCC fillers can be
used to improve the mechanical properties of composites.
CELL 93
Analysis of recalcitrant lignin structures to understand the
impact of alkaline hydrothermal pretreatment on enzyme
digestibility
Ling-Ping Xiao, [email protected], Yuan-Yuan Bai, XiaoHong Chen, Zhi-Min Xue, Run-Cang Sun. Beijing Key
Laboratory of Lignocellulosic Chemistry, College of Material
Science and Technology, Beijing Forestry University, Beijing,
China
Pretreatment is an essential step in biorefineries to disrupt the
recalcitrance of lignocellulosic matrix for enzymatic
saccharification and bioethanol production. Herein a
systematic study has been performed to optimize the alkaline
hydrothermal pretreatment of lignocellulosic biomass shrub
wood (Tamarix ramosissima) with the aim of maximizing the
enzymatic digestibility of cellulose and hemicelluloses in the
treated solids and obtaining a liquid side product with low
inhibitors. Results showed that the enzymatic digestibility could
be efficiently improved by applying a hot-water washing step of
substrates after the pretreatment. Maximum yields of 85.3%
glucose and 98.2% xylose were recovered after 72 h of
enzymatic hydrolysis. Scanning electron microscopy combined
with X-ray photoelectron spectroscopy analyses confirmed that
lignin coalesced within the plant cell wall and appeared as
microscopic droplets on the microfiber surfaces, revealing that
the pretreatment caused significantly changes in lignin
distribution. To further understand the impact of alkaline
hydrothermal pretreatment on enzyme digestibility, the
structural characterization of these deposited lignin was also
analyzed using Fourier transform infrared spectroscopy, 13C
Nuclear Magnetic Resonance Spectroscopy (NMR), and 2D
Heteronuclear single quantum coherence spectroscopy NMR.
These results provided new sights into the mechanism of lignin
change during lignocellulose deconstruction and its effect on
enzymatic hydrolysis.
CELL 94
Synthesis and characterization of novel green wood
adhesives from biorefinery lignin
Prajakta S. Dongre1, [email protected], Mark Driscoll3,
[email protected], Jennifer Smith4, Thomas Amidon1, Biljana
Bujanovic2, [email protected]. (1) Paper and Bioprocess
Engineering, SUNY-ESF, Syracuse, New York, United States
(2) Walters Hall 419, SUNY - ESF, Syracuse, New York,
United States (3) Chemistry, SUNY-ESF, Syracuse, New York,
United States (4) Sustainable Construction Management and
Engineering, SUNY-ESF, Syracuse, New York, United States
Wood adhesives are routinely used as bonding agents in over
two-thirds of wood processing materials such as particle
boards and plywood. One of the widely used adhesive in the
wood industry is the phenol-formaldehyde resin. Apsrt from
being environmentally unfriendly, formaldehyde has also been
classified as a carcinogen by the Environmental Protection
Agency.Furthermore, in accordance with the Department of
Energy’s goal, 750 million tons of biomass will be required to
replace 30% transportation fuels with biofuels in turn producing
225 million tons of lignin. This lignin can be extended for higher
value applications to increase profitability of the biorefinery.
Thus, novel green wood adhesive blends produced from
biorefinery lignin and commercial furfural are proposed as
replacement forphenol-formaldehyde resin.During the hot
water extraction of sugar maple wood chips over 10% of lignin
dissolves in the extract. The extract undergoes membrane
separation and the permeate is subjected to acid hydrolysis.
The acid hydrolyzed permeate undergoes membrane
separation again and the lignin rich retentate from this phase is
used to synthesize adhesive blends. Furfural has shown to be
an efficient cross-linking agent for lignin and can replace
formaldehyde. The lignin and commercial furfural are subjected
to acid catalyzed condensation to produce adhesives. The
lignin rich retentate also contains some xylose-based
carbohydrates which produce furfural in situ as a result of acid
catalyzed dehydration reactions. The adhesive blends are
applied on glass fibers and wood panels and cured in a hot
press for strength testing. Different factors such as the pH of
the reaction, pressure and temperature of curing are varied to
explore their effect on the tensile strength (MTS Sintech 1/S),
phenolic hydroxyl content (differential UV), thermal degradation
(DSC) and sugar content (HPLC). Lignin-furfural blends
competitive in strength with phenol-formaldehyde resins can
fulfill the need for high value products making the
lignocellulosic biorefinery more profitable.
CELL 95
Sulfite pretreatment of post-enzymatic hydrolysis
softwood residue to enhance saccharification and
produce lignosulfonates
Ben Jeuck1, [email protected], Orlando J. Rojas1,2, Hasan
Jameel1. (1) Forest Biomaterials, North Carolina State
University, Cary, North Carolina, United States (2) Forest
Products Technology, Aalto University, Helsinki, Finland
Many pretreatment methods have been designed to facilitate
the biochemical conversion of softwood, with none satisfying
minimum economical requirements to date. Sulfite treatment
has shown to be more effective than other methods, as it
solubilizes both hemicellulose and lignin, and creates valueadded lignosulfonates (Zhu et al. 2013). Previous studies have
shown that addition of certain levels of lignosulfonates may
enhance enzymatic saccharification of cellulose in softwood
material (Wang et al., 2013), however, sulfite pretreatment
requires large doses of expensive chemicals. This research
proposes a way of incorporating sulfite treatment into a multistep process that may enhance sugar yields while reducing
chemical loads substantially, making the process more
economical and environmentally sound. Additionally, it
proposes that the lignosulfonates produced can be used as
surfactants to enhance enzymatic hydrolysis, as has been
shown previously. Loblolly pine (Pinus taeda) was pretreated
using autohydrolysis for 1 hour at 180°C, yielding a 66.7%
solid residue. The residue was refined to pulp and subjected to
three different concentrations of cellulase enzymes for 96
hours: 5, 10, and 15 FPU. Post-enzymatic residues were sulfite
pretreated (8, 12% charge on dry wt.) for 2 hours. These postsulfite treatment residues were then subjected to a second
round of enzymatic hydrolysis. The second round of
saccharification was set to simulate the first, in terms of
enzyme dosage, as it’s desired that all residues undergoing
saccharification will ultimately be loaded together within a
single bioreactor. The expected result of this study is that the
loading of the sulfonated residue into the enzymatic bioreactor
will enhance the initial enzymatic hydrolysis, due to the
lignosulfonates, and ultimately yield a very high level of
saccharification. Additionally, sulfonated lignin holds a high
market value, and the high degree by which it is produced in
this process can enhance the system’s economics.
CELL 96
Properties of regenerated bamboo fibers prepared from
raw materials with different hemicellulose content
Jing-Huan Chen, [email protected], Kun Wang, Feng
Xu, Runcang Sun. Beijing Forestry University, Beijing, China
Regenerated bamboo fibers are man-made cellulose fibers
and have comfortable and antimicrobial properties. In this
work, successive alkaline treatments within creasing
concentrations were employed to obtain bamboo raw materials
with different hemicellulose content. These materials were then
dissolved and spun to regenerated fibers with N-methylmorpholine-N-oxide (NMMO) as solvent. The properties of the
raw materials, the viscosity of the spinning solutions, as well as
the structural and mechanical properties of the regenerated
bamboo fibers were investigated by high-performance anionexchange chromatography (HPAEC), gel permeation
chromatography (GPC), X-ray diffraction (XRD), Solid state
cross polarization/magic angle spinning (CP/MAS) 13C NMR,
scanning electron microscopy (SEM), solution-state 1H NMR,
proton-detected heteronuclear single quantum coherence
(HSQC) NMR, viscometer and universal tensile tester. The
results showed that the removal of hemicelluloses increased
the viscosity of spinning solutions and enhance the
compactness and mechanical property of the fibers, although
negatively affected the crystal structure and the crystallinity of
the regenerated fibers. The maximum viscosity of spinning
solution and the highest tensile strength of regenerated fiber
were observed from the cellulosic materials with 17.5 %
hemicelluloses. It was the synergistic result of the changes in
surface exposure, molecular weight and degradation of
cellulosic substrate during hemicellulose removal and cellulose
dissolution process. The removal of the branched
hemicelluloses, rather than the unbranched components, was
the key to balance these factors and obtain stronger fiber.
CELL 97
Process simulation of biomass fast-pyrolysis into
transportation fuels: Model sensitive to variations in
biomass chemical composition
Carlos E. Aizpurua1, [email protected], Hoyong Kim1, Hasan
Jameel1, Mark Wright3, Stephen S. Kelley1, Sunkyu Park2. (1)
Forest Biomaterials, North Carolina State University, Raleigh,
North Carolina, United States (2) Department of Forest
Biomaterials, North Carolina State University, Raleigh, North
Carolina, United States (3) Iowa State University, Ames, Iowa,
United States
The state of art of the current process simulation around
biomass fast pyrolysis into transportation fuels is focused on
evaluating different technologies and pathways for a single
feedstock. Most of these previous works have centered their
attention on the techno-economic analysis and the potential of
those technologies to lead improvements to the conversion
process. In this work, we have developed a process model in
ASPEN PLUS that allows us to analyze not only the technoeconomics of the process, but also to understand the reaction
pathway and the effects of feedstock variations like ash,
carbon content and so on, on the final product and life cycle
analysis. To understand the effect of the biomass chemical
composition, different types of biomass were prepared and fast
pyrolysis was performed using ten different hardwoods,
softwood bark, and pine. Both ash and carbon content in
biomass found important in terms of product yield and bio-oil
chemistry. In addition, these results were used to build
empirical equations that would be used to construct the
process model.
CELL 98
Characterization and evaluation of the lignin from one-pot
HDA process for chemical transformation of biomass into
hydrocarbons
Chang Geun Yoo3, [email protected], Shuting Zhang5,
Hoon Kim2,1, Jijiao Zeng4, John Ralph2,1, Zhaohui Tong4,
Xuejun Pan3. (1) Wisconsin Energy Institute, University of
Wisconsin-Madison, Madison, Wisconsin, United States (2)
Department of Biochemistry, University of Wisconsin-Madison,
Madison, Wisconsin, United States (3) Biological Systems
Engineering, University of Wisconsin-Madison, Madison,
Wisconsin, United States (4) Department of Agricultural and
Biological Engineering, University of Florida, Gainesville,
Florida, United States (5) National Renewable Energy
Laboratory, Golden, Colorado, United States
One-pot hydrolysis-dehydration-aldol condensation (HDA)
process is an effective process for converting lignocellulose to
hydrocarbon fuel precursors under mild reaction conditions
without any pretreatment of the biomass. The process
integrates hydrolysis of cellulose and hemicellulose to
monosaccharides, dehydration of the monosaccharides to
furans, and Aldol condensation between the furans and
acetone to furan-acetone adducts in acetone in presence of
halide salt and mineral acid. The resultant furan-acetone
adducts, precursors of liquid hydrocarbons, can be easily
converted into drop-in fuels through hydrodeoxygenation.
Lignin in the biomass is also depolymerized during the HDA
process. The HDA lignin has the potential to be converted into
high-value coproducts such as fuel-grade hydrocarbons,
aromatic chemicals, and polymeric composites because of its
high purity, solubility in common organic solvents, and low
molecular weight. In this study, conversion of biomass to dropin fuel precursors and valuable lignin co-products by the HDA
process was investigated. Identification and quantification of
liquid hydrocarbon precursors and characterization of the HDA
lignin were conducted using GC-MS, HPLC, FT-IR, GPC, and
NMR analysis methods.
CELL 99
Structural characterization of annealed bacterial cellulose
by SFG, FTIR and XRD
Yuanyuan Weng1, [email protected], Kabindra Kafle2,
Seong H. Kim2,3, Jeffrey M. Catchmark1. (1) Department of
Agricultural and Biological Engineering, Pennsylvania State
University, University Park, Pennsylvania, United States (2)
Department of Chemical Engineering, Pennsylvania State
University, University Park, Pennsylvania, United States (3)
Materials Research Institute, Pennsylvania State University,
University park, Pennsylvania, United States
Bacterial cellulose (BC) produced by Gluconacetobacter
Xylinus is rich in cellulose Iα. Structural analysis of BC by
Fourier-transform infrared (FTIR) and 13C CP/MAS NMR has
confirmed the transformation of cellulose Iα to Iβ by annealing
BC at a temperature between 260°C and 280°C. However,
there remain uncertainties on the mechanism of allomorphs
transformation of native cellulose during hydrothermal
treatment. In our project, the allomorph of bacterial cellulose
was converted at different temperature and duration (235°C for
5 min; 235°C for 10 min; 235°C for 15 min; 250°C for 15 min;
250°C for 40 min). Two independent techniques - SFG and
FTIR - have been used to show the transformation of cellulose
Iα to Iβ. Deconvolution of hydrogen bonding vibrations region
near the 700~800 cm−1 in IR spectra and OH stretch region
(3100-3800 cm-1) in SFG spectra indicate the Iα portion almost
disappears completely at 250°C treated for 40 min. The dspacing data from X-ray diffraction (XRD) are also in
accordance with cellulose Iα → Iβ transformation. The
alkyl/hydroxyl intensity ratio in SFG spectra (sensitive to mesoscale arrangement of cellulose) decreases with increased
annealing temperature and duration. Previous study reported
that increased alkyl/hydroxyl intensity ratio indicated more
ordered lateral packing. However, XRD shows higher
crystallinity and larger crystal size after annealing and Fieldemission scanning electron microscopy (FESEM) shows very
marginal changes in packing and bundle diameter for control
BC and annealed BC. The alkyl/hydroxyl intensity ratios in
SFG spectra combined with XRD and FESEM indicate there is
unknown structural change during hydrothermal treatment of
BC, and alkyl/hydroxyl intensity ratios in SFG are sensitive to
this structural change.
CELL 100
Study on the characteristics of two marine oil-degraded
yeasts and their utilization for carbon source spectrum of
crude oil
Chao Ma3,1, [email protected], Jiefeng Liu3, ningning
Ma1, Xianbo Mou4, Nongyue He2. (1) biomedical, southeast,
Nanjing, China (2) Southeast Univ Lab Bioelectron, Nanjing,
China (3) Bioengineering, Gdupt, Maoming, Guangdong, China
(4) biomedical, Southeast University, Maoming, China
Using crude oil as the sole carbon source, two yeasts with
strong petroleum-degrading activities separately named SYB-5
and SYB-2 were isolated from oil terminal’s surface water and
the mud by employing enrichment culture, plate streaking and
repeat screening, combining with shake flask fermentations
methods. Adopting the morphology, physiological and
biochemical characteristics assay, especially the molecule
analysis of 26S rDNA and ITS DNA sequences, SYB-5 and
SYB-2 was separately identified as Meyerozyma guilliermondii
(Pichia guilliermondii) and Lodderomyces elongisporus. As for
their petroleum degradation characteristics study, the optimal
conditions of SYB-5 and SYB-2 for their growth and
degradation rates were shown as follows: their optimum culture
temperatures are at 36 °C and 32 °C, their optimum pH values
are 6.5 and 7.5, NaCl concentrations are the same to 3%,
(NH4)2SO4 and(NH4)PO4 are respectively as their optimum
nitrogen sources, and high ventilation rates are kept for their
cultures. Moreover, after using the straight-chain alkanes and
aromatic hydrocarbons in petroleum and common petroleum
products as the sole carbon sources, both two isolated yeasts
have a broad spectrum for the utilization of carbon source, but
show different degradation ability from different components of
crude oil.
CELL 101
Microwave-assisted carbonization of bamboo by wet
torrefaction in diluted acid
Ming-Fei Li, [email protected], Yue Shen, Jian-Kui Sun,
Chang-Zhou Chen, Xun Li, Runcang Sun. Beijing Key
Laboratory of Lignocellulosic Chemistry, Beijing Forestry
University, Beijing, China
Torrefaction is an efficient thermochemical method to recover
energy from lignocelluloses. In this work, bamboo was torrefied
in diluted HCl solution (0-0.4 M) with microwave oven heating
at 180 °C for 5-30 min. It was found that for bamboo torrefied
in water, the yield of the torrefied bamboo decreased slightly
from 96.15 to 85.53% and the hemicellulose content
decreased from 30.45 to 25.00% with increased torrefaction
severity from 3.3 to 3.6. Whereas for bamboo culm torrefaction
in acid solutions, the yield of the solid fractions were below
51% and hemicelluloses were completely removed. Especially,
the torrefaction with 0.2 M HCl solution for as short as 5 min
resulted in the complete elimination of hemicelluloses, and the
cellulose content decreased while the lignin content increased
when further prolongation of the heating time to 30 min. This
indicated that the acid solution played a role to intensify the
decomposition of both hemicelluloses and cellulose. The
carbon content of the bamboo was 48.82% and it increased
slightly after torrefaction in water, but it raised largely up to
67.03% under torrefaction with 0.4 M HCl solution at 180 °C for
30 min. The HHV of the torrefied sample showed a higher
value than that of the original sample and it increased after
torrefaction at 0.2 M HCl for 30 min, which (24.86 MJ kg-1) was
comparable with that of German Braunkohole lignite (25.10 MJ
kg-1 ). In addition, the structural modification of bamboo during
the wet torrefaction was elucidated by XRD and NMR.
CELL 102
Production of furfural from hemicelluloses in biphasic
system by highly efficient and recyclable magnetic solid
acid from glucose
Yuan-Yuan Bai, [email protected], Ling-Ping Xiao, XiaoHong Chen, Run-Cang Sun. Beijing Key Laboratory of
Lignocellulosic Chemistry, Beijing Forestry University, Beijing,
China
A stable, efficient, and reusable solid acid catalyst was
developed for the conversion of hemicelluloses to value-added
chemical (furfural). In this work, glucose was converted into a
magnetic carbonaceous solid acid catalyst by incomplete
hydrothermal carbonization of glucose followed by Fe3O4
grafting and –SO3H functionalization. The synthesized
catalysts were characterized by scanning electron microscopy,
X-ray diffraction, surface area measurement techniques,
Fourier transform infrared spectroscopy and elemental
analysis. The prepared superparamagnetic carbon catalyst
contained –SO3H, –COOH, and phenolic –OH groups and
exhibited good catalytic activity for the hydrolysis of
hemicelluloses in various biphasic systems. The effects of
reaction temperature, residence time and organic solvent to
water ratio on the performance of catalytic conversion were
thoroughly investigated. Moreover, the recyclability of the
superparamagnetic carbonaceous solid acid catalyst was also
investigated and the results showed that it could be easily
separated from the reaction products and reused for
subsequent recycling experiments. These findings in the
present work offer effective alternatives for environmentally
friendly utilization of abundant biomass waste.
CELL 103
Novel production of furfural from biomass based on hot
water extracted pentoses
Christopher D. Wood1, [email protected], Biljana Bujanovic2,
Thomas Amidon3. (1) SUNY ESF, Syracuse, New York, United
States (2) Walters Hall 419, SUNY - ESF, Syracuse, New
York, United States (3) PBE, SUNY ESF, Syracuse, New York,
United States
Hot water extraction (HWE) has been shown to be a useful
technical
method
to
recover
hemicellulosic-based
carbohydrates from biomass, most effectively from
angiosperms. These extracts can be made readily fermentable
through a series of separations, but the high pentose content
of extracted carbohydrates from angiosperms (approximately
70%) makes them less attractive for fermentation than the high
hexose content extracts from food crops or cellulose
hydrolysis. Other applications, such as production of furfural
are therefore attractive uses for HW extracted sugars. In this
study, several methods for converting pentose sugars to
furfural are explored. The primary approach being pursued is
based on work surrounding organosolv pulping which showed
a reduction in furfural degradation in formic and acetic acid
mixtures as compared with mineral acids. Utilizing formic and
acetic acid as catalysts for the dehydration of xylose to furfural
is expected to provide significant improvements in yield over
common methodologies using hydrochloric or sulfuric acid.
This study focuses on xylose reacted in a batch mixed tank
reactor to allow for improved definition of reaction kinetics.
Current work is focused on a solvent of 63/7/30 acetic acid /
formic acid / water, at temperatures ranging from 170-190°C.
An HPLC based method is used for analysis of reaction
samples. Acetylated xylose has been tentatively identified in
reaction samples, and may be affecting reaction kinetics. The
approach under study is expected to provide yields of 80% of
theoretical, with kinetic models to be developed for scale-up.
CELL 104
Cooxidant-free TEMPO-mediated oxidation
crystalline Cladophora nanocellulose
of
highly
Daniel O. Carlsson3, [email protected], Jonas
Lindh4, Leif Nyholm1, Maria Stromme5, Albert Mihranyan2. (1)
Dept. of Chemistry - Ångström, Uppsala University, Uppsala,
Sweden (3) Nanotechnology & Functional Materials, Dept. of
Engineering Sciences, Uppsala University, Uppsala, Sweden
TEMPO-mediated oxidation of cellulose has received
considerable attention, either as a pre-treatment in the
production of nanocellulose, e.g. nanofibrillated cellulose
(NFC), or for post-production surface modification of cellulose
nanocrystals and nanofibers. The oxidation is specific for the
C6 primary alcohols and is considered to be unable to
penetrate into the crystalline interior of the nanocellulose
materials, resulting in surface-confined carboxylic acid or
carboxylate groups. The conventional method involves
stoichiometric amounts of cooxidants, e.g. NaClO, NaBrO and
NaClO2, which continuously generate TEMPO+, the
oxoammonium ion form of TEMPO that carries out the
cellulose oxidation (Fig. 1). A more environmentally friendly
approach is to completely remove the cooxidants and instead
generate TEMPO+ electrochemically through electrogeneration
(Fig. 1). In this work we used electrogeneration of TEMPO+ in
order to oxidize highly crystalline Cladophora sp.
nanocellulose. We demonstrate that complete surface
oxidation can be achieved in approximately the same time as
with a conventional TEMPO-mediated oxidation with
cooxidants. The degree of surface oxidation could easily be
controlled by varying the oxidation time, i.e. controlling the
oxidation charge. The fiber width, specific surface area (>115
m2/g), and the pore characteristics of the resulting dried waterinsoluble fibrous particles was unaffected by oxidation.
However, if the oxidation was carried out for longer times than
required for completely oxidizing the surface, significant
amounts of water-soluble products formed, indicating that the
oxidation in fact may proceed beyond the surface.
Fig.1. Electrogeneration of TEMPO+ for oxidation of cellulose and
conventional TEMPO-mediated oxidation with NaClO and NaBrO
cooxidants.
CELL 105
Systematic evaluation on degradation products during
hydrothermal pretreatment of sweet sorghum basis for
biorefinery
Shaolong Sun, [email protected]. Beijing Forestry
University, Beijing, China
The focus of this study was s systematic evaluation on
polysaccharide and lignin degradation products during
hydrothermal pretreatment of sweet sorghum. The influences
of the pretreatment conditions on the degradation products
(such as xylooligosaccharides, acetic acid, furfural, and
hydroxymethylfurfural) were systematically investigated. It was
found that the maximum yield of xylooligosaccharides of
55.71% was achieved in the case of the material pretreated at
a relatively high temperature (170 °C) for a short reaction time
(0.5 h) with a relatively low level of xylose and other
degradation products. Higher temperature (> 170 °C) and/or
longer reaction time (> 0.5 h at 170 °C) reduced the yield of
xylooligosaccharides, but enhanced concentrations of
monosaccharides (arabinose and galactose) and other
degradation products. All the results indicated that the
degradation of the polysaccharides and lignins occurred under
the harsh pretreatment conditions. These findings will result in
a potential utilization of the degradation products obtained in a
current environmentally friendly biorefinery process, and
enhance the economic benefit of the green biorefinery.
Schematic illustration of the experimental procedure.
CELL 106
Potential for enhancement of enzymatic hydrolysis of
sugar maple (Acer saccharum)
Muhammet A. Uygut3,2, Matthew Zelie2, Christopher D. Wood2,
Derek B. Corbett2, [email protected], Prajakta S. Dongre2,
Biljana Bujanovic1. (1) Walters Hall 419, SUNY - ESF,
Syracuse, New York, United States (2) Paper and Bioprocess
Engineering, SUNY-ESF, Syracuse, New York, United States
(3) Firat University, Elaziğ, Turkey
Electron beam (EB) irradiation and hot-water extraction (HWE)
of wood have been used independently as pretreatment
methods to improve enzymatic hydrolysis (EH) of hardwoods
by reducing cellulose crystallinity and removing most of xylans,
respectively. Moreover, the results of our previous studies
have demonstrated that after acetone:water (9:1) (AW)
washing, the lignin content in HW-extracted wood decreased
while hydrolysability increased. In this study the potential to
increase accessibility of sugar maple (Acer saccharum) for EH
was further explored by performing EB irradiation (bars; 250,
750 and 1000 kGy) followed by HWE (chips; 160 °C, 2 hours)
and/or AW (chips; 120 °C, 20 min). After pretreatments (EB,
HWE, EB_AW, EB_HWE, HWE_AW, EB_HWE_AW), wood
was grounded to 30 mesh and EH was performed (Cellic ®
CTec2, HTec2, Novozymes; 72 hours). Samples of
hydrolysates collected throughout EH (sampling every 4 hour
in duplicates) were analyzed for the concentration of glucose
and xylose while the wood before and after EH was analyzed
for the content of lignin and glucose and xylose-based
polysaccharides. These studies are expected to enhance
pretreatment procedure for the production of glucose from
hardwoods by applying relatively mild and environmentally
friendly procedures.
CELL 107
Sustainable bitumen
Ted Slaghek1, [email protected], Dave v. Vliet2, Ingrid
Haaksman1, Cecile Giesen2. (1) Functional Ingredients, TNO,
Zeist, Netherlands (2) structural Reliability, TNO, Delft,
Netherlands
Bitumen is the residu that remains after distillation of crude oil.
This by-product of the crude oil industry is a complex mixture
of hydrocarbons and is used in applications such as
pavements including highways and for roof sealings. In a
typical pavement application about 5% of the total road
construction bitumen is used as a binder next to other
components such as gravel and sand. About 83% of the
bitumen used is applied in pavement applications. For roof
application the amount of bitumen is much higher (50 - 70%).
Usually bitumen for roof applications contain additional
polymers such as SBS (styrene-butadiene-Styrene) or APP
(Atactic Poly Propylene). They are used to modify the bitumen
mixture and create desirable properties. Since a couple of
years the prices for bitumen have increased while the quality of
bitumen is fluctuating. Therefore the market is looking for
alternative sources preferably combined with a reduction in
carbon
dioxide
emissions
(e.g.
natural
polymers).
The paper describes the use of lignin and chemically modified
lignin as a 'green' additive in bitumen mixtures. Lignin is one of
the most abundant natural polymers on earth and au contriare
to carbohydrates is hydrophobic. The focus of the research is
aimed at applying (chemically modified) sulfer free lignin (e.g.
organosolv or lignin obtained through hydrolysis of the
carbohydrates) as an additive instead of a filler in bitumen
applications. Chemically modified lignin show properties similar
to SBS and APP. The paper will describe the use of lignin and
chemically modified in bitumen and the potential that lignin has
in this field of application including construction of lab samples
of pavement. Up to 50% of the bitumen is replaced by lignin.
CELL 108
Structures of carboxylated cellulose fibers – fates of S1,
S2, and S3 layers
Goeun Sim, [email protected], Md N. Alam, Louis
Godbout, Theo G. van de Ven. Chemistry, McGill University,
Montreal, Quebec, Canada
Many of the cellulose chemistries involve various ways of
carboxylation and the carboxyl groups offer readily available
potential reaction sites. Upon carboxylation, both electrostatic
repulsion and the disrupted interfibrillar hydrogen bonding
facilitate the swelling process. With increased degree of
substitution, the carboxylated fibers become highly swollen,
which leads to an irreversible structural deformation. Changes
in fiber structures may vary depending on the type of pulp
fibers, pretreatments, and chemistries applied. In this study, we
will discuss how the microfibrils in secondary wood cell walls
respond to the environment and how they attribute to some of
the challenges in cellulose chemistries such as low yield and
non-uniformfiber fragmentations. In order to elucidate the
structural changes of carboxylated fibers, softwood kraft fibers
were modified by both chemically and mechanically. Balloonlike structures were formed when non-fibrillated fibers were
carboxymethylated. The innermost S3 layers became visible
inside the balloons and they were effectively isolated for further
characterizations. The carboxymethylated S2 microfibrils that
fill up the balloons have enough mobility to rearrange
themselves upon mechanical breakup, thereby resulting in the
formation of spherical particles. The S1 layers are largely
responsible for the ballooning phenomenon as they create
tightly wound collars that are mechanically resistant. The
ballooning can be avoided by grinding the fiber exterior –
mostly S1 layers – prior to the chemical treatment, or by
applying a chemistry which results in more uniform conversion
than carboxymethylation.
CELL 110
Development of 3 drug combination formulations with
cellulose esters for the effective oral treatment of HIV
Hale Cigdem Arca1, [email protected], Durga Dahal3,
Kevin J. Edgar2. (1) Virginia Tech, Blacksburg, Virginia, United
States (2) Mail Code 0323, Virginia Tech, Blacksburg, Virginia,
United States
Microscopic image of toluidine blue dyed carboxymethylated fiber,
showing partially broken balloon-like structures upon subjected to a
prolonged, gentle magnetic stirring.
CELL 109
Physical and structural changes in cellulose microfibrils
responsible for enzymatic hydrolysis rate deactivation
studied by FTIR, XRD, XPS and SFG
Kabindra Kafle4, [email protected], Christopher Lee3, Heenae
Shin1, Seong H. Kim2, Sunkyu Park1. (1) Department of Forest
Biomaterials, North Carolina State University, Raleigh, North
Carolina, United States (2) Penn State Univ, University Park,
Pennsylvania, United States (3) Penn State University,
University Park, Pennsylvania, United States (4) Pennsylvania
State University, State College, Pennsylvania, United States
The deactivation behavior observed in enzymatic hydrolysis of
cellulose substrate could be due to several different substrate
and enzyme characteristics. A full understanding of the
physical and structural changes in cellulose microfibrils during
the hydrolysis is essential in figuring out the substrate
characteristics which largely contribute to the rate limitation at
longer hydrolysis durations. In this study, several different
analytical techniques like Fourier transform Infrared (FTIR)
spectroscopy, X-ray diffraction (XRD), X-ray photoelectron
spectroscopy (XPS) and sum frequency generation (SFG)
spectroscopy are used to investigate the physical changes
which are apparent during cellulase action on Avicel, bleached
softwood and bacterial cellulose. XPS showed that
accessibility of cellulose microfibril surface by the enzymes
could play bigger role in determining the hydrolysis rate
compared to typical substrate characteristics like crystallinity
and degree of polymerization (DP). Surface coverage of
cellulose microfibrils by inactivated protein and/or the
hydrolysis product generated during the longer hydrolysis
period could have limited the exposure of cellulose chains to
the binding sites of the enzymes. The cellulose source chosen
for enzymatic hydrolysis could manifest difference in hydrolysis
progression. SFG showed changes in meso-scale
arrangement of cellulose microfibrils in bleached softwood and
bacterial cellulose with the increasing hydrolysis duration, but
this did not change the final reaction rate between different
cellulose substrate. FTIR, SFG and XRD also confirmed that
cellulose Iα is preferentially hydrolyzed by the enzymes in
bacterial cellulose.
Human immunodeficiency virus (HIV) is a retrovirus that can
cause acquired immunodeficiency syndrome (AIDS), a
condition in which immune system failure can lead to life
threatening infections, cancer or even neurological problems.
Although HIV has these drastic effects, to date no drug has
been developed to cure it and taking a single medication is not
enough to suppress this virus. Three-drug combinations have
the best efficacy for controlling the virus and protecting the
immune system. Therefore, 3 drug combinations of ritonavir,
etravirine and efavirenz amorphous solid dispersions (ASDs)
were prepared with cellulose esters in order to prepare an
higher bioavailability formulations for daily application, to
enhance patient convenience and compliance and prevent viral
adaptation due to missed doses. Although oral administration
is favored, the poor solubility of HIV drugs (0.1-10 ug/ml) leads
to low bioavailability due to their crystallinity and
hydrophobicity. For this reason, ASDs of HIV drugs have been
implemented to suppress crystallinity of these poorly watersoluble and thereby enhance dissolution rate and
bioavailability. Thus, cellulose acetate suberate (CASub),
cellulose acetate adipate propionate (CAAdP), 6-carboxyl
cellulose acetate butyrate (CCAB) and carboxymethylcellulose
acetate butyrate (CMCAB) micro-milled solvent cast films were
prepared in order to increase dissolution rate of ritaonavir,
etravirine and efavirenz. In some cases, vitamin E TPGS were
also added to the formulations in amounts that would generate
concentrations above the critical micelle concentration in order
increase drug release. The amorphous solid-state properties of
these formulations were shown by XRD. By dissolution studies,
it was shown that 3 drugs were released at small intestine (pH
6.8) slowly (without any burst effect) at a concentration higher
than the crystalline drug itself. Accordingly, these formulations
have great potential to increase the bioavailability of the three
drugs, releasing them over a 10-hour period.
CELL 111
Impact of fractionation time on thermal and chemical
properties of organosolv lignins
Jingming
Tao,
[email protected],
Omid
Hosseinaei,
Pyoungchung Kim, David P. Harper, Joseph J. Bozell, Timothy
G. Rials, Nicole Labbe. The University of Tennessee,
Knoxville, Tennessee, United States
Lignin, the second most abundant biopolymer in the world, has
the potential to be utilized for production of materials,
composites, fuels, and chemicals. Organosolv fractionation is a
promising pathway to produce high-purity lignin among all the
biomass deconstruction processes. In this study, yellow poplar
(Liriodendron tulipifera) was fractionated using a mixture of
methyl isobutyl ketone, ethanol, and H2O with 0.05M sulfuric
acid as catalyst at 140°C over a two-hour period. Black liquor
was collected every 15 min during the fractionation to generate
a series of lignins. The yield and purity of lignins were
measured. The thermal properties of the isolated lignins were
analyzed by differential scanning calorimetry (DSC) and
thermal gravimetric analysis (TGA). The chemical properties of
lignin were assessed by the Fourier transform infrared
spectroscopy (FTIR), pyrolysis-gas chromatography-mass
spectrometry (Py-GC/MS), nuclear magnetic resonance
(NMR), gel permeation chromatography (GPC), and elemental
analysis. The results showed that with the increase of
fractionation time from 30 to 120 min, the yield of lignin
declined from 18.26 to 5.51g; the weight average molecular
weight (Mw) decreased from 7781.3 to 4682.5 g/mol; the
degree of polymerization (DP) diminished from 5.96 to 3.88;
whereas the glass transition temperature (Tg) increased from
117.4 to 137.1°C. Principal component analysis (PCA) of the
FTIR and Py-GC/MS spectral data revealed that the
carbohydrate and syringyl bands were mostly responsible for
the separation of the fractions, demonstrating that the
composition and chemical structure of the isolated lignins are
dictated by the organosolv fractionation time. Overall, this
study demonstrates that thermal and chemical features of
lignin can be controlled by the fractionation time to generate
lignins with desired properties.
CELL 112
In situ catalytic fast pyrolysis of lignin for production of
phenols using oxide catalysts
Vaishakh Nair, [email protected], Vinu
Chemical Engineering Department, Indian Institute
Technology Madras, Chennai, Tamil Nadu, India
R.
of
Lignin is one of the main constituents of biomass and a major
by-product obtained from biorefineries and paper-pulp
industries. The presence of phenolic groups along with various
other functional groups makes it an important raw material for
obtaining value added chemicals. Catalytic fast pyrolysis (CFP)
of lignin is recognized as a viable method to obtain high yields
of bio-oil with high selectivity of phenolic or aromatic
compounds. The present study is focused on CFP of alkali
lignin using various semiconductor oxides like TiO2, CeO2 and
ZrO2 to obtain monomeric phenolic compounds. In this study,
TiO2 was synthesized by sol-gel method, and CeO2 and ZrO2
were synthesized by solution combustion method. The
catalysts were characterized for their structure, stability and
pore size distribution using various techniques like FT-IR
spectroscopy, TGA, powder XRD, TEM and porosimetry. Four
different types of TiO2-lignin mixtures, which included physical
mixture, ball milled mixture, ultrasound mixture and chemical
mixture, were prepared and subjected to fast pyrolysis in a
micropyrolyzer and the vapours were analyzed using gas
chromatograph-mass spectrometer. Effects of various reaction
parameters like catalyst to feed ratio, calcination temperature
and pyrolysis temperature (400-700 oC) were studied.
Amorphous mesoporous TiO2 xerogel, that had high specific
surface area, narrow pore size distribution with small pores
and high surface OH content, was more active in producing
phenolic monomers when compared to other semiconductor
oxides and crystalline TiO2. At an optimum fast pyrolysis
temperature of 500 oC, physical mixtures of TiO2:lignin of 1:10
wt./wt. produced highest yield of phenolic compounds and low
yield of char. An overall conversion of 88.5 wt.% of lignin to
bio-oil with 75 wt.% yield of phenolic compounds was
achieved. The selectivity of guaiacol and derivatives in the
phenolic fraction was 77%, and the yield of guaiacol was 23.8
wt.%. The selective production of monomeric phenols over
aromatic hydrocarbons was due to the higher level of
interaction of lignin with the active OH groups present on the
TiO2 surface. This was found to promote selective cleavage of
alpha-O-4 and beta-O-4 bonds, and hence, the
depolymerization of lignin. The higher selectivity of phenolic
compounds obtained with low catalyst to lignin ratio shows that
this catalyst may be a promising candidate for CFP of lignin to
produce value added chemicals.
CELL 113
Magnetic responsive hybrid paper materials that react to
external magnetic fields
Huaying Wang, [email protected], Markus
Biesalski. Chemistry, TU Darmstadt, Darmstadt, Germany
Paper has been used for more than 2000 years as a material
for writing, painting, printing or packaging. However, besides
these classical applications, there is an increasing interest to
use paper as a base material for the design of novel devices,
progressing from point-of-care devices to paper-based
electronics, flexible actuators or hybrid materials. In the
present study, we report on three novel approaches for the
preparation of magnetic paper materials. Firstly, magnetic
paper is prepared via photo-attachment of a benzophenonecontaining polymer together with magnetic particles onto the
paper substrate and the resulting magnetic paper was
characterized by using different methods. In a second
approach, the surface of the magnetite particles was modified
with benzophenone via a silane anchor group. The resulting
particles can further react with functional polymers, which also
contain benzophenone moieties. Thus, the polymer-modified
particles can be covalently attached to the cellulose fibers
inside the paper substrate. In addition, we demonstrate the
preparation of magnetic paper by incorporation of magnetic
cellulose particles into lab-engineered paper sheets. The
obtained hybrid materials can be used for a variety of
applications, e.g. as novel, cantilever-shaped magnetic
actuators.
CELL 114
Effect of different ratio of CMC and Eu(III) on the
fluorescence properties and structures of CMC/Eu
nanocomposites
Ben Wang, Jun Ye, Jian Xiong, [email protected]. South
China Univ. of Techn., Guangzhou Guangdong, China
A red-emitting composite CMC/Eu(Ⅲ) was synthesized by
employing a microwave heating method(70 , pH7.0,1min)
with different ratio of CMC and Eu(Ⅲ), the ratio of CMC:Eu(Ⅲ)
was 10:1, 15:1, 19:1 and 28:1, respectively. The structures of
the composite were analyzed by X-ray diffraction (XRD),
Fourier-transform
infrared
(FTIR)
and
SEM.
XRD
measurement showed that the CMC/Eu composite had lower
crystallinity compared with CMC. The FTIR results indicated
Eu3+ not only combined with -COO- through the ionic bond but
also coordinated with O atom of the –OH and ether bond in
CMC. The SEM images showed that CMC/Eu composites had
good distribution, and the average particle size was less than
100nm, from which we can say that we had synthesized nanosized CMC/Eu composite materials. The optical solid state
properties were determined using UV-absorption, excitation
and emission spectroscopy. The UV-vis spectrum of Eu/CMC
solid showed composites' ultraviolet absorption curve and peak
position were similar to CMC and their absorption intensities
were much stronger than CMC, among them, the 19:1
composite had the highest absorption intensity. The
photoluminescence (PL) measurements exhibited a strong red
emission band centered at about 616 nm (5D0-7F2) under an
excitation wavelength of 395 nm (see Figure). 19:1 simple had
strongest fluorescence intensity while 10:1 and 15:1 simple
has the minimal fluorescence intensity, which indicated that
there was adequate ratio between CMC and Eu3+ which was
19:1and had fluorescence quenching phenomenon when
improve the ratio to 28:1 for decreasing fluorescence intensity.
Acknowledgement: Supported by the National 973 project
under Grant No. 2010CB732201, the National Natural
Foundation of China under Grant No. 31270617 .
tests and morphological investigations were conducted on the
different thermosetting ACCs. A direct correlation was found
between the DO, the crosslinks density, the morphological
aspects and the macroscopic performances. An optimum was
reached for DO of about 0.65-0.75 for which a good cohesion
is observed between amorphous oxidized parts and nonoxidized crystalline parts, leading to the best mechanical
performances.
[1] Guigo, N.; Mazeau, K; Putaux, J-L.; Heux; L. Cellulose ,
2014, in press.
CELL 116
One-pot formation of 2,3-dialdehyde cellulose (DAC)
beads
Jonas Lindh, [email protected], Daniel O.
Carlsson, Changqing Ruan, Maria Stromme, Albert Mihranyan.
Nanotechnology and functional materials, Engineering
Science, Uppsala University, Uppsala, Sweden
CELL 115
All-cellulose composites from partial periodate oxidation
and thermal crosslinking
Nathanael Guigo1, [email protected], Amandine Codou1,
Laurent Heux2, Nicolas Sbirrazzuoli1. (1) Laboratory of
Condensed Matter Physic, University Nice Sophia Antipolis,
Nice Alpes Maritmes, France (2) CERMAV-CNRS, Grenoble
Cedex09, France
The All-Cellulose Composites (ACCs) present very interesting
properties as a “one-pot” process compared to traditional
nanobiocomposites and are mostly processed so far either
from partial dissolution or derivatization of cellulose. The
present work proposes a third class of ACCs. The idea is to
use a single source of cellulose, but only to functionalize part
of it to yield an in-situ thermosetting-prone matrix that can be
further heat-processed with the remaining un-derivatized part
of the sample. As a widely spread material, icrocrystalline
cellulose (MCC) was selected and subjected to different
degrees of oxidation (DO), by by tuning the conditions of the
reaction. Such oxidation induces a glucosyl ring opening
reaction that leads to the formation of two very reactive
aldehyde groups at the C2 and C3 position which rapidly
recombine with adjacent unreacted OH groups to form intrachain hemiacetals with likely 5 to 8-member fused rings.[1]
Then, in compressed hot environment the hemiacetal groups
reorganize into inter-microfibrillar bonds, leading to ACC
products with strong properties. 13C solid-state NMR
spectroscopy data were collected on the different processed
samples in order to qualitatively and quantitatively highlight the
ultrastructural evolution of crystalline cellulose as a function of
the DO and the hemiacetal crosslinking. Flexural mechanical
A convenient method for formation of 2,3-dialdehyde cellulose
(DAC) beads via periodate oxidation of highly crystalline
nanocellulose from the Cladophora algae in water has been
developed. The periodate oxidation of highly crystalline
nanocellulose to provide DAC has previously been reported to
give moderately oxidized cellulose. With our method degrees
of oxidation up to 100% (∼12 mmol) has been achieved using
nanocellulose from Cladophora algae. At high degrees of
oxidation (>80%) the morphology of the nanocellulose changed
dramatically and spherical beads, which ranged in size from 220 μm, were formed. This method provides DAC beads with an
aldehyde content of up to 12 mmol in a simple one-pot reaction
using water as reaction medium. Further, a route based on
cross-linking with diamines via reductive amination to provide
DAC beads with increased specific surface area (SSA) and
porosity in the mesoporous range has been developed. The
introduction of diamines provide beads with a porous texture
and a SSA increasing from <1 m2/g to >30 m2/g. Both aliphatic
and aromatic diamines were found useful for producing porous
beads having a pore size distribution range between 10 and
100 nm. The total porosity of the beads was, according to
mercury porosimetry, in the range of 54-64%. It was concluded
that introduction of tethered diamines to DAC beads is a simple
and effective method to produce mesoporous beads.
DAC bead
Cross-linked DAC bead
CELL 117
Interactions between cellulose surfaces and cellulases
from different origins studied by QCM
Junlong Song1,4, [email protected], Yan Li2,
[email protected], Orlando J. Rojas3,4. (1) Dept of Paper
Science, Nanjing Forestry Univ, Nanjing Jiangsu, China (2)
Colorado State University, Fort Collins, Colorado, United
States (3) Forest Biomaterials, North Carolina State University,
Raleigh, North Carolina, United States (4) Dept of Forest
Products Technology, Aalto University, Espoo, Finland
The enzymatic hydrolysis of crystalline region of cellulose is
one of the bottlenecks to produce bioenergy and biochemicals. To understand the interactions between the binding
modules of cellulases and the surface of cellulose polymorphs
is helpful to understand the mechanism of enzymatic
hydrolysis of cellulose and therefore is helpful to enhance the
efficiency of enzymatic hydrolysis, to reduce the loading of
enzymes and to improve the recovery rate of enzymes. In this
investigation, microcrystalline cellulose was initially treated with
NaOH and then suffered to hydrolysis to obtain the cellulose
crystals with polymorphs of Cellulose II and the intermediate
polymorphs of cellulose I/II. Followed by modification QCM
sensors with those produced crystals, the interactions between
cellulose crystal surface and four cellulases from different
origins of Trichoderma reesei ATCC 26921, Trichoderma
viride, Aspergillus sp. and Aspergillus niger were monitored by
Quartz Crystal Microbalance at 15 ºC and then the
corresponding hydrolysis was monitored was well at 45 ºC.
The results showed that cellulase from different origin have
different affinity to cellulose surface due to their have different
binding modules. And the polymorpths of cellulose crystals
also have some impacts on the dynamics of adsorption and
have significant influence on the hydrolysis. The results of this
investigation will provide some theoretical evidence to the
pretreatments of lignocellulosics, the oriented culture, and the
recovery of cellulases.
CELL 118
Isolation and structural analysis of novel sulphur-free
lignin fraction from non-wood plant materials
Jussi Sipila1, [email protected], Jussi Kontro1, Paula
Nousiainen1, Yrjö Mälkki2. (1) University of Helsinki, Helsinki,
Finland (2) Cerefi Ltd, Espoo, Finland
Lignin is the second most common ingredient of the biomass
produced by plant kingdom and separated from plant material
in largest amounts in cellulose industries as a by-product.
Purpose of the method1 is to isolate lignin from plant materials
in as native form as possible, and methods for its purification or
fractionation for industrial utilization other than energy
production to various purposes. The isolated lignin can be
applied e.g. or production of adhesives and binding materials,
antioxidants
and
organic
aromatic
chemicals.
Cereal straw, hulls or stover were treated in 3 % w/w sodium
hydroxide solutions at the boiling point at atmospheric
pressure. As the first processing stage residues of cellulose
and mechanical impurities were removed from the black liquor
by filtration. For separating lignin from the solution,
hemicelluloses and residual cellulose were hydrolyzed by
using multifunctional enzymes at one or several stages, after
which lignin was precipitated by acid. The lignin content of the
final product (CEREFI LIGNIN) was at least 80%, and its mean
molecular weight (Mw) from 2000 to 5400 g/mol. Lignins
separated from oat straw contained phenolic hydroxyls at least
1.0 mmol/g. The number of aliphatic hydroxyls was at least 1.5
mmol/g, but at the highest 3.0 mmol/g, indicating a decrease in
the content of side chains, however, maintaining the close
resemblance to native lignin indicated by 13C NMR and
HSQC-NMR.
1Y. Mälkki and J. Sipilä, Separation of lignin from plant
material. PCT Application WO 2012/120184
CELL 119
Vibrational sum-frequency-generation (SFG) spectroscopy
study of cellulose microfibril orientation and assembly in
onion epidermis and reaction woods
Kabindra Kafle1, [email protected], Xiaoning Xi1, Rui Shi6,
Christopher Lee5, Ashutosh Mittal4, Sunkyu Park3, Bernard R.
Tittmann1, Vincent Chiang6, Daniel Cosgrove5, Yongbum
Park1, Seong H. Kim2. (1) Pennsylvania State University, State
College, Pennsylvania, United States (2) Penn State Univ,
University Park, Pennsylvania, United States (3) Department of
Forest Biomaterials, North Carolina State University, Raleigh,
North Carolina, United States (4) Biosciences Center, MS 3323, National Renewable Energy Laboratory, Golden,
Colorado, United States (5) Penn State University, University
Park, Pennsylvania, United States (6) North Carolina State
University, Raleigh, North Carolina, United States
The cellulose microfibril (CMF) orientation in the secondary cell
walls of tension wood, compression wood, and primary cell
walls of onion abaxial epidermis was studied with sum
frequency generation (SFG) vibration spectroscopy. The SFG
spectral features of tension wood and the epidermis of the
outermost onion scale changed depending on the angle
between the polarization of the incident IR beam and the
preferential alignment axis of CMFs. In onions, the epidermal
cells are elongated along the onion bulb axis. SFG showed
that the outer most scales have an average CMF orientation
over the entire thickness of the cell wall, oriented perpendicular
to the bulb axis and more dispersed in the inner scales of the
bulb. The surface orientation of CMFs imaged by AFM also
showed a similar trend. Tension wood contains highlycrystalline and highly-aligned CMFs. The change in
alkyl/hydroxyl intensity ratio in tension wood, with respect to
the azimuthal angle between incident polarization of IR beam
and preferential alignment axis of CMFs, meant that CMFs are
highly aligned along the wood grain axis. Compression wood
did not show any dependence on the orientation of the incident
IR polarization, implying that the overall orientation of cellulose
microfibrils in compression wood is not highly aligned.
However, the change in SFG alkyl/hydroxyl intensity ratio in
compression wood was due to larger separation between
CMFs and lower cellulose content. The SFG analysis of CMFs
in onion epidermis and reaction wood showed that SFG
spectral features are sensitive to average CMF orientation and
inter-fibrillar separations. This capability of SFG analysis is
useful to understand the correlation of CMF orientation and
assembly with cell wall biomechanical properties, growth
mechanism, and cell wall response to external stress.
CELL 120
Determination of the molecular weight distribution of
highly oxidized dialdehyde cellulose by size exclusion
chromatography
Irina Sulaeva2, Thomas Rosenau1, Antje Potthast2, Karl
Klinger3, [email protected]. (2) Chemistry, University
of Natural Resources and Life Sciences, Vienna, Austria (3)
Chemistry, McGill University, Montreal, Quebec, Canada
Periodate oxidation has recently gained considerable attention
with regard to cellulose utilization and modification. Periodates
selectively cleave the C2-C3-bond of the cellulose
anhydroglucose unit with formation of carbaldehyde groups.
The dialdehyde cellulose promises a rich follow-up chemistry,
which can be used for cross-linking, immobilization of chemical
entities, enzymes, microbia, and for further conversion into
other functional groups, such as amines, alcohols, acids and
sulfonates. While dialdehyde cellulose of low to intermediate
degree of oxidation is insoluble due to formation of inter-chain
hemiacetal bonds, highly oxidized DAC (>80% oxidation
degree) dissolves upon heating in water. This renders it
accessible to standard polymer characterization methods, such
as size exclusion chromatography (SEC). Aqueous SEC,
however, entails some problems usually not found in SEC with
organic solvents. Due to aggregation effects, the elution profile
often changes greatly in dependence of ionic strength and pH.
Furthermore, the limited chemical stability of dialdehyde
cellulose makes careful optimization of sample preparation
necessary.In this study, we investigated the determination of
the molecular weight distribution by aqueous SEC coupled with
a MALLS detector. Different substrates, concentrations,
sample preparation methods and eluents were tested in order
to find optimal conditions for reliable SEC measurements.
CELL 121
Nanofibrillation of dried pulp in NaOH solutions and their
regenerations
Kentaro
Abe,
[email protected].
University, Uji, Japan
Kyoto
The drying process in typical pulp production generates strong
hydrogen bonding between cellulose microfibrils after the
removal of the matrix, which seems to make it difficult to obtain
thin and uniform cellulose nanofibers. In the present study, we
tried the fibrillation of pulps under alkaline condition in order to
obtain fine nanofibers from dried pulps.
CELL 122
Characterization of cellulose nanofibrils sheet mixed with
synthetic or natural pulp fiber
Kyujeong Sim, [email protected], Hye Jung Youn, Jegon
Lee, Hyeyoon Lee. Seoul National University, Seoul, Korea
(the Republic of)
Cellulose nanofibrils (CNF), prepared by mechanical shearing
action, has a great potential to many industrial fields due to
their advantages such as biodegradability, high mechanical
strength, and high aspect ratio. CNF would be used as a
filtration media by converting to porous sheet form. The pore
characteristics of sheet made by CNF are important. In this
study, the porous CNF sheet mixed with synthetic fibers
(polyethylene terephthalate) or natural wood pulp fibers
(softwood or hardwood bleached kraft pulp) was prepared and
then its pore characteristics were investigated. The CNF
sheets mixed with other fibers were prepared by wet-laid
forming. The porosity of sheet could be controlled by CNF
content, the type of mixed fibers, and drying condition. The air
permeability, tensile properties such as tensile index and
elastic modulus, and pore size distribution were changed
depending on the CNF content, the type of mixed fibers, and
drying conditions.Acknowledgement: This work was supported
by the National Research Foundation of Korea (NRF) grant
funded
by
the
Korea
government
(NRF2012R1A2A2A01011091).
CELL 123
Theoretical models of electron transfer processes in
LPMOs and model peptide systems
Laura Berstis1, [email protected], Michael F. Crowley2,
Gregg Beckham3. (1) National Renewable Energy Laboratory,
Golden, Colorado, United States (2) National Renewable
Energy Lab, Lakewood, Colorado, United States (3) NREL,
Golden, Colorado, United States
Electron transfer (ET) reactions are critical steps in enzymatic
reactivity across a broad range of biological processes. ET has
been also been revealed as a key step in the novel, oxidative
mechanism of the newly discovered class of cellulosedegrading enzymes, lytic polysaccharide monooxygenases
(LPMOs). Beyond the fundamental value of improving our
understanding of this biochemical process, elucidation of
LPMO's novel reactivity would also have far-reaching
implications for biofuel production pretreatment processes.
However, the complexity and sensitivity of ET through proteins
poses a challenge for the development of reliable electronic
structure models capable of predicting electron tunneling
probabilities in protein, highlighting the need for improvement
of theoretical tools in this field. The present work further
develops and characterizes several recent theoretical
advancements using molecular mechanics and quantum
mechanics methodologies for the prediction of biological ET
processes ranging from fast hopping processes, to single-step
non-adiabatic tunneling mechanisms. Model peptides are
designed and utilized for the characterization of these
approaches, and to furthermore evaluate a spectrum of
electronic properties of amino acid side chains. Additionally,
through the study of these model systems, we depict the
influence of individual amino acids and peptide sequences on
available electron tunneling pathways. Through the application
of these QM and MM methods, and the detailed knowledge
gained from model systems, we report theoretical predictions
of the novel ET reaction mechanisms in biomass-degrading
enzymes.
CELL 124
Continuous hydrolysis of carboxymethyl cellulose with
cellulase aggregates trapped inside membranes
Le Truc Nguyen1, [email protected], Kun-Lin Yang2. (1)
Chemical and Biomolecular Engineering, National university of
Singapore, Singapore, Singapore (2) NUS, Singapore,
Singapore
Enzymatic hydrolysis of cellulose is often conducted in batch
processes in which hydrolytic products may inhibit enzyme
activity. In this study, we report a method for continuous
hydrolysis of carboxymethyl cellulose (CMC) by using crosslinked cellulase aggregate (XCA) trapped inside membrane.
The XCA, prepared by using a millifluidic reactor, has a
uniform size distribution around 350 nm. Solutions containing
XCA particles can be filtered through a polyethersulfone
membrane to trap XCA inside the membrane with high trapping
efficiency. This membrane with impregnated XCA can be used
for continuous hydrolysis of soluble CMC in aqueous solutions
flowing through the membrane. When the CMC concentration
is 1.0 g/l, 53.9% of CMC can be hydrolyzed by XCA and
becomes reducing sugars. After 72 h of reaction, 97.5% of the
XCA remains on the surface of membrane. This result shows
that membrane with XCA is stable and has good stability even
under reaction conditions.
CELL 125
Novel materials from wood component
Linn K. Carlsson, [email protected], Paula Martirez, Mikaela
Helander, Ana Lopéz Cabezas, Oskar Schmidt. Cellutech AB,
Stockholm, Sweden
Cellutech is a company focused on innovation, development
and commercializing of new sustainable materials based on
wood. The innovations within Cellutech are developed in close
collaboration with the scientists in the research center
Wallenberg Wood Science Center (WWSC), Sweden.
Cellutech offers technologies for preparation of hollow
cellulose spheres, nanocellulose foams, magnetic cellulose
composites, non-toxic superhydrophobic surfaces, and various
polymers for cellulose fiber modification.A technique for
preparing hollow spheres from cellulose has been developed.
The properties of the hollow cellulose spheres can be tailored
and the sizes can be varied from micrometers up to
millimeters, and are of particular interest for encapsulation. The
shells can either be porous or solid depending on the desired
application. The spheres with porous shells can release
desired compounds through the shells, and gas filled spheres
with solid shells can be used as filling or packing material. A
highly porous, lightweight solid nanocellulose material has
been prepared. The solid foam has very good mechanical
properties in relation to its weight and other parameters such
as, stiffness and flexibility can be varied according to
application The cellulose foam material has potential
applications such as insulation, packaging and absorption
material.
CELL 126
Production of nanocellulose through hydrolysis without
mineral acids using sub-critical water
Lísias Pereira Novo1,2, [email protected], Araceli Garcia2,3, Antonio Aprigio da Silva Curvelo1,4,
Naceur Belgacem2, Julien Bras2. (1) Departamento de Físicoquímica, Instituto de Química de São Carlos, Universidade de
São Paulo, São Carlos, São Paulo, Brazil (2) Laboratoire de
Génie des Procédés Papetiers (LGP2), Grenoble INP-Pagora,
Saint-Martin-d’Hères, France (3) Department of Chemical and
Environmental Engineering, University of the Basque Country
UPV/EHU, Donostia-San Sebastián, Spain (4) Laboratório
Nacional de Ciência e Tecnologia do Bioetanol , Centro de
Pesquisa em Energia e Materiais (CNPEM), Campinas, São
Paulo, Brazil
In the present study, an innovative method of production of
nanocellulose (NCC) was studied. The conventional method of
obtaining NCC utilizes concentrated solutions of strong acids
to promote the hydrolysis of cellulose, however water could
also hydrolyses polysaccharides with the increase of the
severity of the reaction conditions. In this sense, the increase
of temperature and pressure allows higher diffusion and
activity of water, enabling partial hydrolysis of cellulose. The
source of cellulose used was commercial microcrystalline
cellulose (Avicel®). The obtained hydrolyzed cellulose were
submitted to different analytical techniques in order to evaluate
their morphology (DLS, TEM, AFM, FEG-SEM) and
physicochemical properties (XRD, conductimetry, TGA). The
use of water as the main reagent and the absence of any
inorganic acid makes it a promising process, since these are
“green” chemistry characteristics. Also, this method shows
great possibilities of an upsize to an industrial use for its low
corrosion and low cost of reagents.
CELL 127
New nanohybrid materials from sugar cane bagasse: The
role of acid hydrolysis
Lurayni Diaz1, [email protected], Roberto Hernandez Ortiz1,
Monica Tete1, Euribel Mata2, Eleida Sosa1, Reinaldo Atencio1.
(1) Centro de Investigación y Tecnología de Materiales,
Instituto Venezolano de Investigaciones Científicas, Maracibo,
Zulia, Venezuela, Bolivarian Republic of (2) Departamento de
Quimica, Universidad del Zulia, Maracaibo, Zulia, Venezuela,
Bolivarian Republic of
The chemistry of micro and nanostructured carbon materials
currently occupies a unique place in the scientific debate.
Knowledge of the structural composition and the structureproperty becomes a key tool to enhance their applications.
There are various techniques for obtaining these kind of
materials, but the hydrothermal carbonization stands out for to
be quick and easy, it is also possible to use Lenna, foliage of
cassava, bagasse and sugarcane as synthetic precursors.
However, this technique are limited by the strong bonds of the
molecules that make up the structure, majority: cellulose,
hemicellulose and lignin. For this reason, in this work we
propose to use a pre-treatment before the hydrothermal
carbonization: the acid hydrolysis using HNO3 acid in a rang of
concentration between 2-20 % v / v, under reflux conditions.
We also adjusted the mass / volume ratio resulting of the
mixture of the material/acid. The acid hydrolysis contribute to
breakdown of fibrous material bonded strongly, leaving
available fragments of molecules that make up the cell walls of
the biomass, acting as precursors for the formation of new
carbon structures with different morphologies with high added
value. Under specific conditions during acid hydrolysis and
treatment via hydrothermal carbonization was possible to
obtain hybrid nanomaterials with well defined morphologies
without the use of catalysts.
CELL 128
Imaging cellulose nanocrystals by transmission electron
spectroscopy
Madhu Kaushik1, [email protected], Wei Chen1,
Theo G. Van De Ven2, Audrey H. Moores3. (1) Chemistry,
McGill University, Montreal, Quebec, Canada (2) Pulp Paper
Bldg, McGill University, Montreal, Quebec, Canada (3) Chem
Dept, McGill University, Montreal, Quebec, Canada
Although transmission electron microscopy (TEM) is a method
of choice for the analysis of cellulose nanocrystals1 (CNC), it is
still a challenging technique to use due to the low electron
density and agglomeration issues associated with this material.
This work presents a robust and reproducible method to
perform TEM characterization of CNC, without the need for
staining. It is demonstrated that low pH and hydrophilic TEM
grids favored high dispersion of the sample for optimal
imaging. Electron beam and voltage settings are also
discussed. Three distinct types of CNC are analyzed: neverdried, freeze-dried and spray-dried CNC2. Although a few
reports accounted for mushroom structures, we demonstrate
herein that, regardless of sample history, this nanomaterial is
always rod-shaped. By dismissing the use of heavy metal
staining, multi-component systems, for instance palladium
nanoparticles onto CNC4 could be imaged by TEM. In addition,
3D-imaging of the CNCs are carried out to better understand
its morphology.
Engineering, Auburn University, Auburn, Alabama, United
States (4) Chemical Engineering, University of Connecticut,
Mansfield, Connecticut, United States (5) Materials
Engineering, Auburn University, Auburn, Alabama, United
States
CELL 129
Evaluation of various parameters in the production of
whey protein concentrate-based films
Magdalena Víquez1, [email protected], Manuel
Molina Cordoba 1, Marianelly Esquivel Alfaro2, Marta Montero
Calderon 1. (1) Ingeniería Química , Universidad de Costa
Rica, San Pedro, Montes de Oca , San José, Costa Rica (2)
Polymer Research Laboratory (POLIUNA), Universidad
Nacional de Costa Rica, Heredia, Costa Rica
About 90% of the milk becomes whey after being subjected to
a coagulation process for casein obtaining used in the cheese
production; the whey obtained as a byproduct is a highly
polluting substance if it is not properly treated, due to its high
biological oxygen demand.Among the whey components are
lactose, protein, and other minerals, that is why this had been
used as raw material for several applications such as:
development of sports drinks, alcoholic beverages, Ricotta
cheese,ethanol, lacticacid ,among others.Another application is
the films production, using the proteins present in the whey,
with possible implementation in the food industry, since they
work as a barrier between the food and the environment.
On this work it was studied the influence of variables such as:
amount of plasticizer, preservative concentration and film
formation conditions (temperature, time) on the impact on
tensile, water absorptivity and water vapor permeability of films
produced from whey protein concentrate.Preliminary results
obtained on the project indicated that temperatures above 78 °
C and times longer than 10 minutes during the film formation,
generate coagulation of the solution and hinder the formation
of the films. On a second stage of this work, the films obtained
with the best properties will be analyzed by thermal analysis
and biodegradation.
CELL 130
Immobilization of glucose oxidase in cellulose supports
Maria L. Auad2, [email protected], Ricardo A. Ballestero1,
Oscar Nordness4, Mary Arugula5, Aleksandr L. Simonian3. (1)
Polymer and Fiber Engineering, Auburn University, Auburn,
Alabama, United States (2) Polymer and Fiber Eng., Auburn
University, Auburn, Alabama, United States (3) Mechanical
The immobilization of enzymes has come to serve a significant
role in bio-sensing technologies over the past 50 years. A
particular focus within this field has been the implementation of
the glucose oxidase enzyme for the monitoring of glucose
levels within the bloodstream. This technology holds inherent
value for diabetes research and treatment as glucose
monitoring is essential to controlling blood sugar levels. In
order to be effectively applied, glucose oxidase must be
immobilized to a conductive support structure in order to
provide accurate readings. In this study glucose oxidase was
immobilized on a cellulose support using multiple approaches.
In the first one, silica particles were deposited onto micro
crystalline cellulose using the sol-gel procedure, followed by an
epoxidation reaction with epichlorohydrin. This modified
cellulose was then placed in solution and reacted with glucose
oxidase in a phosphate buffered saline (PBS) pH 6.0 buffer. In
the second approach, MCC which was acid hydrolyzed forming
cellulose nano fibers (CNF), which was subsequently
epoxidized. The CNF was then placed in solution and reacted
with the glucose oxidase in the same PBS buffer. A third and
final approach was taken in which Silica particles with attached
epoxide groups were attached to CNF following the sol-gel
Procedure with 3-Glycidoxypropyl-trimethoxysilane.
CELL 131
Thermal protection of vitamins B1, B2, B3, B6 and B12
with bacterial nanocellulose
Marlon Andres Osorio Delgado2, [email protected],
Diego Sanchez2,1, Jorge Velásquez-Cock2,1, Robin Zuluaga
Gallego2, Piedad Gañán2, Claudio Jiménez4, Orlando J.
Rojas3, Lina Velez-Acosta2, Beatriz Gómez2, Cristina Isabel
Castro Herazo2. (1) New Materials Research Group, Pontificia
Bolivariana University, Medellín, ANT, Colombia (2)
Universidad Pontificia Bolivariana, Medellin, Antioquia,
Colombia (3) Forest Biomaterials, North Carolina State
University, Raleigh, North Carolina, United States (4) Grupo de
investigación aplicada al medio ambiente-GAMA., Corporación
Universitaria Lasallista, Caldas, Colombia
Vitamins of B complex are precursors of gene redox reactions
[1]. A low intake of them can produce diseases as pellagra,
cancer and so on [2].Vitamins of B complex are found in most
foods, nonetheless due to their heat sensitiveness, they
degrade during cooking [3]. Bacterial nanocellulose (BNC)
have been used in food formulations as fibre dietary,
thickening and water-binding agent [4]; additionally in
composite materials the inclusion of BNC improves the thermal
stability of polymeric matrices [5]. With this background, the
aim of this research is to evaluate the use of BNC as a thermal
protection agent for vitamin B1, B2, B3, B6 and B12. Vitamins
were added in a suspension of BNC at 0.5 wt% and dried by
spray drying. Thermogravimetrical analysis (TGA) was carried
out to compare the thermal behaviour of these vitamins in the
presence or not of BNC. Additionally, they were characterized
by scanning electron microscopy, in order to observe the BNC
morphology, absorption/desorption isotherms and optical
microscopy. BNC enhances the heat stability of the vitamins up
to 300 °C in onset temperature. The morphology of BNC dried
by spray dry is like crumpled paper balls of 7.5 ± 5.5 µm that is
nanostructure by BNC nanorribbons. BNC can absorb/desorbs
enough micronutrient to supply the daily human requirements.
Optical microscopy shows that micronutrient prevalent on the
surface of the BNC, nonetheless because the establishment of
secondary forces trough hydrogen bonds the micronutrient is
thermally protected.
[1] D. O. Kennedy, R. Veasey, A. Watson, F. Dodd, E. Jones,
S. Maggini, and C. F. Haskell, “Effects of high-dose B vitamin
complex with vitamin C and minerals on subjective mood and
performance in healthy males.,” Psychopharmacology (Berl).,
vol. 211, no. 1, pp. 55–68, Jul. 2010.
[2] J. B. Kirkland, “Niacin requirements for genomic stability.,”
Mutat. Res., vol. 733, no. 1–2, pp. 14–20, May 2012.
[3] E. C. P. Moreschi, J. R. Matos, and L. B. AlmeidaMuradian, “Thermal analysis of vitamin PP Niacin and
niacinamide,” J. Therm. Anal. Calorim., vol. 98, no. 1, pp. 161–
164, Jul. 2009.
[4] Z. Shi, Y. Zhang, G. O. Phillips, and G. Yang, “Utilization of
bacterial cellulose in food,” Food Hydrocoll., vol. 35, pp. 539–
545, Mar. 2014.
[5] J. George, K. V Ramana, a S. Bawa, and Siddaramaiah,
“Bacterial cellulose nanocrystals exhibiting high thermal
stability and their polymer nanocomposites.,” Int. J. Biol.
Macromol., vol. 48, no. 1, pp. 50–7, Jan. 2011.
CELL 132
Effects of time, temperature, and pH
Interconversion of cellulose I to cellulose II
on
the
Md
Shariful Islam1, [email protected],
Chemar J. Huntley3, Willard E. Collier2, Michael L. Curry2,3. (1)
Chemistry, Tuskegee University, Tuskegee, Alabama, United
States (2) Department of Chemistry, Tuskegee University,
Tuskegee, Alabama, United States (3) Materials Science and
Engineering, Tuskegee University, Auburn, Alabama, United
States
Interest in the use of cellulose to replace or include in the
fabrication of sustainable and biodegradable polymer
composites for use in technological devices has intensified in
the last decade due to its environmentally friendly attributes.
From a materials perspective, the contrasting properties of the
different cellulose polymorphs have great potential, for
example, cellulose I “CI” has limited applications because of its
insolubility in common solvents and thermal degradation upon
melting whereas cellulose II “CII” has a greater thermal stability
and higher chemical reactivity than CI. Numerous literature
reports have explored the extraction of cellulose from biomass
sources and the different polymorphs; however, much is still
unclear about the extraction of cellulose and the mechanism of
polymorph interconversion. In addition, many questions remain
regarding the effect of extraction and solvent parameters on
cellulose’s resulting physical and chemical properties. Hence,
in this study, we have explored the influence of some
parameters (temperature, time, and pH) on the conversion and
cellulose from CI to CII for commercially purchased cellulose.
This study reports the conversion of Cellulose I to Cellulose II
at optimized times and temperatures with 15% NaOH (w/v)
solution and the effect of pH on the interconversions using an
acetate buffer. In short, XRD reveals that time, pH, and
temperature play significant roles in the maximum conversion
possible for CI to CII. Furthermore, for comparative studies, the
effect of these parameters on cellulose extracted under various
hydrolysis conditions is currently under investigation as well.
Acknowledgements: The authors gratefully acknowledge the
National Science Foundation under Grant Nos. NSF EPS1158862, NSF HRD-1137681, NSF IGERT on Sustainable
Electronics DGE-1144843 and the Department of Chemistry
for support of this research
CELL 133
Polymeric functionalized beads from alginate for targeted
release of auxin into water
Mei Li1, [email protected], Gisela Buschle-Diller1,
Thomas J. Elder2. (1) Polymer and Fiber Engineering, Auburn
University, Auburn, Alabama, United States (2) USDA Forest
Service, Pineville, Louisiana, United States
A large amount of agricultural water in the U.S. and worldwide
is polluted by different types of contaminants discharged by
various agricultural operations. Chemicals applied for plant
growth, such as auxin, can be entrapped by materials made
from abundant, low cost polysaccharides. Controlled release of
these compounds is a feasible approach to deal with rapid
chemical run-off problems. In this research, a series of bipolysaccharide beads from alginate combined with other
natural polysaccharides, e.g. cellulose, starch, xylan, were
synthesized. Kaolin and polyelectrolyte were incorporated into
the bead system for improved mechanical properties and
enhanced entrapment capacity as well as controlled release
rate of auxin from the beads. The average diameters and size
distribution of beads were assessed by optical microscopy and
differences in morphology observed by scanning electron
microscopy.
CELL 134
Moisture
and
solvent
nanocomposite materials
responsive
cellulose/SiO2
Meng He1,2, [email protected], Bo Duan2, Lina zhang2.
(1) Jiangsu Provincial Key Laboratory of Eco-Environmental
Materials, Yancheng Institute of Technology, Yancheng, China
(2) Department of Chemistry, Wuhan University, Wuhan, China
Water responsive SiO2/cellulose nanocomposite hydrogels and
films were constructed, for the first time, by dispersing SiO2
nanoparticles into cellulose solution in LiOH/urea solvent, and
then by crosslinking with epichlorohydrin (ECH) or
regeneration in coagulation bath, respectively. The
SiO2/cellulose nanocomposites at wet state or in water
displayed unique behaviors, which exhibited higher light
transmittance than those before contacting with water. The
results revealed that strong hydrogen-bonding interaction
among water, cellulose and SiO2 led the good dispersion of
SiO2 nanoparticles in the cellulose matrix, resulting in a good
miscibility. The transmittance and mechanical properties test
revealed that the incorporation of SiO2 nanoparticles not only
improved the transmittance and mechanical strength of the
cellulose hydrogels, but also improved the mechanical strength
of the composite films. Especially, the cellulose/SiO2
nanocomposite films were milky at dry state and changed to
transparent after being soaked in water. The analysis of results
proved that SiO2 and cellulose in existence of water could form
strong hydrogen bonding to create a homogenous network
structure. Furthermore, the cellulose/SiO2 smart composite film
exhibited moisture and solvent responsiveness, showing
potential applications in moisture detection and usability at wet
state.
CELL 135
Paper-based microfluidics for typing of primary and
secondary human blood groups in “text”
Miaosi Li1, [email protected], Whui Lyn Then2, Junfei
Tian1, Wei Shen1. (1) Monash University, Melbourne, Victoria,
Australia (2) Chemical Engineering , Monash University,
Clayton, Melbourne, Victoria, Australia
Blood groups have been considered the best human genetic
markers for many years since they carry a significant amount
of information for mapping the human genome. The discovery
of the ABO blood group has first made blood transfusion
feasible. The later discovery of the RhD antigens has led to the
understanding and subsequent prevention of haemolytic
disease of the newborn (HDN). To date, 30 blood group
systems, including the primary blood groups-ABO, RhD-and
other secondary blood groups, have been classified. Each of
these blood groups contains unique sub-type antigens and the
correct typing of the human blood groups is clinically significant
in blood transfusion and blood banking.Patterned bioactive
paper and other low-cost bioactive materials have become
platforms for making low-cost and user-operated devices for
diagnosis. The potential of this platform to deliver affordable,
rapid, and user-friendly diagnostic sensors in the developing
countries has become increasingly clear. Research to date has
successfully generated a few blood typing devices and
diagnostics. However the major requirements for new
generation of home- or field-based blood typing sensors are
that they must be able to rapidly and unambiguously report the
blood typing result to non-professional users. Therefore this
work utilises paper and printing technologies in combination
with biochemistry and haematology to explore engineering
designs of a new class of diagnostic blood analysis devices.
This work reports a break-through in design of a novel paperbased blood-typing device, which reports the blood-typing
assay results with written text, instead of by visual observation
of red blood cell agglutination. This novel device reports the
assay result in an unambiguous way and does not require the
users to have the knowledge to interpret their blood typing
results from the first principle. This break-through significantly
reduces the possibility of misinterpretation of the blood-typing
assay; it makes this invention highly suitable for point-of-care
products and for blood analysis in developing countries. This
work can also potentially reduce cases of result
misinterpretation in hospital bed-side tests in developing or
even developed countries, which is a one of the leading
causes of medical complications in blood transfusion.
CELL 136
In vitro synthesis of cellulose under various conditions
Paavo A. Penttilä, [email protected], Junji
Sugiyama, Tomoya Imai. Research Institute for Sustainable
Humanosphere, Kyoto University, Uji, Kyoto, Japan
Despite extensive studies over several decades, many factors
related to the biosynthesis of cellulose remain unclear. In
particular, the cellulose-synthesizing machinery of higher
plants is known to be especially complicated, working under
limited space and involving simultaneous production of other
polysaccharides. For this reason, understanding the function of
more primitive cellulose-synthesizing systems will be useful.
Cellulose-producing bacteria, such as the Gluconacetobacter
xylinus (Gx), have been widely used to understand the basic
requirements and key components of cellulose biosynthesis. In
the past, this approach has enabled for instance the
identification of the genes necessary for synthesizing cellulose,
allowing later recognition of their equivalents in higher plants.
However, even in the case of bacteria, the factors underlying
the formation of supermolecular ordered structures, like the
cellulose microfibril, still remain to be elucidated.
In this work, cellulose was synthesized in vitro by cellulose
syntheses extracted from Gx. The effects of reaction
conditions, such as temperature and physical stimulation, on
the quantity and structure of the cellulosic products were
studied. Cellulose structures synthesized under different
conditions were characterized using transmission electron
microscopy (TEM) and FT-IR spectroscopy. Special care was
taken to minimize the effects of washing on the reaction
product sprior to the analyses.The results are expected to
contribute to our understanding on how the activity of bacterial
cellulose syntheses is changed under different conditions and
on their working mechanism in general. This kind of
information could eventually enable the in vitro synthesis of
desired cellulosic structures, in particular the native-like
cellulose I microfibril.
CELL 137
Method for studies of oxidoreductase catalyzed oxidation
of synthetic lignin in presence of co-oxidants
Paula Nousiainen2, [email protected], Jussi
Kontro2, Helmiina Manner2, Annele Hatakka1, Jussi Sipila1. (1)
University of Helsinki, Helsinki, Finland (2) Organic chemistry,
University of Helsinki, Helsinki, Finland
Fungal oxidative enzymes, such as peroxidases and laccases,
are the key catalysts in lignin biodegradation in vivo, and
consequently provide an important source for industrial
ligninolytic biocatalysts. Recently, it has been shown that some
syringyl-type phenolics have potential as industrial co-oxidants
or mediators, both in laccase and peroxidase catalyzed
modifications of lignocellulosic material. A great deal of
research in this area is performed on different types of model
systems requiring application of solvent combinations that
produce difficulties for example in terms of precipitation of
substrates and reaction products.We have now developed a
new type of reaction system based on the oxidation of
dehydrogenation polymer, DHP, in cellulose slurry more
closely resembling natural lignocellulose, and this cellulose
bound DHP material was treated as substrate in
oxidoreductase-mediator –system with isolation by simple
solvent extraction to give oxidized low and high molecular
weight fractions for further analysis. In these experiments, the
DHP was oxidized in the presence of oxidoreductases from
white-rot fungi: laccase from Trametes villosa (NS 51002) and
two peroxidases, manganese peroxidase from Phlebia sp. Nf
b19 and versatile peroxidase (VP) from Bjerkandera adusta
under mediative oxidation conditions. After isolation, the high
molecular fractions of SG-DHP were analyzed by standard
solution state NMR procedures (1H, 13C, HSQC, HMBC), 31P
NMR, and SEC The structural analysis of the oxidized
polymers show clear modifications in the polymer outcome,
e.g. markedly reduce the average molecular weight of the
samples with apparent structural deformations in the sidechain area.
CELL 138
Regenerated cellulosic fiber from ionic liquid-waste cotton
solution by dry-jet wet spinning
Shirin Asaadi2, [email protected], Michael Hummel2,
Herbert Sixta1. (1) Forest Products Technology, Aalto
University, Espoo, Finland (2) Forest product Technology,
Aalto university, Espoo-02650, Finland
Man-made fibers constitute 60 percent of the world fiber
consumption. Consequently, the textile industry has a
significant interest in a constant further development of these
fibers. In this field, an environmentally friendly production is
one of the dominant challenges- and opportunity at the same
time. The textile industry is looking for more sustainable
technologies in fiber and fabric manufacture. One of the most
important issues that need to be investigated is the resource
efficiency that deals with waste, water and energy
management. Reducing the use of toxic chemicals in fiber
manufacturing processes is also of significant importance.
A so called closed loop of fibers is one of the interesting
challenges in this field. This closed loop is formed once a
worn-out garment is recycled through conversion to its original
fiber form to create new products. According to the Council for
Textile Recycling, the U.S. EPA estimates that textile waste
occupies nearly 5% of all landfill space. While the EPA
estimates that approximately 3.8 billion pounds of postconsumer textile waste (PCTW) is recycled each year, this only
accounts for about 15% of all PCTW, leaving 85% as landfills.
These statistics show the necessity for a thorough recycling of
textiles. Along with increasing environmental awareness, the
need to develop “green” fiber production technologies is getting
increasingly important.Recently, studies on the application of
ionic liquids (ILs) in the field of cellulose chemistry have
attracted much attention, including the production of
regenerated cellulose fibers which has gained considerable
commercial interest. We have studied a dry-jet wet spinning
process utilizing a super-base derived IL by considering cotton
based waste textiles for the production of fibers. The spinning
parameters have been optimized by extensive rheological
studies. Mechanical properties, i.e. tenacity, moduli of
elasticity, elongation and filament orientation are determined.
Thus, an understanding of this novel process is developed and
the advantages are demonstrated for producing high-value
products such as textiles and also biocomposites.
CELL 139
Evaluation of nanocelluloses as flooding additives for the
petroleum industry
Silje Nedland N. Molnes2,1, [email protected], Kristin
Syverud1,3, Skule Strand2, Kristofer G. Paso3. (1) Paper Fibre
Research Inst, Trondheim, Norway (2) Department of
Petroleum Engineering, University of Stavanger, Stavanger,
Norway (3) Department of Chemical Engineering, The
Norwegian University of Science and Technology, Trondheim,
Norway
Various qualities of nanocellulose will be investigated for
potential use in enhanced oil recovery for the petroleum
industry. Solutions containing low concentration of either
crystalline nanocellulose (CNC) or cellulose nanofibrils (CNF)
will be characterized rheologically. Both TEMPO-oxidized and
carboxymethylated CNFs will be investigated. After the suitable
nanocellulose particles have been identified, they will be
subject to further relevant testing. The ultimate goal will be to
use nanocellulose solutions as flooding agents in tertiary oil
recovery, to improve the microscopic sweep efficiency. The
work is done as a part of the NORCEL project led by the Paper
and Fibre Research Institute (PFI) in Trondheim, Norway. This
work is done in collaboration with the University of Stavanger
and the Ugelstad Laboratory at NTNU, Norway. It has received
funding from the Research Council of Norway, on the NANO
2021 program.
CELL 140
Modification and optimization of cellulose nanocrystallatex interactions
[email protected],
Zahra
Stephanie
Kedzior1,
Dastjerdi2,3, Marc A. Dubé2,3, Emily D. Cranston1. (1) Chemical
Engineering, McMaster University, Hamilton, Ontario, Canada
(2) Chemical and Biological Engineering, University of Ottawa,
Ottawa, Ontario, Canada (3) Center for Catalysis Research
and Innovation, University of Ottawa, Ottawa, Ontario, Canada
In order to optimize the use of cellulose nanocrystals (CNCs) in
polymer systems it is important to understand the interactions
between CNCs and polymerization components. In this work,
CNCs have been added to polymer latex solutions and the
interactions between CNCs, latex particles, surfactants and
salts are studied. Confocal and optical microscopy show the
morphology and distribution of CNCs within the system.
Anionic, cationic, and polymer grafted CNCs were compared.
We have shown that blending CNCs with polymer latex
particles results in films with increased tack, shear, and peel
strength. These results can be generalized to extend the
potential of CNCs as nanofillers, strengthening agents,
emulsifiers and rheological modifiers.
CELL 141
Structural stability of the molecular chain sheets
composing the crystal structures of cellulose allomorphs:
A theoretical study
Takuya Uto1,3, [email protected], Toshifumi Yui2. (1)
Faculty of Engineering, University of Miyazaki, Miyazaki, Japan
(2) Faculty of Engineering, University of Miyazaki, Miyazaki,
Japan (3) Research Fellow of Japan Society for the Promotion
of Science, Miyazaki, Japan
(FFPRI), Tsukuba Ibaraki, Japan (2) Kyushu University,
Faculty of Agriculture, Fukuoka, Japan
The crystal structures of cellulose allomorphs can be
characterized by stacking of the molecular chain sheets
composed by hydrogen-bonded molecular chains. The present
paper reports the systematic assessment of the structural
stability of the isolated molecular chains sheets (4×8mer
chains) extracted from the cellulose crystal allomorphs. (Fig.1)
The structures of the molecular chain sheets were optimized
by DFT calculations. As a comparable study, the crystal
models with the finite dimensions (36 to 48×40mer chains)
were examined by molecular dynamics (MD) calculations in
solution state. The linear chain sheets of cellulose Iα and Iβ
crystals exhibited the right-handed twist forms with similar
extent, whereas the cellulose Iα crystal model displayed more
distinct twist than the Iβ one, suggesting weaker inter-sheet
interactions involved in the former crystal structure. While the
DFT optimization completely deformed the structure of the
(100) chain sheet of cellulose IIII crystal, the (1-10) chain sheet
essentially retained the initial structure and so did the cellulose
IIII crystal model during the MD calculations. The results
suggested that the crystal structure was more appropriately
described by the layered (1-10) chain sheets. The isolated
(010) and (020) chain sheets of cellulose II crystal, both
aligned in parallel in the crystal structure, twisted with the
opposite chirality to each other. The isolated (110) chain sheet,
on the other hand, was slightly deviated by the DFT
optimization. The crystal structure of cellulose II was also
characterised by the layered (010) and (020) chain sheets. The
present DFT calculations may have revealed the interior stress
along the (010) and (020) lattice planes so as to deviate to the
opposite mode, which probably resulted in a moderate
deformation of the crystal model in the MD calculations.1
We have been investigating molecular assembly states of β1,4-glucan chains in noncrystalline regions of pure cellulose
materials using Fourier transform infrared (FTIR) spectroscopy.
The difficulty in analyzing hydroxyl (OH) bands of
noncrystalline regions of pure cellulose arises from the
overlapped bands due to various vibrational modes of OH
groups. In this paper, a regioselectively methylated cellulose
derivative, 2,3-di-O-methylcellulose (23MC) having controlled
formation of hydrogen bonding, was focused by the analytical
method using a combination of FTIR spectroscopy, vaporphase deuteration and a kinetic analysis of the reaction rates.
The combined method could provide information on molecular
assembly states in noncrystalline regions. Then, the
generalized two-dimensional correlation analysis was
performed to yield information on hydrogen bonding
engagements.
As the result, the films were found to be built up with no less
than four types of domains. The detected hydrogen bonds at
3446 cm-1 in domains in the noncrystalline regions were likely
to be derived from the intramolecular hydrogen bonds between
the OH groups at C-6 of the anhydroglucose ring and the OH
groups at C-2 of the adjacent ring. Thus, our FTIR method was
successful to provide detailed information on the noncrystalline
regions of 23MC films.
(1) Uto, T.; Mawatari, S.; Yui, T. J. Phys. Chem. B 2014, 118,
9313-9312
Thomas J. Elder1, [email protected], Ariana Beste2. (1) USDA
Forest Service, Pineville, Louisiana, United States (2) Joint
Institute for Computational Sciences, The University of
Tennessee, Oak Ridge, Tennessee, United States
CELL 143
Density functional theory calculations on concerted lignin
pyrolysis mechanisms
The pyrolysis of lignin is an essential component of the
biorefinery concept and as such has been the subject of
considerable experimental and computational attention. The
proposed initial reactions are generally thought to involve
homolytic cleavage, but the products may also be accounted
for by concerted mechanisms. The latter have been evaluated
using density functional theory, resulting in activation energies
that are somewhat lower than homolytic bond dissociation
energies. The kinetics of competing concerted reactions will
also be discussed.
CELL 144
Figure 1. The chain sheet model extracted from the cellulose crystal
CELL 142
Characterization
of
noncrystalline
regions
in
regioselectively methylated cellulosic films using vaporphase deuteration and generalized 2D correlation infrared
spectroscopy
Yukako Hishikawa1, Tetsuo Kondo2, [email protected]. (1) Forestry and Forest Products Research Institute
Effect of urea as an additive in the alkali pretreatment of
cellulose I to cellulose II
Vanshi Uniyal2, [email protected], P. K. Gupta2,
Sanjay Naithani1. (1) Chemistry of Forest Products Division,
Institute of Wood Science and Technology, Malleswaram,
Bengaluru, India (2) Centre for Advanced Studies in Chemistry
of Forest Products, Forest Research Institute, Dehra Dun,
India
The effect on crystalline structural transformation from
cellulose I to cellulose II polymorph in cotton linter was studied
by treating it with variable concentration (0%, 5%, 10%, 15%)
of sodium hydroxide with and without urea as an additive and
analyzed by wide-angle X-ray diffraction analysis. Cotton linter
treated with increasing sodium hydroxide concentration at 15
wt% showed sudden transformation from cellulose I to
cellulose II polymorph. When urea (5 wt%) was used as an
additive along with 15 wt% sodium hydroxide concentration the
magnitude of the transformation reduced largely. The
crystallinity index showed a gradual decrease with increasing
concentration of sodium hydroxide. The crystallinity index
showed a gradual decrease with increasing concentration of
sodium hydroxide with or without addition of urea, nevertheless
with addition of urea a further slight more transformation was
also observed.
CELL 145
Iridescent 3D structures produced by evaporation of
droplets of cellulose nanocrystal suspensions
Xiaoyue Mu, [email protected], Derek G. Gray.
Chemistry, McGill University, Montreal, Quebec, Canada
The evaporation of aqueous suspensions of cellulose
nanocrystals (CNC) gives iridescent chiral nematic films with
reflection colors at visible wavelengths1,2. Possible applications
as structural pigments, photonic materials and as templates for
other porous and inorganic chiral nematic materials have been
proposed. A key problem is controlling the chiral nematic pitch,
P, and hence the reflection colors of CNC films. By adding D(+)-glucose to the suspension, we showed experimentally that
the change in P during evaporation must occur in two distinct
stages3. A second effect was observed during evaporation of
droplets on a flat surface. Mass transfer of the rod-like
cellulose nanocrystals within the evaporating droplet leads to a
radial distribution of CNC, giving a raised outer ring at the edge
of the final dry film. This is analogous to the “coffee-stain”
effect) described by Deegan et al.4 , but in the case of the rodlike cellulose nanocrystals, the suspension is already in the
ordered state, and the increase in CNC concentration at the
edge of the evaporating droplet leads to the formation of
iridescent colors as P approaches visible wavelengths. The
concentration gradient also favors gel formation at the edge of
the droplet. The buildup of chiral nematic gel at the edge of the
film was demonstrated by surface profilometry on the dry film,
and the distribution of iridescent reflection colors, from red at
the outside of the film to blue in the centre, also results from
the preferential gelation at the edge of the droplet.
1. Revol, J.-F.; Godbout L.; Gray, D. G. Solid Films of
Cellulose with Chiral Nematic Order and Optically Variable
Properties. J. Pulp Paper Sci. 1998, 24, 146-149.
2. Beck, S.; Bouchard, J.; Chauve, G.; Berry, R. Controlled
production of patterns in iridescent solid films of cellulose
nanocrystals. Cellulose 2013, 20(3), 1401-1411.
3. Mu, X.; Gray, D. G. Formation of chiral nematic films from
cellulose nanocrystal suspensions is a two-stage process.
Langmuir 2014, 30, 9256-9260.
4. Deegan, R. D.; Bakajin, O.; Dupont, T. F.; Huber, G.; Nagel,
S. R.; Witten, T. A. Capillary flow as the cause of ring stains
from dried liquid drops. Nature 1997, 389, 827–829.
CELL 146
3D nanofiber scaffolds of bacterial cellulose and chitosan
generated from solution blowing spinning using an
airbrush
Xueqiong Yin1,2, [email protected], Lucian A. Lucia2,4,
[email protected], Avinav Nandgaonkar3. (1) College of
Materials and chemical engineering, Hainan University,
Haikou, China (2) Departments of Forest Biomaterials and
Chemistry, North Carolina State University, Raleigh, North
Carolina, United States (3) Fiber and Polymer Science, North
Carolina State University, Raleigh, North Carolina, United
States (4) Key Laboratory of Pulp & Paper Science and
Technology of the Ministry of Education, Qilu University of
Technology, Jinan, Shandong, China
Solution blowing spinning is a method combining the elements
of electrospinning and melt blowing technologies to generate
non-woven webs of micro- and nanofibers with fiber diameters
similar to those produced by electrospinning. To prepare 3D
nanofiber scaffolds with potential application in biomedical
topics (e.g., wound healing), a variety of chitosan solutions
were sprayed onto bacterial cellulose (BC) through solution
blowing spinning with a commercial airbrush. The preparation
condition optimization and structural characterization of the
scaffolds were carried out. In vitro wound healing was
measured through cell cultures with human dermal fibroblasts
and epidermal keratinocytes. BC is an excellent platform to
support the development of chitosan nonwoven fibers and
supply good mechanical strength to enable higher value
operations. The scaffolds have promising applications as
tissue wound healing bandages and artificial skin.
CELL 147
Hydrophobic functionalization of jute fabric via enzymatic
grafting of octadecylamine
Xuerong Fan2, [email protected], Aixue Dong2, Qiang Wang2,
Ping Wang1, Jiugang Yuan2. (1) Jiangnan University, Wuxi,
China (2) Jiangnan University, Wuxi, China
Enzymatic grafting of foreign molecules onto lignins provides a
mild and eco-friendly alternative for the functionalization of
lignocellulosic materials. In this study, the laccase-mediated
grafting of octadecylamine (OA) onto lignin-rich jute fabrics for
enhancing hydrophobicity was investigated in terms of FT-IR,
XPS and SEM. The nitrogen content of the jute fabric was
subsequently determined by the micro Kjeldahl method, from
which the grafting percentage (Gp) and the grafting efficiency
(GE) of the enzymatic reaction were calculated. Then the
surface hydrophobicity of the jute fabrics was estimated by
means of contact angle and wetting time measurements.
Finally, the effects of OA concentration and incubation time in
the enzymatic grafting process on the Gp and GE of the
reaction coupled with the contact angle and wetting time of the
jute fabrics were studied. The results revealed that the OA
monomers were successfully grafted to the lignin moieties of
the jute fiber surface by laccase with Gp and GE of 0.712%
and 10.571% respectively. Meanwhile, the modified jute fabrics
via OA-grafting showed increased wetting time of 18.5 min and
contact angle of 116.72o, indicating that the surface
hydrophobicity of the jute fabric was increased after the
enzymatic graft modification with hydrophobic OA. The Gp and
the jute hydrophobicity were enhanced with the OA
concentration and incubation time in the enzymatic grafting
reaction. The OA concentration enhancement led to a
decrease in the GE while the incubation time did the opposite.
CELL 148
Textile fibers from recycled waste materials
Yibo Ma1, [email protected], Shirin Asaadi2, Marjo Maattanen3,
Airi Sarkilahti3, Michael Hummel1, Ali Harlin3, Herbert Sixta1.
(1) Forest Products Technology, Aalto University, Espoo,
Finland (2) Forest product Technology, Aalto university,
Espoo-02650, Finland (3) VTT Technical Research Centre of
Finland, Espoo, Finland
Driven by the global demographic development, the demand
for cellulosic textile fibres has increased significantly during
recent years. This has also affected the demand and,
consequently, price for dissolving pulps as raw-material for
special fibers. Thus, cheaper and more sustainable sources as
alternative raw material for textile fibers are sought. The
increasing environmental and economic concerns have
promoted the recycling of waste cellulosic material to reduce
landfill and harvest of trees for the production of cellulose. The
efficient recycling of these materials significantly reduces the
environmental impact and can potentially upgrade them to
valuable products (e.g. textile fibres). In this study we evaluate
the spinnability of recycled fibre materials, such as fine paper
and card board, with a dry jet-wet spinning process which
utilizes an ionic liquid as solvent, referred to as IONCELL-F
process. Compared to the viscose and Lyocell fibre processes,
the IONCELL-F process is considered to have a reduced
environmental impact. The recycled raw materials contain
varying amounts of lignin, hemicelluloses, extractives, and
inorganic impurities – unwanted components in dissolving
pulps used for the production of traditional viscose fibres. Ionic
liquids do not require such a high purity of the raw material
which allows for a significant simplification of the purification
process for the recycled fibres.Recycled cellulosic materials of
different purity were directly dissolved in a selected ionic liquid.
A highly viscous cellulose-IL solution was prepared using a
vertical kneader. Long fibres were successfully spun using a
dry-jet wet fibre spinning process. The spun fibres showed
higher strength properties than viscose fibres and a
comparable strength to Lyocell fibres. Fibres spun from
recycled material proved suitable for textile applications due to
their excellent tensile properties. In addition, the high Young’s
modulus suggests that the fibers can be even utilized in biocomposites (e.g. automotive applications). Using recycled
materials as cellulose sources ensures the ecological
sustainability of the fibres and also reduces the raw material
costs, which typically constitute a main share of the production
costs. Finally, this study demonstrates the possibility of using
recycled materials for fibre spinning and the potential of the
IONCELL-F process as an alternative to Viscose and Lyocell
fibre spinning processes.
CELL 149
Hemicellulose-based
hydrogel
containing
nanoparticles for antibacterial application
Ag
Ying Guan1, [email protected], Feng Peng1, Runcang
Sun2. (1) Beijing Forestry University, Beijing, China (2) South
China Univ of Tech, Guangzhou Guangdon, China
A novel approach was developed to introduce antimicrobial
property into hydrogel network without any reductants. Ag
nanoparticles coated hemicelluloses-based hydrogel was
prepared by reduction of Ag ions in cross-linked dialdehyde
hemicelluloses (DHC)/chitosan hydrogels. The structure and
morphology of hydrogels were characterized by FT-IR, 1H and
13C NMR, SEM, and TEM. The results of FT-IR and NMR
indicated that the hydrogel formed through the Schiff-Base
reaction between the amino groups of chitosan chains and the
aldehyde groups of DHC. The swelling property of hydrogel
was decreased sharply after the addition of silver ions, and the
equilibrium swelling ratio was decreased from 1129 g/g to 54.8
g/g. The DHC/chitosan/Ag hydrogel possessed an
antimicrobial activity against the model microbes Escherichia
coli (Gram-negative) and Staphylococcus aureus (Grampositive), which was a promising antimicrobial material for the
applications in the biomedical field.
CELL 150
Antibacterial cellulose acetate films containing N-halamine
modified nanocrystalline cellulose
Ying Liu1, [email protected], Xuehong Ren1, Gisela
Buschle-Diller2. (1) College of Textile and Clothing, Jiangnan
University, Wuxi Jiangsu, China (2) Auburn Univ, Auburn,
Alabama, United States
Cellulose acetate (CA) is a well-known polymer derived from
cellulose with many advantages, such as good mechanical
properties, good hydrolytic stability, low toxicity, environmentalfriendly properties and relatively low cost. In this paper, nanocrystalline cellulose was modified by grafting with
methacrylamide and then mixing with CA to make films. The
CA films with modified nano-crystalline cellulose showed good
antibacterial properties after chlorination. In addition, solidstate NMR spectroscopy and transmission electron microscopy
(TEM) of modified nano-crystalline cellulose were investigated.
FTIR spectroscopy, scanning electron microscopy (SEM), Xray crystallography and thermogravimetric analysis (TGA) were
used to study the CA films containing modified nano-crystalline
cellulose and their cytocompatibility was assessed.
CELL 151
Direct chemical modificationand separation of biomass
components using ionic liquids based organocatalysts
Yoshiki Shibata, [email protected], Ryohei
Kakuchi, Kenji Takahashi. Institute of Science and
Engineering, Kanazawa University, Kanazawa, Japan
As boosted by a growing demand on alternative resources,
chemists have been intensively working on utilization of raw
biomass to produce chemicals. In 2002, Rogers and coworkers reported that ionic liquids (ILs) had a unique potential
to dissolve cellulose under mild conditions. Triggered by this
report, ILs have been discovered to dissolve other bio based
materials under mild conditions. Because lignocellulosic
biomasses have been known to be scarcely soluble in any
solvents, these basic studies re-triggered a chemical treatment
of biomass, which had been suppressed for long years.
Lignocellulosic biomasses are based on three main
components, namely the cellulose, the hemicellulose, and the
lignin with highly sophisticated architectures. Usually, utilization
of biomass has been depending on the depolymerization
processes of biomass components. Hence, reported studies of
biomass
applications
were
economically
and
thermodynamically disadvantageous. In this context, an ideal
application of biomass is expected to be a direct separation of
the lignin and the polysaccharides keeping their polymeric
characters because such polymeric materials can be employed
for many industrial applications. However, it has been
extremely difficult to directly separate components in biomass
structure because the lignocellulose structure is highly
complicating. Herein, a new biomass application, essentially
realizing a direct modification and fractionation of the
polysaccharide and lignin of the lignocelluloses, will be
proposed. We considered the hydroxyl groups of each biomass
components as the ubiquitous reaction point. In addition,
organic transformation reactions in ILs were very recently
revealed to undergo with ILs as both a solvent and organocatalyst. In this presentation, two main points will be described.
These include 1) a direct chemical reaction of raw biomass in
ILs with ILs as an organo-catalyst to afford polysaccharide and
lignin derivatives without the aid of metals and strong acids
and 2) subsequent separation of polysaccharide and lignin
derivatives with taking advantage of differences in their
solubility.
CELL 152
Preparation of butyl levulinate through the acid catalysed
solvolysis of cellulose using a single reaction process
Yukako
Hishikawa1,
[email protected],
Mami
Yamaguchi2, Satoshi Kubo1, Tatsuhiko Yamada1. (1) Forestry
and Forest Products Research Institute (FFPRI), Tsukuba
Ibaraki, Japan (2) Paper Technology Center, Ehime Institute of
Industrial Technology, Shikokuchuou, Ehime, Japan
Renewable energies such as solar power, wind power and
biomass are anticipated to be stable and harmless domestic
energy sources. Biodiesel is derived from biomass,
predominantly from oilseed plants, and is mainly comprised of
fatty acid esters. Some of esters could be used as bio-based
liquid fuels because the esters have physical properties that
resemble those of diesel fuel. Therefore, biodiesel is expected
to be major alternative transportation fuels. Cellulose is one of
sustainable products from biomass and has the potential to
produce liquid ester compounds of levulinates (levulinic acid
esters) since it can be transformed into levulinic acid. Thus,
cellulose is likely converted into biodiesel. Authors focus on the
direct production of levulinic acid mono alcohol esters using
cellulose
as
the
starting
material.
Authors had reported the preparation of butyl levulinate
through the acid catalysed solvolysis of cellulose powder using
sulfuric acid as a catalyst and 1-butanol in one step reaction
system under atmospheric pressure. In this paper, we
attempted to prepare butyl levulinate from the acid solvolysis of
cellulose
powder
employing
p-toluenesulfonic
acid
monohydrate as a catalyst. It is one of aromatic sulfonic acids
and is soluble in most organic solvents. The presence of ptoluenesulfonic acid monohydrate as a catalyst provides
organic synthesis. The result revealed that butyl levulinate was
produced up to 70% of the theoretical yield while the yield of
butyl levulinate using sulfuric acid was 60%, which indicated
that p-toluenesulfonic acid monohydrate is more suitable as a
catalyst in our solvolysis process. Moreover, these high yields
suggested that our simple solvolysis process using alcoholic
reaction media has high potential for conversion of cellulosic
biomass into butyl levulinate.
CELL 153
Effect of molecular weight and chain length on surface
and interfacial tension, emulsification and cleaning
properties of polysaccharide-based surfactants derived
from pectin
Zarif
Farhana
Mohd
Aris1,
[email protected], Vishal Bavishi1, Nina
Tchirkova2, Ramaswamy Nagarajan1. (1) Plastics Engineering,
University of Massachusetts Lowell, Lowell, Massachusetts,
United States (2) Winchester High School, Winchester,
Massachusetts, United States
Naturally occurring polysaccharides derived from plants are
often non-toxic, abundantly available and biodegradable. Such
properties make them suitable as renewable feedstock for
synthesizing various additives including surfactants. However
one of the limiting factors in the use of polysaccharides as biobased surfactants is the high molecular weight, which renders
it poor solubility. Molecular weight influences mobility of a
surfactant in aqueous phase, thus affecting overall properties
including surface activity and cleaning ability. Therefore it was
necessary to reduce the molecular weight of these
polysaccharides to achieve improved properties. This paper
describes the synthesis of a novel polysaccharide-based
surfactant derived from pectin obtained primarily from citrus
peels and apple pomace. A series of pectin-based surfactants
having low to medium and high molecular weight were
hydrophobically modified using long chain alkyl amines. The
molecular weight of pectin were lowered using both chemical
and
enzymatic
methods.
The effect of molecular weight on surface and interfacial
tension of these pectin-based surfactants were studied using
the Du Noüy Ring method. The results show that there was a
slight reduction in surface tension with lowering molecular
weight of pectin, whereas the interfacial tension dramatically
decreased for low molecular weight pectin based surfactants.
The presence of the hydrophobic groups also improved
cleaning ability due to higher wettability on greasy surfaces.
However, a very high degree of substitution of the hydrophobic
groups further reduced solubility, thus requiring appropriate
hydrophilic-lipophilic balance (HLB). Structural and molecular
weight characterization, emulsification and stain removal
efficiency of these polysaccharide-based surfactants will also
be presented. This research has unlocked opportunities for
developing novel, non-toxic and bio-derived surfactants from
renewable resources.
Comparison to commercial surfactants and molecular weight effect of
polysaccharide based surfactant on (a) surface and (b) interfacial
tension
CELL 154
Update
on
Zip-lignins™:
deconstruction
Lignins
designed
for
John Ralph2, [email protected], Fachuang Lu7, Steven D.
Karlen6, Dharshana Padmakshan5, Matt Regner6,5, Rebecca
Smith5,6, Hoon Kim6, Yimin Zhu8, JORGE RENCORET1, John
Grabber3, Curtis G. Wilkerson9, John C. Sedbrook5,10, Shawn
Mansfield4. (1) IRNAS, CSIC, Seville, Spain (2) U. WisconsinMadison, Madison, Wisconsin, United States (3) USDA-ARS,
Madison, Wisconsin, United States (4) University of British
Columbia, Vancouver, British Columbia, Canada (5) GLBRC,
University of Wisconsin, Madison, Wisconsin, United States (6)
Wisconsin Energy Institute, University of Wisconsin-Madison,
Madison, Wisconsin, United States (7) Wisconsin Energy
Institute, Madison, Wisconsin, United States (8) Chemistry,
Penn State University, Altoona College, Altoona, Pennsylvania,
United States (9) Plant Biology, Michigan State University,
East Lansing, Michigan, United States (10) Illinois State
University, Normal, Illinois, United States
Lignin remains one of the most significant barriers to the
efficient utilization of lignocellulosic substrates, in processes
ranging from ruminant digestibility to industrial pulping, and in
the current focus on biofuels production. Lignification is,
however, a remarkably metabolically plastic process. A few
approaches toward altering the composition and structure of
lignin (and, therefore, its reactivity) hold considerable promise
for reducing the severity and energy demands of industrial
processes. Researchers are now contemplating actually
designing lignins, by introducing novel phenolic monomers into
the plant lignification process, to improve the ease with which
the resulting lignins can be removed from the cell wall. One
such method, via the so-called ‘zip-lignin’ approach, is showing
particular promise. Poplar trees have already been engineered
to incorporate monolignol ferulate conjugates into the
lignification process, resulting in the introduction of readily
cleavable ester linkages into the backbone of the polymer, and
portending significantly improved processing. We shall
describe the advances, including getting the monolignol
ferulate conjugates into grasses, in which we were concerned
that the natural p-coumaroylation of monolignols might
compete. In addition, now that we have sensitive methods for
determining if/when/whether plants are making monolignol
ferulate conjugates and using them for lignification (methods
that have not previously been available!), it appears that
Nature herself may have in fact already been exploring this
avenue. We’ll provide insight into the plants that seem to be
doing this and try to elucidate how they are, or are not, doing it.
[The question of why is likely to require a lot more time,
research, and insight].
CELL 155
Cross-coupling and oxidation of novel lignin monomers
with conventional monolignols
Thomas J. Elder2, [email protected], John Ralph1. (1) U.
Wisconsin-Madison, Madison, Wisconsin, United States (2)
USDA Forest Service, Pineville, Louisiana, United States
The presence and nature of lignin in biomass can negatively
affect processes associated with the biorefinery concept. As
such, the modification of lignin by the incorporation of alternate
monomers that may facilitate the breakdown of the polymer
have been proposed. Using computational chemical methods,
the current paper evaluates the energetics associated with
cross-coupling of cinnamyl alcohols with proposed monomers,
and the subsequent oxidation of the products required for
polymer chain growth. Comparisons of these computational
results with experiment may allow for the a priori prediction of
successful incorporation.
CELL 156
Recent advances in lignin chemistry
Mikhail Balakshin, [email protected]. R&D, Renmatix,
King of Prussia, Pennsylvania, United States
Growing interest in lignin commercialization has resulted in
significant increases in fundamental and applied activity in both
academia and industry. This presentation reviews recent
achievements in lignin chemistry and their practical
implications. It discusses such important issues as
advancements
in
analytical
methodology,
structural
characteristics of new untraditional lignin feedstock, lignin
branching, linkages between lignin and carbohydrates and
others. The effect of these fundamental issues on biorefinery
optimization and lignin commercialization will be discussed.
CELL 157
Multistep lignin degradation method for the isolation of
lignin-carbohydrate-complex (LCC) bonding sites
Daisuke Ando1, [email protected], Fumiaki
Nakatsubo1, Toshiyuki Takano2, Hiroyuki Yano1. (1) Research
Institute for Sustainable Humanosphere (RISH), Kyoto
University, Uji, Kyoto, Japan (2) Graduate School of
Agriculture, Kyoto University, Kyoto, Kyoto, Japan
There still hasn’t been enough to elucidate the chemical
structures of the bonding site in Lignin-Carbohydrate-Complex
(LCC). It is believed that there are some types of LCC linkages
between the components in wood biomass. However, the
isolation and the structure identification of the bonding sites in
LCC have not been successful because it is difficult to obtain
the bonding sites by conventional methods. In several
degradation methods such as acidolysis, thioacidolysis and
DFRC method, the information on the α-substituent patterns in
lignin such as benzyl ether linkage in LCC is lost. Accordingly,
there was no suitable lignin degradation method, such as a
selective degradation for β-O-4 linkages with retention of LCC
linkages at α-position in lignin. Here, we report the
development of the appropriate novel lignin degradation
method and the trial for the isolation of LCC bonding sites with
the method.First, the novel degradation method, referred to as
the γ-TTSA method, has been developed for the cleavage of βO-4 linkages in lignin. It consists of four steps: (1) γ-tosylation,
(2) thioetherification (substitution reaction with 1-dodecanethiol
to γ-thioether), (3) sulfonylation (oxidation from γ-thioether to γsulfone) and (4) mild alkali degradation of γ-sulfone (Figure 1).
The method was tested on lignin model compounds and the
native lignin. It was demonstrated that each reaction
proceeded efficiently, and β-O-4 linkage was cleaved under
mild alkali condition although other linkages, such as β-5 and
β-β linkages, were also present. As a result, molecular weight
of native lignin was decreased. These results indicated that the
γ-TTSA method was useful for lignin degradation. Second, βO-4 substructures in Lignin-Carbohydrate-Complex (LCC)
were selectively degraded by γ-TTSA method to obtain the
degradation products consisting lignin fragments and
polysaccharides. Further, the HSQC NMR spectra revealed
that the degradation products consisted mainly of β-β
substructure units and xylan in spite of the degradation of
lignin. The result suggested that the β-β substructure plays an
important role in the bonding between lignin and xylan.
CELL 158
Determination of molecular mass and molecular mass
distribution of TEMPO-oxidized celluloses (TOCs) and
TOC nanofibrils (TOCNs) using SEC-MALLS
Ryoya Hiraoki, Yuko Ono, Tsuguyuki Saito, Akira Isogai,
[email protected]. Univ Tokyo, Tokyo, Japan
TEMPO-oxidized wood celluloses (TOCs) with carboxylate
contents > 1 mmol/g can be converted to completely
individualized TOC nanofibrils (TOCNs) with uniform widths of
~3 nm by mechanical disintegration of TOCs in water. TOCNs
have potential applications as TOCN-containing composite
materials, TOCN hydrogels, aerogels, films, and others having
unique properties and functions. In these cases, not only
length/length distribution but also molecular mass/molecular
mass distribution of TOCs and TOCNs are supposed to have
strong influence on the mechanical and other functional
properties of the resulting bulk TOCN materials and TOCNcontaining composites. So far, freeze-dried TOCs and TOCNs
have been dissolved in 0.5M copper ethylenediamine, and
viscosity average degrees of polymerization (DPv) have been
used to evaluate their molecular mass values based on some
assumptions. In this paper, a position-selective methylation of
carboxyl groups was carried out to TOCs and TOCNs with
trimethylsilyldiazomethane under mild conditions, and the
carboxyl groups-methylated TOCs and TOCNs are dissolved in
8% LiCl/DMAc followed by subjecting to SEC-MALLS analysis
after diluting to 1% LiCl/DMAc to determine their molecular
masses and molecular mass distributions. The results showed
that molecular masses of TOCs decreased with increasing
NaClO addition level in the TEMPO-mediated oxidation, and
those of TOCNs further decreased with increasing sonication
time in disintegration treatment in water. Moreover, the
viscosity method underestimated the molecular mass values of
TOCs and TOCNs. A part of hemicelluloses originally present
in wood cellulose partly remained in TOCs, depending on the
oxidation conditions. Based on the obtained results, the
distribution patterns of disordered regions susceptible to
TEMPO-oxidation present periodically along the longitudinal
direction of each cellulose microfibril are discussed.
CELL 159
Recent advances in biorefinery process stream analysis
Antje Potthast, [email protected]. Chemistry
renewable resources, BOKU Vienna, Vienna, Austria
/
Increasing efforts in utilizing renewable resources for
production of bulk and specialty chemicals or new materials in
biorefineries have evoked manifold challenges with regard to
separation of the product streams and identification of
individual components. While cellulose, lignin and
hemicelluloses are the principal main components in all
approaches, different starting materials (ranging from wood
over annual plants to agricultural waste), natural variability and
different processing add to a huge changeability and
complexity of biorefinery process streams. Current problems
comprise the realm of both carbohydrates and lignin. As to
carbohydrates, both low-molecular weight components and
polymers are well accessible to analysis, separability provided:
the former by suitable gas or liquid chromatographic methods,
the latter by size exclusion techniques. A problem is posed by
the analysis of the oligomeric fraction “in between”, which is to
“large” for GC or LC methods and too small for classical SEC
approaches. Similarly, lignin analysis has so far mainly focused
on native lignins, whereas technical lignins are only
insufficiently covered by the means available. In the present
paper, novel analytical approaches for the analysis of celloand xylo-oligosaccharides (up to twenty subunits) as well as
technical lignins are described. Focus is given to robust and
fast, yet accurate and comprehensive methods that allow for
coverage of large sample numbers.
CELL 160
Mass spectrometry analysis of structural details in Oacetylglucuronoxylans
Sun-Li Chong1, Päivi Tuomainen1, Minna Juvonen1, Marta
Derba-Maceluch2, Ewa Mellerowicz2, Maija Tenkanen1,
[email protected]. (1) University of Helsinki, Helsinki,
Finland (2) University of Agricultural Sciences, Umeå, Sweden
Mass spectrometry (MS) is a powerful tool for the biosynthetic
studies of plant cell walls. The method requires only minute
amount of sample and is capable of elucidating the structural
differences of heterogenic wall polysaccharide derived
fragments (oligosaccharides). O-acetylglucuronoxylans (AcGX)
are abundantly present in the secondary cell of flowering
plants. The AcGX backbone is formed by beta-D-xylopyranosyl
residues,
some
of
which
carry
alpha-(4-Omethyl)glucopyranosyluronic acid and acetyl residues at the 2O/and 3-O positions. Enzymatic hydrolysis releasing
oligosaccharide directly from the plant material for the MS
analysis was exploited to study O-acetylation of
glucuronoxylan in different hardwood species and of
Arabidopsis thaliana xylan biosynthesis mutants. The released
oligosaccharides were further analyzed by the atmospheric
pressured-matrix assisted laser desorption ionization-ion trap
mass spectrometry (AP-MALDI-ITMS). The AP-MALDI-ITMS
offers the advantage to analyze the mass (fingerprint
spectrum) and structure (MS/MS analysis) of complex
oligosaccharides in one system. The % intensities of the mass
peaks were compared and analyzed further by principal
component analysis (PCA) to identify the Arabidopsis mutants
with altered O-acetylation in glucuronoxylan. The MS/MS
analysis also revealed information on the spatial distribution on
O-acetyl residues. Moreover, a novel pentose branching in
Arabidopsis glucuronoxylan was identified. Endoxylanase
hydrolysis followed by AP-MALDI-ITMS detection was shown
to be a selective and sensitive tool for studying the structural
details of O-acetylglucuronoxylans in a semi-high throughput
manner. The method is well suited to analyze large numbers of
samples.
CELL 161
Cellulose degradation during deformation processing and
analytics
Thomas Roeder1, [email protected], Gerhard Kliba1,
Walter Milacher1, Gregor Kraft1, Antje Potthast2, Thomas
Rosenau3. (1) Lenzing AG, Lenzing, Austria (2) Chemistry /
renewable resources, BOKU Vienna, Vienna, Austria (3) Dept
of Chemistry, University Fo Agr Sciences, Vienna, Austria
With 75 years of experience in fiber production, the Lenzing
Group is the only company worldwide combining under one
roof the manufacturing of all three man-made cellulose fiber
generations on a large industrial scale– from the classic
viscose to modal and lyocell (TENCEL®) fibers. Due to the
infusibility of cellulose, production of cellulose fibres for textile
and non-woven applications needs to dissolve the cellulose to
obtain spinning dopes. Dissolving of cellulose means to break
up the strong hydrogen bonds between the cellulose chains
and to replace them by interactions with a solvent, by
derivatization or by complexation of the cellulose OH-groups.
During this dissolution process, depending on the solvent
used, degradation might occur. As examples LiCl/DMAc, ionic
liquids and viscose solutions are compared in terms of desired
and undesired degradation reactions and their impact on
processability.
CELL 162
Functionalization of nanocelluloses by supramolecular
motifs to combine competing properties
Jason R. McKee1, Eric Appel2, Emma-Rose Janacek2, Heikki
Tenhu3, Eero Kontturi4, Oren A. Scherman2, Olli T. Ikkala1,
[email protected]. (1) Dept of Applied Physics, Aalto
University, Espoo, Finland (2) Univ Cambridge Melville Lab,
Cambridge, United Kingdom (3) Univ of Helsinki Poly Chem
Lab, Helsinki, Finland (4) Department of Forest Products
Technology, Aalto University, Espoo, Finland
Long and entangled native nanofibrillated cellulose (NFC) and
rod-like nanocrystalline cellulose (CNC) have extensively been
exploited in nanocomposites to reinforce for higher stiffness
and strength. In some applications, however, competing
capability for controlled structural reorganizations may be
needed, for example in designing toughness, self-healing, and
switchable structures and properties. Nanocellulose films
(nanopapers) are based on dense nanocellulose networks, and
upon deformations, the cracks typically tend to propagate
catastrophically. Here we show that CNCs with polyacrylate
side chain brushes, containing ureidopyrimidone hydrogen
bonding supramolecular groups suppress uncontrolled crack
growth in mechanical deformations (J. McKee et al, Angew.
Chem, 53, 5049, 2014). The architecture allows mutual
dissipative movement of the CNCs as well as ureidopyrimidone
bond exchanges which dissipate fracture energy where the
strong ureidopyrimidone-mediated supramolecular interactions
still allow promoted cohesion of the material. Our other
examples of incorporating supramolecular interactions with
nanocelluloses deal hydrogels. In this case CNC is decorated
with polyacrylate brushes containing naphthyl moieties. The
hydrogel contains also polyvinyl alcohol polymers with methyl
viologen
side
chains
and
dispersed
cucurbit[8]uril
supramolecular host molecules that can bind simultaneous the
naphthyls and viologens (J. McKee et al, Adv. Funct. Mater.
24, 2706, 2014). The combination of the competing
nanocellulose reinforcement and the rapid dynamics of the
host/guest binding leads to rapid sol-gel transitions and selfhealing even after long storage times. Another concept is
based on similar host-guest chemistry of cucurbit[8]uril, where
interpenetrating molecular and colloidal level hydrogels show
synergistic improvement of the modulus. In addition, the
cucurbit[8]uril-mediated molecular level hydrogel allows
improved strain levels vs. the pure colloidal NFC hydrogel, this
promoting the interconnectivity of the colloidal gel (E. Janacek
et al, submitted). Finally, rheological strain hardening is
demonstrated in CNC-reinforced methyl cellulose gels, where
the adsorption of methyl cellulose on CNC is expected to be
crucial to mediate physical interactions (J. McKee et al, ACS
Macro Letters, 3, 266, 2014). The examples demonstrate
possibilities to combine colloidal and molecular level motifs and
interactions in balanced ways to combine competing
properties.
CELL 163
Controlling the elastic modulus of cellulose nanofibril
hydrogels – scaffolds with potential in tissue engineering
Kristin Syverud1,2, [email protected], Sigurd R.
Pettersen3, Kurt I. Draget4, Gary Chinga-Carrasco1. (1) Paper
Fibre Research Inst, Trondheim, Norway (2) Department of
Chemical Engineering, Norwegian University of Science and
Technology, NTNU, Trondheim, Norway (4) Department of
Biotechnology, Norwegian University of Science and
Technology, NTNU, Trondheim, Norway
Cellulose nanofibrils (CNF) form hydrogels at low
concentrations. These hydrogels are held together by transient
interactions such as entanglement of fibrils, non-specific ionic
interactions and hydrogen bonds; and are thus vulnerable for
changes in the chemical environment or the influence of
mechanical forces. By a covalent crosslinking of the fibrils,
stable permanent gels can be formed. In this study we have
produced CNF by using TEMPO mediated oxidation followed
by fibrillation. During this procedure, carboxyl and aldehyde
groups are introduced on the CNF surfaces. The aldehyde
groups are suitable sites for crosslinking, as aldehydes readily
form covalent bonds to primary amines through formation of
Schiff bases. For this purpose the diamines ethylenediamine
(EDA) and hexamethylenediamine (HMDA), differing with four
carbon atoms in the chain, were used as crosslinker
molecules. The results show that by varying the concentration
and length of the crosslinker molecules, the elastic modulus of
the gels could be controlled. The reversible gels were in this
way transformed to irreversible gels by a simple water based
reaction. Controlling gel strength is one important premise for
the use of CNF in applications such as tissue engineering.
CELL 164
Aerogels and foams from cellulose nanocrystals as
superabsorbents, shape recovery materials, and templates
Xuan
Yang,
Zhen
Hu,
Emily
D.
Cranston,
[email protected]. Chemical Engineering, McMaster
University, Hamilton, Ontario, Canada
Cellulose nanocrystals (CNCs) are promising renewable
nanoparticles with unique properties including high mechanical
strength and a large aspect ratio. As such, CNCs form strong
gels and networked structures. We demonstrate two solid
“entangled” CNC systems: (1) a chemically crosslinked aerogel
of CNCs and (2) a physically crosslinked foam prepared by
drying CNC-polymer aqueous foams. The chemically
crosslinked CNC aerogels possess some of the lowest
reported densities to-date, are strong and can absorb 70-160
times their weight in both water and non-polar solvents, without
disintegrating. Furthermore, they can recover their shape by
85% after being compressed over 80%. The physically
crosslinked CNC aerogels are also strong and elastic with
controllable pore structure. Both systems can be postfunctionalized to vary the surface chemistry and enhance
functionality or used as templates for metallic structures and
polymer composites.
CELL 165
Biocompatible cellulose-based cell scaffolds: Generation
of interconnected micron-size pores embedded in
frameworks of nanoporous PMMA-reinforced cellulose
struts
[email protected],
David
Nicole
Pircher1,
Fischhuber1, Leticia Mercedes Carbajal Galan2,3, Christine
Strauβ4, Jean-marie Nedelec2,3, Cornelia Kasper4, Thomas
Rosenau1, Falk Wolfgang Liebner1. (1) Department of
Chemistry, University of Natural Resources and Life Sciences,
Tulln, Austria (2) Institute of Chemistry of Clermont-Ferrand,
Clermont Université, Ecole Nationale Supérieure de Chimie de
Clermont-Ferrand, Clermont-Ferrand, France (3) Institute of
Chemistry of Clermont-Ferrand, Centre national de la
recherche scientifique, Clermont-Ferrand, France (4)
Department for Biotechnology, University of Natural Resources
and Life Sciences Vienna, Vienna, Austria
Cell scaffolding materials for tissue engineering have to fulfill a
series of requirements with regard to biocompatibility,
mechanical properties, surface topology and pore features.
Even though lightweight cellulose aerogels are promising
materials in this respect, insufficient mechanical stability and
lack of upscale micron-size porosity (> 100 µm) – a key
prerequisite to cell migration, proliferation and differentiation –
were the main impediments so far.In the current work,
temporary templates of fused paraffin or PMMA spheres
(variation of size fraction) were used to generate
interconnected micron-size pores (≤ 500 µm) within
frameworks of nanoporous cellulose II struts. After subsequent
reinforcement with PMMA, the obtained materials of multiscale porosity were supposed to fulfil the above requirements.
The specimens were comprehensively characterized with
regard to both material properties (density, morphology,
specific surface area, porosity, mechanical stability under
uniaxial
compression)
and
biocompatibility
(viability,
attachment and morphology of fibroblast cells).
CELL 166
Photoactive materials for wound care purposes based on
bacterial cellulose
Hubert Hettegger1, [email protected], Salvatore
Sortino2, Antje Potthast1, Thomas Rosenau1. (1) Department of
Chemistry, University of Natural Resources and Life Sciences
Vienna (BOKU), Vienna, Austria (2) Department of Drug
Sciences, University of Catania, Catania, Italy
Photocatalytically active materials find wide use in biosciences
and medicine. Besides chemical synthesis, applications based
on light-activation include e.g. antimicrobial surfaces,
photodynamic therapy of cancer, sterilization of blood or
wastewater treatment. The objective of the current work is the
development of photoactive materials based on microbial
cellulose as the matrix material for the inactivation of bacteria
and the destruction of odorous compounds emitted from
chronic wounds. This is triggered by the release of singlet
oxygen (1O2) as the actual active agent. 1O2 is a highly reactive
form of atmospheric oxygen, produced by the action of a
respective photosensitizer. Different sensitizers based on
xanthene derivatives were synthesized and characterized
spectroscopically with regard to their singlet oxygen production
properties, including both excited triplet state and singlet
oxygen quantum yields and respective lifetimes, by means of
nanosecond laser flash photolysis. The most promising
compounds were linked to appropriately pre-modified bacterial
cellulose by a Cu(I)-catalyzed Huisgen-Meldal-Sharpless 1,3dipolar cycloaddition, a so-called click chemistry approach.
Covalent attachment allows for potential application in wound
coverage materials with the advantage of longer durability and
the minimization of leaching compared to mere adsorption onto
the
backbone
material.
The
pre-modification
and
functionalization of aqueous wet bacterial cellulose was carried
out according to an alkoxysilane chemistry approach under
mild and environmentally friendly reaction conditions. (3Azidopropyl)triethoxysilane as a surface grafting agent was
hydrolyzed in aqueous solution and the respective silane was
covalently bound to the cellulosic matrix by condensation
during rapid thermal treatment. The resulting silanized sheets
were comprehensively analytically characterized by means of
ATR-FTIR, solid state NMR, thermogravimetry, elemental
analysis and scanning electron microscopy in combination with
EDX. The potential oxidative action and applicability in modern
wound treatment approaches is currently studied in further
experiments by means of GC/MS, ELISA and antibacterial
tests, which have been especially developed for this particular
analytical scenario.
CELL 167
Functionalization of cellulose nanofibril surfaces to
enhance crystallization and mechanical properties of polyl-lactide
Shuji Fujisawa2,1, [email protected], Tsuguyuki Saito1,
Akira Isogai1. (1) Department of Biomaterials Science, The
University of Tokyo, Tokyo, Japan (2) Forestry and Forest
Products Research Institute, 1 matsunosato, Tsukuba, Ibaraki,
Japan
Cellulose nanofibrils surfaces were functionalized for the
design of poly(L-lactide) (PLLA)-nucleating surfaces. PLLA is
one of the most widely used biodegradable polymers.
However, a major drawback of PLLA is its low heat resistance.
Although the crystallization of PLLA itself is a simple and
effective way to solve the problem, the crystallization rate of
PLLA is very low. Therefore, in this study, the nucleating ability
of the surface functionalized cellulose nanofibrils were
investigated to widen the application range of PLLA. Cellulose
nanofibrils with a width of ~3 nm were obtained from wood
cellulose via the oxidation using 2,2,6,6-tetramethylpiperidiniyl1-oxyl as a catalyst and successive mechanical treatment. The
surface carboxyl groups of the nanofibrils were selectively
modified with amine-terminated poly(ethylene glycol) chains,
via simple ionic bonds. The isothermal and non-isothermal
crystallization kinetics of the PLLA in the composites were
studied using differential scanning calorimetry and polarized
optical microscopy. The surface functionalized cellulose
nanofibril/PLLA nanocomposite films were successfully
prepared using a solvent casting method with chloroform. With
the aid of the surface modification, the nanofibrils, which have
extraordinary large specific surface areas, were individually
dispersed in the PLLA matrix. As a result, the nanofibrils
efficiently increased the nucleation rate of the PLLA on the
surfaces. After isothermal crystallization for 5 minutes, the
thermal expansion values were more than 10 times lower than
neat PLLA films, because of the increased degree of
crystallization of the PLLA in the nanocomposite. Therefore,
the surface functionalized cellulose nanofibrils showed
nucleating ability for PLLA, and effectively improved the
thermomechanical properties.
CELL 168
Phase behavior of water-in-oil emulsions stabilised solely
by hydrophobised bacterial cellulose nanofibrils
Koon-Yang Lee1, [email protected], Jonny Blaker3,
Ryo Murakami4, Jerry Y. Heng5, Alexander Bismarck2. (1)
Department of Chemical Engineering, University College
London, London, United Kingdom (2) Department of Chemical
Engineering, Imperial College London, London, United
Kingdom (3) School of Materials, The University of
Manchester, Manchester, United Kingdom (4) Chemistry and
Functional Molecules, Konan University, Kobe, Japan (5)
Chemical Engineering, Imperial College London, London,
United Kingdom
Emulsions are a dispersion of two immiscible liquids, which
can be kinetically stabilised by suitable emulsifiers, such as
surfactants or colloidal particle. The first use of cellulose
particles as particulate emulsifiers was described by Oza and
Frank, who used food-grade microcrystalline cellulose to
stabilize heavy mineral oil-in-water emulsions. Since then,
numerous types of cellulose have also been used.
Nevertheless, the hydrophilic nature of pure cellulose always
resulted in the formation of oil-in-water (O/W) emulsions. To
produce water-in-oil (W/O) emulsions, cellulose had to be
hydrophobised and when a monomer is used as the oil phase,
highly porous polymers can be produced. Therefore in this
work, the advanced application and phase behaviour of
bacterial cellulose (BC)-stabilised emulsions is discussed. We
show that stable w/o high internal phase emulsions (HIPEs)
stabilised solely by hydrophobized BC can be produced and
the maximum water volume fraction hydrophobised BC could
stabilise is a function of time. Starting with freeze-dried
hexanoic acid hydrophobised BC (C6-BC) and dodecanoic acid
hydrophobised BC (C12-BC), a maximum water volume fraction
(ϕw) of only 60% could be stabilised initially. However, this
maximum ϕw increased to ~80% 7 days after initial
emulsification, thereby creating HIPEs. The observed timedependent behaviour of these emulsions is consistent with the
disentanglement
and
dispersion
of
freeze-dried
hydrophobisedd BC bundles into individual nanofibres with
time. Furthermore, these emulsions exhibited catastrophic
phase separation when ϕw was increased, as opposed to
catastrophic phase inversion observed for other Pickering
emulsions. In addition to this, the pH-triggered transitional
phase behaviour of C6-BC and C12-BC is also discussed in this
work. We show that C6– and C12–BC stabilised emulsions
exhibited a pH-triggered reversible transitional phase
separation. Lowering the pH of the aqueous phase to 1 did not
affect the emulsion type. Increasing the pH to 14, however,
caused the emulsions to phase separate, which is caused by
electrostatic repulsion between hydrophobised BC as a result
of dissociable acidic surface groups.
CELL 169
Ag particles-filled cellulose hybrids: green synthesis,
characterization and antibacterial activity
YanYan
Dong,
[email protected],
Ke
Yao,
[email protected], Mingguo Ma, [email protected].
Beijing Forestry University, Beijing, China
The purpose of our work is to explore the synthesis,
mechanism, and properties of cellulose-silver hybrids using
microcrystalline cellulose solution as a reducing agent. Herein,
a simple microwave-assisted method was applied as the
preparation of Ag particles filled cellulose hybrids using AgNO3,
AlCl3·6H2O, cellulose solution, and ethylene glycol (EG). EG
acts as a solvent and a microwave absorber. Influences of the
volume ratio of EG to cellulose solution and reaction
temperatures on the cellulose-based hybrids were investigated
in detail. In addition, silver particles filled cellulose hybrids were
first successfully synthesized using microcrystalline cellulose
solution, AgNO3, and AlCl3·6H2O by a hydrothermal method.
There are no additional reducing agents existed in the reaction
systems. The cellulose solution was firstly prepared by the
dissolution of the microcrystalline cellulose (MCC) in
NaOH/urea aqueous solution. X-ray powder diffraction (XRD),
Fourier transform infrared spectrometry (FTIR), scanning
electron microscopy (SEM), thermogravimetric analysis (TGA),
and differential thermal analysis (DTA) were used in
characterizing the as-prepared products. Experimental results
indicated the existence of silver nanoparticles in the cellulose
matrix and silver nanoparticles well dispersed on the surface of
cellulose and penetrated into the cellulose network. The
microcrystalline cellulose solution played an important role in
the synthesis of silver crystals and displayed an amazing
reducing ability as a reducing reagent. The reducing
mechanism from AgCl to silver by microcrystalline cellulose
solution was proposed in detail. Furthermore, antibacterial
experimental results displayed that the as-prepared hybrids
exhibited excellent antimicrobial activity against both E. coli
(Gram-negative) and S. aureus (Gram-positive). This green
strategy for the synthesis of cellulose-silver hybrids may be
useful for the extensive applications of inorganic-polymer
hybrids and the materials may be promising materials in
biomedical field and public health area.
CELL 170
Silver nanoparticles synthesis mediated by cellulose
nanocrystals: Role of surface chemistry in nucleation
phenomena
Khan Mohammad Ahsan Uddin1, [email protected],
Arcot R. Lokanathan1, Janne Laine1, Orlando J. Rojas1,2. (1)
Aalto Univ School of Chemical Technology, Espoo, Finland (2)
Forest Biomaterials, North Carolina State University, Raleigh,
North Carolina, United States
Due to its unique and well defined physical-chemical
properties, cellulose nanocrystals (CNC) have been used to
mediate silver nanoparticles synthesis, which depend on CNC
surface chemistry. Sodium borohydride was used to reduce
precursor Ag ions and the effect of hydroxyl, sulfate half-ester
and carboxyl groups on the nucleation and size distribution of
AgNPs was investigated by using transmission electron
microscopy (TEM) and UV-Vis spectroscopy. Sulfuric acid
hydrolysis followed by NaOH treatment was carried out to
prepare sulfated CNC and hydrochloric acid hydrolyzed
followed by TEMPO oxidation was allowed the production of
carboxylate CNC. The rate of silver nanoparticle formation was
found to be inversely related to sulfate and carboxyl content of
CNC. Overall, the anionic charges were found to be
responsible for AgNP stability and better size distribution while
the hydroxyl groups were responsible for the nucleationcontrolling ability of CNC. The figure below shows
representative TEM images comparing the best size
distribution obtained using pristine CNC, partially desulfonated
CNC and TEMPO Oxidized CNC. These detailed studies shed
light on mechanistic aspects including nucleation control,
nanoparticle size growth and stabilizing properties of CNC.
CELL 171
Nanocomposites from holocellulose and silver with
enhanced antimicrobial activity
Lian-Hua Fu, [email protected], Fu Deng, Ming-Guo
Ma. Beijing Key Laboratory of Lignocellulosic Chemistry,
College of Materials Science and Technology, Beijing Forestry
University, Beijing, China
In this study, the holocellulose/silver nanocomposites with
enhanced antimicrobial activity were synthesized using
holocellulose, AgNO3 and water as reactants through a facile
one-step hydrothermal method. The phase, microstructure,
thermal stability and morphologies of the specimens were
characterized by means of XRD, FTIR, TG/DSC and SEM,
respectively. The pure phase of silver nanoparticles with high
density and a grain size of about 16.0-26.8 nm were
homogeneity dispersed on the holocellulose matrix. The
antibacterial activities of the specimens have been investigated
against the Gram-negative bacteria Escherichia coli (E. coli)
and the Gram-positive bacteria Staphylococcus aureus (S.
aureus) by the disc diffusion method. The inhibition zones of
the composites for E. coli and S. aureus were up to 8.5-13.0
mm and 12.0-16.0 mm, respectively, which revealed high
antibacterial activity and could be a candidate for the field of
antibacterial. Moreover, the influence of experimental
parameters on the composites were investigated in details,
including reaction time, temperature and additives. The
holocellulose not only served as the matrix, but also played the
role of reducing agent that there is no need for other additives,
also, using holocellulose instead of cellulose reduced the steps
of separating process that simplifying and lowering the cost of
the preparation process of the composites. All of the above
results indicating that the holocellulose/silver nanocomposites
are promising biomaterials in the antibacterial field.
CELL 172
Biobased materials from lignocellulosic fibers: A brief
overview
Elisabete
Frollini,
[email protected],
Bruno
M.
Rodrigues, Elaine C. Ramires, Fernando de Oliveira, Ilce A. T.
Razera, Rachel Passos de Oliveira Santos. Institute of
Chemistry of Sao Carlos, Macromolecular Materials and
Lignocellulosic Fibers Group, Center for Research on Science
and Technology of BioResources, University of Sao Paulo,
Sao Carlos, Sao Paulo, Brazil
Our studies targeted the use of renewable resources obtained
from lignocellulosic fibers in the preparation of bio-based
materials, from macro to nanoscale. Some examples are
described herein. The performance of coconut fibers as a
reinforcing material is usually inferior when compared to those
of other lignocellulosic fibers, which is attributed to their low
cellulose content. The high lignin content of this fiber was
considered as a possible fiber/matrix compatibilization factor,
since the lignophenolic (Ligno-PHs) matrices also presented
high typical organosolv lignin units content. The impact
strength of the composites correlated positively with the
percentage of substitution of phenol by lignin (from 40 to 100
wt%) in the preparation of the Ligno-PHs matrices [from
approximately 40 Jm-1 (40 wt% lignin) to 400 Jm-1 (100%
lignin)]. Lignosulfonates (LS) are produced worldwide and are
somewhat sparsely applied in the preparation of polymeric
material. In this context, LS (unmodified or chemically
modified) mixed or not with CO, were used to prepare lignopolyurethanes (LS-PUs), reinforced or not with sisal fibers.The
results indicated that the properties of the lignopolyurethanes
can be tuned by modifying the LS and/or by association with
castor oil. The LS-PUs reinforced with sisal fibers exhibited
impact strength and flexural strength considerably higher than
the respective neat polymer, evidencing the excellent action of
sisal fiber as reinforcement of crosslinked matrices. Sisal fiber
has also been considered in the preparation of mats from
electrospinning of solutions prepared from Cellulose
acetates/sisal fibers and PET/sisal fibers. Room temperature
electrospinning was successfully applied to these solutions
containing lignocellulosic sisal fiber and mats of nano/ultrathin
fibers were generated. Materials prepared from a high content
of renewable materials and with good properties have been
obtained in recent years, meeting the current expectations
towards bio-based materials.
CELL 173
Efficient adsorbents based on nanoporous carbon fibers
from cellulosic precursors
Dusan Berek1, [email protected], Ivan Novak1, Karol
Munka2. (1) Poly Inst Slovak Acad of SCI, Bratislava, Slovakia
(2) Research Institute of Water Economy, Bratislava, Slovakia
Original procedure for preparation of efficient sorbents was
developed. The starting materials are cellulose fibers, both
natural and delignified, which are carbonized under inert
atmosphere in presence of suitable porogens. In dependence
on both the type of the starting cellulose and the course of
carbonization, as well as on the nature and the amount of
porogens, the resulting carbon fibers, C-fibers exhibit surface
area from about 2 to almost 2,000 m2g-1. Unexpectedly,
effective pore sizes of C-fibers assessed with help of
positronium annihilation spectroscopy do not depend on the
surface area of material and persist in the range of 0.6 nm.
Appropriate carbonaceous substances added to starting
cellulose exhibit a coopeative effect so that the total recovery
of carbonization is about doubled. In other words, the amount
of resulting carbon is much higher than produced by separate
carbonization of constituents. The C-fibers were employed as
carriers of various substances to create adsorbents suitable for
different purification procedures. The most efficient proved
Fe(OH)3x(H2O)n in the form of nanoparticles unevenly
scattered on the outer surface of C-fibers. The resulting
sorbents exhibited both high efficiency and capacity in removal
of various metals such as As, Sb, Cd, Ni, Cr, and Pb, as well
as natural radionuclides from drinking water, much higher
ability than the best commercial materials. The sorbents based
on C-fibers also efficiently trapped technecium, an important
radionuclide produced in the nuclear plants. Compared with
particulate sorbents, the fibrous structure reduces flow
resistance of above materials in the flow-through applications.
The sorbents possess dual surface, the original carbonaceous
one and that of the deposited substance. The carbonaceous
surface can be further modified to arrive at new clasess of
sorbents suitable for dual applications.
CELL 174
Curing behavior and bond performance of wood adhesive
from enzymatic hydrolysis residues of lignocellulosic
biomass
Islam Hafez, [email protected], Han-Seung Yang, William
T. Tze. Bioproducts and Biosystems Engineering, University of
Minnesota, Saint Paul, Minnesota, United States
The enzymatic hydrolysis of lignocellulosic biomass has
captured a tremendous attention as a conversion route for
producing alternative energy products. This hydrolysis process
leaves behind in the waste stream solid residues that are rich
in lignin. Lignin is a natural phenolic polymer in all vascular
plants which include woody plants. Lignin serves as the binder
for plant fibers; thus, it is not surprising that utilization of lignin
as adhesives has long been investigated. Complexity of lignin
structure however renders it challenging to utilize in a cost
effective manner. Adhesive applications of this renewable
material are limited by its low reactivity compared to phenols.
The main goal of this study was to examine the technical
feasibility of directly utilizing saccharification residues of woody
biomass for adhesive applications without pre-purifying for
lignin. Aspen wood flour were pre-treated with NaOH and then
enzymatically hydrolyzed to 80% glucose removal. The
saccharified samples were ground to nano size using a disk
mill before treated with a natural crosslinker to prepare
adhesive. The strength of adhesive bond on wood substrates
was evaluated through lap shear testing. Cure kinetics and
other bond performance of the adhesive were also studied.
Results showed that the bond strength attained 92% of that of
commercial phenol-formaldehyde resin, which is a common
wood adhesive. Findings from this study show that a fully biobased adhesive could be prepared from saccharification
residues, providing a potential alternative to synthetic
adhesives.
CELL 175
Electrospinning of lignin based composite nanofibers with
nanocrystalline celluloses
Mijung Cho1, [email protected], Frank K. Ko2, Scott H.
Renneckar1. (1) Wood Science, University of British Columbia,
Vancouver, British Columbia, Canada (2) Materials
Engineering, University of British Columbia, Vancouver, British
Columbia, Canada
Lignin is one of the most abundant natural materials after
cellulose constituting about one fourth of the cell wall of plants.
In this study, composite nanofibers were fabricated from
renewable biomaterials, such as softwood kraft lignin (SKL),
nanocrystalline cellulose (NCC) and polyethylene oxide (PEO)
by using electrospinning. NCCs were isolated from cotton filter
papers by sulfuric acid hydrolysis and the water in the NCC
suspension was solvent exchanged to N,N-Dimethylformamide
(DMF) by rotary vacuum evaporation. The electrospinninability
and morphology of nanofibers were studied with various lignin
concentrations and different NCC loadings. The average fiber
diameter increased as a function of lignin solution
concentration with a constant NCC loading (5 wt%).
Subsequently, the as-spun composite fiber mats were
thermally stabilized in air and carbonized in nitrogen to form
carbon fibers. The effects of stabilization temperature, heating
rate, and holding time were investigated on yield, thermal
stability and chemical structure. The thermal temperature had
the largest effect on yield.
CELL 176
Preparation and properties of composite Lyocell fibers
using hemicelluloses as regulator
Jing-Huan Chen, [email protected], Ying Guan, Kun
Wang, Feng Xu, Runcang Sun. Beijing Forestry University,
Beijing, China
Lyocell fibers are normally derived from high α-cellulose
content materials, and hemicelluloses have been considered to
have a negative impact on the Lyocell process due to the
original connections between hemicelluloses and cellulose. In
this work, composite Lyocell fibers were successfully prepared
from the mixture of cellulose and hemicelluloses raw materials
with N-methyl-morpholine-N-oxide (NMMO) as a solvent. To
understand the effect of hemicelluloses on the preparation and
properties of these composite Lyocell fibers, the properties of
the raw materials, the viscosity of the spinning solutions, as
well as the structural and mechanical properties of the
composite fibers were investigated by gel permeation
chromatography (GPC), high-performance anion-exchange
chromatography (HPAEC), Solid state cross polarization/magic
angle spinning (CP/MAS) 13C NMR, solution-state 1H NMR,
proton-detected heteronuclear single quantum coherence
(HSQC) NMR, X-ray diffraction (XRD), scanning electron
microscopy (SEM), viscometer and universal tensile tester.
The results showed that the addition of hemicelluloses
increased the concentration of the spinning dopes and
decreased the average molecular weight of the materials,
synergistically resulting in a variation of the viscosity of the
spinning solutions. Although the crystal and morphological
structure of the fibers were slightly influenced by the presence
of hemicelluloses, the tensile strength and modulus of the
fibers were improved by adding appropriate amount of
hemicelluloses. The distribution of hemicelluloses in the
solutions and in the composite fibers were proposed to
illustrate the regulating effect of hemicelluloses. This study
provided an effective method to improve the properties of
Lyocell fibers and to enlarge the utilization of hemicelluloses.
The prepared composite Lyocell fibers, which are based on
natural and renewable resources, can be used for clothing,
automotive filters, ropes, abrasive materials, bandages and
other purposes.
CELL 177
Repeated homogenization, a route for decreasing the
energy consumption in the nanofibrillated cellulose
manufacturing process?
Ali Naderi, [email protected], Tom Lindström. Paper
chemistry and nanomaterials, Innventia AB, Vällingby, Sweden
Energy-efficient manufacturing is a requirement for the largescale production of nanofibrillated cellulose systems. Today,
most strides involve the development of new physicochemical
pre-treatment processes or invention of new or furtherdevelopment of existing mechanical delamination processes;
these approaches are often costly. In this presentation, it will
be shown that significant reduction in energy consumption (~
30-50%) of the nanofibrillated cellulose (NFC) manufacturing
process is possible by the wise employment of existing
machinery and processes – without deterioration of the
attractive properties of the NFC product. The suggested
approach has further the additional advantage of increasing
the yield of nanofibrillation, robustness of the manufacturing
process, and increasing the out-put of the process. These
notions can lead to significant savings in the NFC production
cost. The novel manufacturing protocol involves repeated
homogenization of the pulp suspension at lower applied
homogenization pressures (as compared to those currently
applied). It is hypothesized that this manufacturing protocol
leads to a more homogeneous and effective shearing of the
fibres, than is achievable by one time homogenization of the
pulp slurry at high applied pressures.
CELL 178
Recent advances in cellulose ester performance and
applications
Jacob D. Goodrich, [email protected]. Eastman
Chemical Company, Kingsport, Tennessee, United States
Cellulose esters have been a major polymeric material of
commerce for over 100 years and still continue to find use in a
wide variety of applications and end markets due to their
desireable property sets and product attributes. This review will
examine some more recent cellulose ester application areas
investigated over the last 25 years. The focus will be on
studying cellulose ester structure as it relates to properties and
performance in select end uses.
CELL 179
Biopolymer modification: Converting biopolymers into
processable thermoplastics
Wolfgang G. Glasser1,2, [email protected]. (1) Sustainable
Biomaterials, Virginia Tech, Richmond, Virginia, United States
(2) cycleWood Solutions, Inc., Dallas, Texas, United States
The use of sustainable, renewable plant biopolymers in manmade materials necessitates the attainment of properties not
usually found in nature, especially solubility and thermal
deformability. The properties of plant biopolymers are designed
to suit Nature’s needs while often conflicting with the
processing requirements of man-made polymeric materials.
Resolving this conflict has long been industrial practice in the
case of cellulose, but it has only recently seen the advent of
industrial application in the case of lignin. This lecture will
review some aspects of structure-property relationships of both
saccharidic and aromatic plant biopolymers in terms of thermal
processability.
CELL 180
Willow as a potential source of lignin raw material
Tarja Tamminen2, [email protected], Ari M. Koskinen1,
Tapani Vuorinen3. (1) Department of Chemistry, Aalto
University School of Chemical Technolog, Aalto, Finland (2)
VTT Technical Research Centre of Finland, Espoo, Finland (3)
Department of Forest Products Technology, Aalto University,
Espoo, Finland
Willow (Salix sp) has been studied widely as an energy crop,
but its other potential uses are still underexploited.
Fractionation of the willow biomass into wood and bark, and
further to chemical components, opens new avenues to add
value to this fast growing biomass source, well above the
baseline energy value. In our new concept to be studied, the
bark fraction will be used for the production of fibers, while the
wood fraction will be used as raw material for the sugar
platform. During the pretreatment and saccharification, lignin is
released. It will be recovered, characterized and studied as raw
materia lfor chemicals, fuels and biomaterials.Willow hybrids
can be developed in order to tune the properties and
composition much in the same way as for Eucalyptus. Four
potential hybrids have been selected for the study. One of
them, “Karin” will be used as raw material for the optimization
of the steam pretreatment process and following enzymatic
saccharification. The saccharifiation will be extended over the
practically applicable level in order to recover the residual
hydrolysis lignins in pure form for the analyses. The lignins will
be characterized for their structure by 31P NMR, 2D HSQC
and SEC, and for their thermal properties by DSC and TG in
order to evaluate their properties and suitability for material
applications as such, and as raw material for catalytic
depolymerization. All four hybrids will be characterized in detail
by microscopic methods and by compositional analyses, and
the most potential ones will be tested more thoroughly for the
practical applications. The paper reports the first results on the
structures and properties of the willow lignins.
CELL 181
CELL 182
New mutiplexed assay for lignin depolymerization
Sub- and supercritical water liquefaction of alkali lignin in
presence of carbon dioxide and ammonia
Michael Kent1,2, [email protected], Isaac Avina1, Nadeya
Rader1, Victor Chavez1, Michael Busse1. (1) Sandia National
Labs, Albuquerque, New Mexico, United States (2) Joint
BioEnergy Institute, Emeryville, California, United States
We have developed a new methodology for detecting and
quantifying lignin depolymerization. The assay is based on
casting films of lignin on silicon wafers and measuring loss of
mass through decrease in thickness. A silicone mold in the
form of a standard 96-well plate is pressed against the silicon
wafer to create a highly multiplexed format. The assay is highly
sensitive, quantitative, and compatible with standard 96-well
plate robotic fluid handling systems. This assay will enable
assessment of the ligninolytic potential of a large number of
catalytic chemistries, ligninolytic enzymes, and reaction
conditions, and rapid identification of ligninolytic organisms and
microbial communities. The multiplexed device was
constructed, refined through several stages, and then several
trials were performed involving the Fenton reaction. The
Fenton reaction, reaction of hydrogen peroxide and ferrous
salt, is used to treat industrial waste and organic contaminants
in groundwater and has been employed in biomass
pretreatment strategies. The trials demonstrated that up to 80
different reaction conditions can be assayed simultaneously.
The mass of soluble fragments released from the film went
through a maximum as a function of the concentration of each
reactant. This is very likely due to competing factors involving
the physical chemistry of the oxidative reactions resulting in a
competition between depolymerization and repolymerization.
The concentration of ferrous salt that yielded the maximum
release of soluble fragments increased with increasing
concentration of hydrogen peroxide.
Abu
Md
Numan-Al-Mobin1,
[email protected], Chris Lynde1, Praveen Kolla1, David
J. Dixon1, Alena Kubatova2, Alevtina Smirnova1. (1) South
Dakota School of Mines & Technology, Rapid Ctiy, South
Dakota, United States (2) University of North Dakota, Grand
Forks, North Dakota, United States
Selective oxidation of lignin yielding high-value liquid chemical
products is one of the major goals of the biomass reforming.
Our results demonstrate that selective oxidation of alkali lignin
in sub- and supercritical water (T=200, 300, 400oC; P=22MPa)
produce liquid phenolic compounds, however their yields (1578%) demonstrate high sensitivity to residence time and
temperature.To understand the observed trends and
mechanisms, a methodology of using binary mixtures of suband supercritical fluids has been developed. The known
thermodynamic properties of supercritical mixtures (e. g.
solubility of CO2 in H2O or NH3 in H2O) indicate that these
systems can be used for lignin oxidation due to high (up to 50
mol%) solubility. We assume that these systems can
significantly change the lignin oxidation potential, de-/repolymerization, and oligomerization capability due to self- and
cross-association. Liquefaction of alkali lignin (Alfa Aesar) was
performed in at 200, 300, and 400°C and residence times of
10-120 min at 22MPa. Alkali lignin (0.1g) was added to 6 mL of
water in a 12mL 316 SS vessel with a capability of continuous
T and P monitoring that was connected to an ISCO 260D
syringe pump. After removing the liquid phase from the
quenched vessel, the H2O-organic phase was separated using
liquid-liquid extraction method developed at NDU. The organic
compounds in liquid phase were analyzed and identified by a
Hewlett Packard 5890 Series II gas chromatograph and
HP5970 Series mass spectrometer.The results indicate that in
all the tests performed at different temperatures (200, 300, and
400oC) and constant pressure (P=22MPa) a significant
difference in chemical composition and yields exists between
the systems (e.g. H2O-CO2 and H2O-N2). In these conditions,
no char formation upon lignin decomposition was detected. At
400oC and 10 min resident time, H2O-CO2 and H2O-N2 systems
contain almost the same amount of phenolic compounds.
Among them guaiacol had the largest percentage reaching
37.91% and 39.69% for H2O-CO2 and H2O-N2, respectively.
Liquefaction of lignin will be discussed in terms of process
parameters, selectivity, chemical composition of the organic
phase, and mechanisms of lignin de-/re-polymerization in
binary H2O -CO2 and H2O -NH3 supercritical mixtures in
comparison to H2O-N2. The support from NSF EPSCoR
Cooperative Agreement #IIA-1330842 BIOCON is gratefully
acknowledged.
CELL 183
Lignin oxidation depolymerization using graphene oxide
as a metal-free catalyst
Photo of lignin film showing results for 76 Fenton reactions after 18
hr at 20 C
Jijiao Zeng, [email protected], Zhaohui Tong. University
of Florida, Gainesville, Florida, United States
The depolymerization of lignin into value added chemicals or
liquid fuels provide an additional revenue for current
polysaccharides based biorefinery processes. Lignin is usually
depolymerized into low molecular chemicals via either
oxidation or reduction approaches and the conversion
processes require the use of expensive metal catalyst such as
Nobel metals. Therefore, it is significant to develop sustainable
and metal-free catalyst. Graphene oxide (GO) has great
potential as sustainable “carbocatalyst” because it contains a
variety of functionalities (e.g. hydroxyl, epoxide and carboxylic
groups) on its edge and basal plane, which providing powerful
oxidizing properties. Herein, we explore capabilities of GO for
facilitating oxidation, cleavage and depolymerization of two
typical lignin model compounds with β-O-4 linkage at ambient
condition. The effects of solvents (e.g. water, THF, DMSO,
Ethanol and acetone), the catalyst loading (10 -100 wt. %) as
well as temperature (25 -120 oC) were studied to achieve the
optimized conditions to depolymerize lignin. The results
indicated that 100% conversion rate of lignin models to liquid
products was achieved at the selected condition. The main
products were identified by GC/MS providing substantial
evidences for depicting the reaction mechanisms.
CELL 184
Catalytic hydrogen-free conversion of lignin in key
aromatics
Richard Gosselink, [email protected]. Biobased
Products, Wageningen UR Food & Biobased Research,
Wageningen, Netherlands
Lignin conversion into monomeric bio-aromatics is of high
interest to the chemical industry to substitute fossil derived
aromatics, which are becoming more expensive. However,
most conversion processes so far show low to moderate
conversion yields and selectivities. In this work, a novel solvent
assisted catalytic process has been developed to depolymerize
technical lignin into a depolymerized lignin oil with a less
complex mixture of mono-aromatics [1]. The use of a
heterogeneous catalyst based on Pd/C under hydrothermal
conditions enables a higher selectivity without the need for
external hydrogen addition.In this process in-situ hydrogen
formation is occurring by aqueous phase reforming of lignin
degradation products or an added solvent. Conversion yields
of more than 50% of lignin oil with about 10% of identified
monomeric aromatic products can be obtained at the current
status.This novel catalytic solvent assisted hydrothermal
process allows the selective conversion of lignin into
industrially relevant bulk chemicals with in-situ hydrogen
generation.
[1] van der Klis, F., Gosselink, R.J.A., van Haveren, J. van Es,
D.S. Lignin valorization, patent filed (2013)
Acknowledgement: The financial support of the Dutch funded
Topsector Energy project YXY Fuels (TKIBE01006) is kindly
acknowledged.
CELL 185
Metal-organic frameworks as selective catalysts for
carbon-oxygen bond cleavage in lignin model compounds
Vitalie Stavila1, [email protected], Kirsty Leong1,
Ramakrishnan Parthasarathi2, Kenneth Sale2, Ryan Davis1,
Mark Allendorf1. (1) Energy Nanomaterials, Sandia National
Laboratories, Livermore, California, United States (2) Joint
BioEnergy Institute, Emeryville, California, United States
Lignocellulosic biomass is becoming an increasingly important
alternative resource for biofuel and chemical production.
However, in order to be commercially viable, a biorefinery must
make use of all the major components of lignocellulose,
including lignin. Indeed, the aromatic lignin polymer holds great
potential for the sustainable production of renewable aromatics
and phenolics, such as benzene, toluene, phenol,
cyclohexanol, cresols, etc. However, because of lignin’s
recalcitrance and heterogeneous structure, lignin valorization
represents a major challenge. Catalytic cleavage of aryl ether
bonds is a crucial step for lignin conversion and valorization, as
the carbon-oxygen bonds are the frequent linkages found in
natural lignin. Previous studies on lignin conversion were
mostly focused on using precious metal (e.g. Pd, Pt, Ru, Ir, Rh)
nanoparticles or difficult to synthesize organometallic catalysts.
We are developing nanoporous Metal-Organic Frameworks
(MOFs) to catalyze reductive and oxidative bond cleavage in
lignin model compounds. MOFs are being increasingly
investigated in catalysis because of their high porosity, tunable
pore environment and high thermal/chemical stability required
for industrial-scale processes. In this presentation we describe
proof-of-concept experiments demonstrating carbon-oxygen
bond cleavage in a series of lignin model compounds using
both reductive and oxidative approaches. The reductive
chemistry is based on the MOF-catalyzed hydrogenolysis of
aromatic ether bonds, while the oxidative chemistry hinges on
the MOF-assisted C-O bond cleavage in the presence of
hydrogen peroxide. Conversions as high as 82%, coupled with
excellent selectivity (up to 97%), highlight the potential of MOFbased catalysts for the selective cleavage of recalcitrant arylether bonds found in lignin and other biopolymers.
CELL 186
Comparative separation and characterization of lignin by
catalytic hydrothermal pretreatment with metal chlorides
Miao Wu1, [email protected], Xueming Zhang1,
Runcang Sun2,1. (1) Beijing Forestry University, Beijing, China
(2) South China Univ of Tech, Guangzhou Guangdon, China
Lignocellulosic biomass, the fibrous materials derived from
plant cell walls, is potentially a clean and sustainable feedstock
for liquid fuel and chemical production in future biorefineries.
Lignin, which has the unique chemical properties to produce a
wide variety of potential fine chemicals, still needs to be further
investigated because of its complex structures. A catalytic
method for the isolation of lignin in high purity from cotton stalk
was presented in this study. Lignin fractions were obtained by
the extraction of cotton stalk under catalytic hydrothermal
conditions in the presence of metal chlorides including AlCl3,
CrCl3, FeCl3 and ZnCl2 as catalysts. The results showed that
the separated lignin fractions possessed higher purities than
milled wood lignin (MWL). 2D NMR spectra demonstrated that
guaiacyl (G) and syringyl (S) units were predominant in these
lignin fractions, similar to the typical lignin types of hardwood. It
was also found that the cleavages of β-O-4′ linkages occurred
remarkably due to the presence of catalysts, and their
decreasing severities were consistent with the acidity of the
metal chlorides. Meanwhile, the degradation was still
accompanied by a mild repolymerization although degradation
far exceeded condensation. In consideration of the relatively
high yield and purity, isolation of lignin from raw materials by
using catalytic hydrothermal pretreatment catalyzed by AlCl3
provided us a more effective approach for biomass
pretreatment.
of
Applied
Polymer
Science,
131(18),
40799.
[2] Lange, H., Sevastyanova, O., Sette, M., Crestini, C. (2014).
University of Rome ‘Tor Vergata’, manuscript in preparation.
CELL 188
Integrated approach to uncover ligands for heparan
sulfate binding proteins
G Boons, [email protected]. Complex Carbohydrate
Research Center, University of Georgia, Athens, Georgia,
United States
The 2D HSQC NMR spectra of these six lignin fractions.
CELL 187
Correlating structural features of lignin with physical
properties: Toward a descriptive-predictive database
[email protected],
Olena
Heiko
Lange1,
Sevastyanova2, Claudia Crestini1. (1) Department of Chemical
Sciences and Technologies, University of Rome 'Tor Vergata',
Rome, Italy (2) Department of Fibre and Polymer Technology,
KTH Royal Institute of Technology, Stockholm, Sweden
Although hundreds of heparan sulfate binding proteins have
been identified, and implicated in a myriad of physiological and
pathological processes, very little information is known about
ligand requirements for binding and mediating biological
activities by these proteins. This difficulty results from a lack of
technology for establishing structure-activity-relationships,
which in turn is due to the structural complexity of natural HS
and difficulties of preparing well-defined HS-oligosaccharides.
To address this deficiency, we have developed an integrated
approach for the identification of ligands for HS-binding
proteins employing affinity purification, sequencing of HS
oligosaccharides by novel mass spectrometric approaches and
the chemical synthesis of libraries of HS oligosaccharides for
structure activity relationships. The methodology has been
employed to identify ligands for the ROBO-1 which is a protein
involved in cell signaling and development.
CELL 189
The efficient use of all available biomass components is of
utmost interest with respect to a sustainable use of renewable
resources. Lignin as the second most-abundant component in
forest biomass is, however, currently not exploited to its fullest
potential. The straight-forward use is impeded by several
lowdowns on the molecular level: i) the structures of isolated
lignins differ depending on the isolation process; ii) the size of
poly- and oligomeric structures are very different among
different lignins; iii) the distribution and or abundance of basic
building blocks and bonding motifs differ among different
lignins. Current research efforts are aiming at a better
understanding of both, the structural features of isolated
lignins, and the physical properties of isolated lignins,
fractionated isolated lignins, and chemically modified lignins.[1]
These important research activities – detailed structural
characterization and determination of physical properties –
should be closely linked, however, for different types of lignins,
to arrive at a more fundamental understanding of lignin: a
descriptive model for lignin that would also allow predictions of
physical properties based on structural features, and vice
versa, would drastically simplify any work related to the
valorization of lignin.In an all-encompassing approach for the
characterization of lignin, physical data such a glass transition
temperature, decomposition temperature, etc. that were
obtained for a collection of representative types of lignins as
well as fractions thereof, were correlated systematically with
detailed structural features and molecular mass key data to
form a database that can serve as quick reference for the
selection of the right lignin type for a envisaged application.[2]
Current efforts are aimed at adding functionalized lignins to this
database.
[1] Sevastyanova, O., Helander, M., Chowdhury, S., Lange, H.,
Wedin, H., Chang, L., Ek, M., Kadla, J.F., Crestini, C.,
Lindström, M.E. (2014). Tailoring the Molecular and Thermo–
Mechanical Properties of Kraft Lignin by Ultrafiltration. Journal
Proteoglycan mimics:
nanobiomaterials
Glycoscience
opportunities
in
Matt Kipper, [email protected]. Dept of Chem Biol
Engineering, Colorado State University, Fort Collins, Colorado,
United States
Proteoglycans are glycosylated proteins with an impressive
repertoire of biochemical and biomechanical functions. Many of
the diverse biological functions of proteoglycans are imparted
by their glycosaminoglycan (GAG) substituents. This
presentation will discuss recent advances in the development
of GAG-based nanomaterials designed to mimic features and
functions of proteoglycans. We will begin by briefly describing
examples of the important biological functions of
proteoglycans. We will use examples that have implications for
musculoskeletal and cardiovascular health and disease. The
majority of the talk will discuss tuning the composition and
structure of proteoglycan mimics to study how their physical
chemistry and composition influence their emergent
biochemical and biomechanical properties. The techniques
discussed will include three examples: polyelectrolyte
complexation to form nanoparticles, synthesis of graft
copolymers, and controlled modification of surfaces with
GAGs.1-6 These three examples illustrate tuning biochemical
properties, biomechanical properties, and a tissue engineering
application. In the first example we will show how
proteoglycan-mimetic nanoparticles can be used to stabilize
and deliver growth factors, and even outperform the highly
glycosylated proteoglycan aggrecan. In the second example
we will discuss tuning composition of proteoglycan mimetic
graft copolymers to alter the mechanical properties of
hydrogels. In the third example we will show how modifying
surfaces with controlled nanoscale features can exploit the
biological properties of GAGs, using an example related to
bone tissue engineering. We will conclude by discussing
opportunities for advances in glycoscience to impact the
development of functional nanobiomaterials, and conversely,
how the refinement of these materials might lend tools to better
understanding glycobiology.
1. Almodóvar, J.; Bacon, S.; Gogolski, J.; Kisiday, J. D.;
Kipper, M. J. Biomacromolecules 2010, 11, 2629-2639
2. Almodóvar, J.; Kipper, M. J. Macromol. Biosci. 2011, 11, 7276
3. Almodovar, J.; Mower, J.; Banerjee, A.; Sarkar, A. K.;
Ehrhart, N. P.; Kipper, M. J. Biotechnol. Bioeng. 2013, 110,
609-618
4. Place, L. W.; Kelly, S. M.; Kipper, M. J. Biomacromolecules
2014, 15, 3772-3780
5. Place, L. W.; Sekyi, M.; Kipper, M. J. Biomacromolecules
2014, 15, 680-689
6. Volpato, F. Z.; Almodovar, J.; Erickson, K.; Popat, K. C.;
Migliaresi, C.; Kipper, M. J. Acta Biomater. 2012, 8, 1551-1559
CELL 190
Gagomers: Safe, lipid-based- nanoparticle clusters coated
with a glycosaminoglycan for systemic delivery of
therapeutic payloads
Dan Peer, [email protected]. Tel Aviv University, Tel Aviv,
Israel
CD44, a well-documented cell surface receptor, is involved in
cell proliferation, migration, signaling, adhesion, differentiation
and angiogenesis, which are important properties for normal
and cancerous cell function. We recently developed particle
clusters coated with hyaluronan, CD44 ligand, (termed
gagomers; GAGs), and showed that they can deliver paclitaxel,
and separately Mitomycin C (MMC) directly into CD44overexpressing tumors in mouse tumor models. We also
showed that GAGs can bind to primary head and neck cancers
(HNC) and deliver MMC to these cells in an efficacious
manner, but not to normal cells taken from the same patient.
Here we show that GAGs can entrap high amounts of RNAi
payloads and deliver them directly into tumor-bearing mice in a
selective manner without any bystander delivery. Next, we
show that RNAi formulated in GAGs do not elevate cytokines,
or induce interferon response or activate complement in
human peripheral blood mononuclear cells, mice and rats. In
addition, histology sections do not reveal any pathological
changes in organs of the mononuclear phagocytic system
(MPS) such as the liver, spleen, and lungs. In addition, no liver
enzyme release or changes in metabolic parameters are
observed. These results demonstrate the selective recognition
of GAGs towards cancerous cells with an exquisite capability
to deliver RNAi payloads and induce robust therapeutic gene
silencing together with excellent safety profile. These
credentials position GAGs as an attractive alternative to
cationic formulations, which might be applicable in many types
of cancer.
CELL 191
Carbohydrate signaling in the brain
Linda C. Hsieh-Wilson, [email protected]. Division of
Chemistry and Chemical Engineering, California Institute of
Technology, Pasadena, California, United States
Chemical neurobiology is rapidly evolving and providing
insights into the molecules and interactions involved in neural
development, sensory perception and memory storage. We will
describe the synergistic application of organic chemistry and
neurobiology to understand how specific carbohydrate
molecules contribute to the wiring of the brain during
development. Chondroitin sulfate glycosaminoglycans have
traditionally been viewed as passive, “barrier” molecules that
impede neuronal growth. By combining synthetic organic and
polymer chemistry, computational chemistry, cell biology and in
vivo biology, we now show that these molecules actively
participate in signaling events that underlie the formation of
neural circuits.
CELL 192
Carbohydrate
biosynthetic
enzymes
multienzyme (OPME) chemoenzymatic
glycans and glycoconjugates
for
one-pot
synthesis of
Xi Chen, [email protected]. Dept of Chemistry, UC Davis,
Davis, California, United States
One-pot
multienzyme
(OPME)
systems
containing
glycosyltransferases and sugar nucleotide biosynthetic
enzymes have seen great applications for synthesizing
complex glycans and glycoconjugates including those
containing naturally occurring and non-natural carbohydrate
modifications. Identifying enzymes and mutants with good
solubility and stability, high expression level in simple
Escherichia coli expression systems, high activity, and
promiscuous substrate specificity is the key to the high
efficiency of the OPME chemoenzymatic synthesis. Our
group's and others' efforts on this aspect, challenges, and
future directions will be presented and discussed.
CELL 193
Using chemistry to
GlcNAcylated proteins
identify
and
characterize
O-
Matthew Pratt, [email protected]. University
Southern California, Los Angeles, California, United States
of
The monosaccharide N-acetyl-glucosamine (O-GlcNAc) can be
posttranslationally added to proteins in the cytosol, nucleus,
and mitochondria of cells. O-GlcNAcylation is required for
development in mammals and contributes to a variety of
human diseases. Here I will present the development and
application of new metabolic chemical reporters (MCRs) of OGlcNAcylation. Specifically, I will highlight the use of these
molecules to both uncover unexpected cellular metabolism and
identify key proteins in cell survival.
CELL 194
Nanoscale natural recourses important to life: Surface
design
of biotech nanocellulose hydrogels
for
applications as medical implants and tissue engineering
scaffolds
Dieter O. Klemm1, [email protected], Wolfgang
Fried1, Friederike Kramer1, Sandor Nietzsche2, Katrin PetzoldWelcke3, Thomas Richter3, Ulrike Udhardt3. (1) Nanocellulose
R&D, Polymet Jena Association, Weimar, Germany (2) Center
of Electron Microscopy, University Hospital Jena, Jena,
Thuringia, Germany (3) Jenpolymer Materials Ltd. & Co. KG,
Jena, Germany
In contrast to all other cellulose types, Biotech Nanocellulose
(BNC) is built up biotechnologically from low molecular weight
sugars as a dimensionally stable hydrogel. That offers the
unique possibility to design the surface of these hydrogel
bodies directly during biosynthesis as required for the
application and function as medical implants and tissue
engineering scaffolds. By cell and animal studies (rat, pig,
sheep) it could be demonstrated that the interaction of BNC
implants and tissue engineering scaffolds with living cells as
well as with body's own tissue and blood can be controlled by
the nature of the BNC surfaces. Their design succeeds directly
in the bioreactor and by postprocessing steps. In the order of
(a) dense surface with native water film, (b) post-treated
surface (roughened, partially dewatered), (c) gel-like surface
with cavities and pores, and (d) perforated hydrogels increases
the interaction significantly. This is very positive for an
intensive cell ingrowth and for integrating the implant into the
body (surfaces c, d). In case of the intergrowth with organs
(e.g. abdominal hernia repair) and thrombus formation in blood
contact (blood vessel implants) are surfaces type (a) required.
The said surfaces can be designed at the interface to the air
(a), to the liquid culture medium or else to matrix materials as
metal, glass, polymer, or silicone (c) as well as by
aftertreatment of the surfaces (b), or by laser perforation of the
hydrogel (d). In case of the Mobile Matrix Reservoir
Technology, the BNC surface design is achieved by the BNC
formation on a matrix/template moving between culture
solution and air. In particular, the perforation by means of laser
radiation leads to interconnecting channel structures without
changing the BNC own material properties.
CELL 195
Preparation of nanocellulosic biointerfaces
Erkko I. Filpponen, [email protected], Hannes
Orelma, Luis O. Morales, Maija Vuoriluoto, Orlando J. Rojas.
Aalto Univ, Espoo, Finland
Conjugation of proteins to cellulose nanofibrils (CNF) and
bacterial nanocellulose (BNC) was employed to demonstrate
the possibility for using cellulose as a platform for diagnostic
assays and biofiltration. Both physical and covalent attachment
of proteins were applied. Pre-adsorbed carboxymethyl
cellulose (CMC) provided the electrostatic counterpart to attach
the given proteins. In addition, the carboxyl groups of CMC
were utilized for the covalent conjugation of proteins. As
prepared cellulose substrates were then applied as
biointerfaces for detection of various proteins. The
bioseparation of human serum albumin was demonstrated by
using BNC tubes. Main results and possible applications for
such systems will be discussed.
Cellulose beads or microspheres are suitable for a broad range
of applications. Utilisation of beads in pharmaceuticals requires
the availability of non-toxic dopes and sustainable preparation
process. In this talk, we present our recent work about
cellulose beads for pharmaceutical applications. Cellulose
microspheres were prepared using alkaline cellulose solutions
and coagulation in acidic medium. Preparation conditions were
altered to achieve beads with controllable specific surface area
and pore sizes. Oxidised microspheres were utilised as a drug
carriers. They demonstrated high mass uniformity, which would
enable their use for personalised dosing among different
patients, such as children. The drug was solidified in
microspheres in amorphous form. This enhanced the solubility
and could be used for more challenging drugs with poor
solubility. Also the pores of the microspheres remained open
after the drug was loaded and beads were dried. Regardless
the swelling, the drug was released at constant rate in all
environments.
CELL 197
Surface modification
responsive materials
of
nanocellulose
to
rngineer
Yanxia Zhang1, Justin O. Zoppe2, Orlando J. Rojas1,
[email protected]. (1) Forest Biomaterials, North Carolina
State University, Raleigh, North Carolina, United States (2)
Institute of Materials, Polymers Laboratory, EPFL, Lausanne,
Switzerland
Responsive polymer layers grafted on cellulose were produced
by utilizing random copolymers. Specifically, an antifouling
hydrophilic
copolymer,
poly(2-aminoethyl
methacrylate
hydrochloride-co-2-hydroxyethylmethacrylate) (poly(AMA-coHEMA)) and a thermo-responsive poly(N-isopropylacrylamide)
were grafted via surface initiated polymerization from an
initiator coupled to cellulose nanofibrils (CNF). The poly(AMAco-HEMA) was used as a spacer and support layer for
immobilization of a peptide with specific affinity with target
biomolecules while the thermo-responsive molecules endowed
the cellulose-based systems with electrolyte and temperature
responsiveness. These two effects will be used to illustrate the
versatility of cellulose for surface functionalization and to obtain
active systems. The CNF-based networks were examined on
solid supports by atomic force microscopy (AFM) imaging and
colloidal probe technique. Extreme resolution imaging with
ultralow electron landing energies and XPS were also used to
access details about the surface topography and chemical
composition. The interactions with surrounding media were
evaluated with quartz crystal microgravimetry (QCM) and
surface plasmon resonance (SPR). The application of the
developed systems in the stabilization of multiphase systems
that can trigger events by given stimuli as well as the
development of platforms for affinity separation will be
presented.
CELL 198
CELL 196
Ioncell-F: A high-strength regenerated cellulose fiber
Functional cellulose microspheres for pharmaceutical
applications
Pedro E. Fardim, [email protected]. Abo Akademi University,
Turku, Finland
Herbert Sixta1, [email protected], Lauri K. Hauru1, Shirin
Asaadi1, Yibo Ma1, Alistair King2, Michael Hummel3, Ilkka
Kilpelainen4. (1) Forest Products Technology, Aalto University,
Espoo, Finland (2) Chemistry, Helsinki University, Helsinki,
Finland
The development of a novel regenerated cellulose fibre
process of the Lyocell type, denoted as Ioncell-F, is reported.
The process is characterized by the use of a powerful direct
cellulose solvent, 1,5-diazabicyclo[4.3.0]non-5-enium acetate
([DBNH][OAc]) a superbase-based ionic liquid. Compared with
the commercial NMMO-based Lyocell fibre process, airgap
spinning can be conducted at higher cellulose concentration in
the dope, while simultaneously the temperature during
dissolution and spinning can be maintained at a lower level.
Owing to the generally milder process conditions, the cellulose
is less degraded which contributes to both higher fibre yield
and better strength properties. In this study we demonstrated
the effect of different cellulose concentrations, 10-17 wt%, and
draw ratios, 0.9-18, on the fibre properties. The highest
tenacities, consistently above 50 cN/tex, were achieved by
spinning from 15 and 17 wt% cellulose solutions. A very high
initial modulus of up to 34 GPa makes the Ioncell-F fibres very
interesting for technical applications such as a reinforcing fiber
in composites. The chain orientation in the fibre direction,
particularly in the amorphous regions, revealed the best
correlation with the elastic modulus and the tensile strength of
the Ioncell-F fibres, in agreement with other high-tenacity
regenerated cellulose fibres as reported in the literature. The
Ioncell-F process is still at a very early stage of its
development. One of the next important research goals is the
development of a viable solvent recycling concept.
CELL 199
Revisiting regenerated cellulose fibers
Stephen J. Eichhorn3, [email protected], Sameer
Rahatekar2, Tom Welton4, Kevin D. Potter2, Alexander
Bismarck1, Nandula Wanasekara3. (1) Department of Chemical
Engineering, Imperial College London, London, United
Kingdom (2) University of Bristol, Bristol, United Kingdom (3)
Physics, University of Exeter, Exeter, United Kingdom (4)
Imperial College, London, United Kingdom
This talk will cover some previous work to better understand
structure property relationships of regenerated cellulose fibres
[1,2] using Raman spectroscopy and other techniques (X-ray
diffraction). Some of the main issues for producing high
performance fibres (stiffness, strength) such as the control of
orientation and the microstructure will be presented. Some
more recent work, funded by the UK's research council
(EPSRC) on ionic liquid spinning of cellulose will also be
presented. This work will be compared against previous liquid
crystalline spun filaments e.g. Bocell [3] and other ionic liquid
spun fibres. Prospects for the future will be discussed in light of
recent developments in the area.
1. Kong, K. and Eichhorn, S.J. 2005. Crystalline and
amorphous deformation of process-controlled cellulose-II
fibres. Polymer, 46, 6380-6390.
2. Kong, K., Davies, R.J., McDonald, M.A., Young, R.J.,
Wilding, M.A., Ibbett, R.N., Eichhorn, S.J. 2007. Influence of
domain orientation on the mechanical properties of
regenerated cellulose fibers. Biomacromolecules, 8, 624-630.
3. Eichhorn, S.J., Young, R.J., Davies, R.J. and Riekel, C.
2003. Characterisation of the Microstructure and Deformation
of High Modulus Cellulose Fibres. Polymer, 44, 5901-5908.
CELL 200
Cellulose man-made fibers reinforcing bio-based
thermoplastics – the role of fiber diameter and fiber-matrix
interphase
Johannes Ganster, [email protected],
Erdmann Jens, Hans-Peter Fink. Fraunhofer Institute for
Applied Polymer Research IAP, Potsdam, Germany
Apart from textile applications, man-made cellulose fibers play
an important role for the reinforcement of rubber goods, first of
all tires. In accord with current sustainability concepts,
possibilities are sought to find “green” solutions also in the field
of short fiber reinforced thermoplastics. Here mainly glass
fibers are used today with market volumes of 1 million tons of
reinforced PP and PA in Europe alone. The potential of
cellulose man-made fibers to substitute glass fibers in these
applications was proven by extensive investigations carried out
at Fraunhofer IAP.In the present paper, on overview will be
given with emphasis on the combination of rayon (man-made
fiber manufactured via the viscose process) and bio-based
plastics, in particular poly(lactic acid) (PLA), a biodegradable
and bio-based aliphatic polyester available on the market in
amounts exceeding 150 kt and representing a possible future
green commodity polymer. In more detail, rayon fibers with
three different diameters and practically the same tensile
properties were used to study the effect of fiber thickness on
mechanical properties including impact behavior. For the latter
property it turned out that thicker fibers are more appropriate
due to less fiber breakage during the manufacturing process
and thus higher fiber length. Moreover, a tailored interphase
modification (weak coupling) was carried out in order to
facilitate an energy absorbing fiber pull out mechanism leading
to extraordinary notched Charpy impact strengths. With the
thickest fibers (17 µm) in these tests, notched Charpy values
as high as 27 kJ/m2 could be found while un-notched values
reached 95 kJ/m2, compared to 2.5 kJ/m2 and 25 kJ/m2 for the
unreinforced PLA, respectively.While all rayon types
investigated gave considerable improvements in the
mechanical and fracture mechanical characteristics of the
composites, properties can be fine-tuned by the choice of the
fiber diameter with advantages of thicker fibers for processing
stability and notched impact properties. Weak coupling was
established as a method to generate extraordinary high impact
properties without sacrificing composite strength and modulus.
CELL 201
Polysaccharides and blends for enhanced drug delivery
Xiangtao Meng2, Joyann A. Marks4, Haoyu Liu5, Grace
Ilevbare1, Lynne Taylor1, Kevin J. Edgar3, [email protected]. (1)
Purdue University, West Lafayette, Indiana, United States (2)
Virginia Tech, Blacksburg, Virginia, United States (3) Mail
Code 0323, Virginia Tech, Blacksburg, Virginia, United States
(4) Macromolecules & Interfaces Institute, Virginia Tech,
Blacksburg, Virginia, United States
Enhancement of solubility of drugs and drug candidates is a
crucial element in improving the therapeutic armament and the
performance of the existing therapeutic armament. Poor
aqueous solubility is a major impediment to the innovation of
new drugs to treat human maladies. We will describe the
development of polysaccharide derivatives with superior
performance in creating supersaturated solutions of otherwise
poorly soluble drugs through amorphous solid dispersion. We
will describe new chemistries that have been developed to
expand the set of polysaccharide derivatives available for this
structure-property work and the broad potential created by this
new chemistry. We will also describe the potential of combining
these new polymers in miscible blends with other polymers to
enhance key parameters like release rate and control of
release timing.
CELL 202
High consistency fibrillation of pulps with enzymes benefits and application foresights
Jaakko J. Pere, [email protected]. Biotechnology, VTT
Technical Research Centre of Finland, Espoo, Finland
Interest on microfibrillated cellulose has increased steadily due
to its wide application potential within material science. Today
microfibrillated cellulose can be produced either by mechanical
means, e.g. by refining or by high pressure fluidization, or by a
chemical pre-treatment, e.g. oxidation, followed by mechanical
disintegration. In both cases the microfibrillated cellulose
produced appears as a hydrogel with low solids content,
typically 1-2%. High water content hampers its transportation
and limits end-use applications. Enzymes are known as
sustainable and efficient tools for modification of natural
materials and they can be used for targeted modification of
cellulose. Here we introduce a new enzymatic method to
produce microfibrillated cellulose characterized by high
consistency, up to 30-40%. The method can be applied on
different cellulose materials without any refining stage.
Properties of the enzymatically fibrillated material will be
presented and potential end-use applications highlighted.
CELL 203
Customizing the mechanical performance of water stable
TEMPO oxidized cellulose nanofibril films
1,
Salminen3,
Minna Hakalahti [email protected], Arto
Jukka Seppälä3, Tekla Tammelin1, Tuomas A. Hanninen2. (1)
VTT, Espoo, Finland (2) VTT Technical Research Centre of
Finland, Espoo, Finland (3) Aalto University, Espoo, Finland
Hygroscopic nature of cellulose is one of the most difficult
limiting factors to overcome in utilization of nanocellulose.
When unmodified nanocellulose structure is subjected to
humidity or immersed in water it loses its structural integrity
very quickly. Nanoscaled cellulose fibrils form very tightly
packed films, which can be used, for example, as excellent
barriers or membranes. Water stability of nanocellulose films
has been improved by preparation of multilayered structures,
reduction of free volume, surface modification and additives.
Polyvinyl alcohol (PVA) can be used to significantly enhance
water stability of films prepared from TEMPO oxidized
cellulose nanofibrils (TOCNs). In water swollen TOCN films,
PVA has two functions; it can either improve the wet strength
by forming interfibrillar bridges or act as a plasticizer. The
interfibrillar bridging is result of two mechanisms: 1) hemiacetal
bonding between PVA hydroxyls and aldehydes in TOCNs and
2) acid catalysed formation of ester bonds between PVA
hydroxyls and carboxylic groups in TOCNs. Sufficient bonding
between TOCNs to achieve water stability could not be
observed. Mechanical properties of the films can be tuned
without losing the water stability merely by changing the
amount of PVA. Even after being immersed in water for several
months, TOCN/PVA films maintain their structural integrity.
The water stability increases to such extent that TOCN/PVA
films can be used as water filtration membranes.
CELL 204
Polyelectrolyteinterdigitation across interfaces and wet
adhesion: Influence of polyvinylamine on wet adhesion
between cellulose model surfaces modified with
carboxymethylcellulose
Emil Gustafsson1, [email protected], Lars Wagberg2, Robert H.
Pelton3. (1) KTH Royal institute of technology, Stockholm,
Sweden (2) KTH Fibre Polymer Techn, Stockholm, Sweden (3)
Department of Chemical Engineering, McMaster University,
Hamilton, Ontario, Canada
The surface of regenerated cellulose membranes were
modified by irreversible adsorption of carboxymethylcellulose
(CMC). Pairs of wet CMC-modified membranes were
laminated with polyvinylamine (PVAm) at room temperature
and the delamination force for wet membranes was measured
for both dried and never-dried laminates. The wet adhesion
was studied as a function of molecular weight, amine content
of and adsorption pH for the PVAm. Surprisingly the PVAmCMC system gave substantial wet adhesion for both the dried
and never-dried laminates. The greatest adhesion was
achieved for fully hydrolyzed high molecular weight PVAm.
Bulk carboxymethylation of cellulose membranes gave inferior
wet adhesion combined with PVAm compared to CMC
adsorption which indicates that a thick CMC layer was
necessary. There are no obvious covalent crosslinking
reactions between CMC and PVAm at room temperature and
we are instead attributing the wet adhesion to interdigitation of
PVAm chains into the CMC layer where polymer
entanglements and specific interactions between the two
polymers contribute to the wet adhesion.
CELL 205
Versatile modification of cellulose by UV-induced surfaceinitiated ATRP
Eva E. Malmström, [email protected], Emma Larsson, Tahani
Kaldéus, Samuel Pendergraph, Anna Carlmark. Fibre and
Polymer Technology, KTH Royal Institute of Technology,
Stockholm, Sweden
Over the past 12 years, numerous papers discussing the
grafting of a range of various cellulose substrates by controlled
radical polymerizations, such as atom transfer radical
polymerization (ATRP) and reversible-addition fragmentation
chain-transfer (RAFT), have been published since the first
paper on this subject by Malmström et al.1,2 The field of
controlled radical polymerizations is evolving and recently
Haddleton et al. showed that ATRP can be induced by UVlight.3 Inspired by this work, we utilized the same system for
the modification of cellulose surfaces. Methyl acrylate was
polymerized from the surface of filter paper utilizing UVinduced ATRP. The polymerization resulted in large amounts
of grafted PMA from the paper already after 90 minutes of
polymerization, as shown by FTIR and SEM. By employing a
cleavable ATRP-initiator the polymer grafts were cleaved from
the surface and separately analyzed by SEC and the results
showed that the polymer had fairly narrow dispersities and that
the molar mass of the chains could be controlled. In another
part of the work and in order to increase the functionality of the
grafting, α-chloro-ε-caprolactone (αCleCL) was copolymerized
with e-caprolactone (e-CL) from the filter paper employing
surface-initiated ring opening polymerization. In a graft-on-graft
approach, the chloride-functions on the grafted P(αCleCL-b-eCL) were subsequently utilized as initiators for the UV-induced
ATRP grafting of di(ethylene glycol) ethyl ether acrylate
(DEGA). The grafted PDEGA chains rendered the paper
thermoresponsive, giving rise to a complete adsorption of a
water drop at low temperature and increasing hydrophobicity
when the temperature was raised.
1) A. Carlmark, E. Malmström, E. J. Am. Chem. Soc., 2002,
124(6), 900-901
2) E. Malmström, A. Carlmark, A. Polym. Chem., 2012, 3 (7),
1702 – 1713
3) A. Anastasaki, V: Nikolaou, Q. Zhang, J. Burns, S. R.
Samanta, C. Waldron, A. J. Haddleton, R: McHale, D. Fox, V.
Percec, P. Wilson, D. M. Haddleton, J. Am. Chem. Soc., 2014,
136 (3), 1141-1149
CELL 206
Nanomechanical properties of single pulp fibers
Niklas Nordgren1, [email protected], Viveca Wallqvist1,
Mats Fredlund2. (1) SP Technical Research Institute of
Sweden, SP Chemistry, Materials and Surfaces, Stockholm,
Sweden (2) Stora Enso, Karlstad Research Centre, Karlstad,
Sweden
Nanomechanical and interfacial properties of single pulp fibers
were studied using atomic force microscopy (AFM). The role of
fiber dimension and effects of starch treatment on the surface
properties were investigated by a combination of quantitative
nanomechanical analysis and colloidal probe AFM. The results
indicate a smoothening effect and modulus reduction of the
fiber surface due to the adsorbed starch layer. Moreover, an
observed increase in both surface dissipation and deformation
demonstrates the ability of the layer to promote viscoelasticity
with only minor effect on the nanoscale adhesion. Taken
together the results suggest that the effectiveness of a
macroscopic strength promoter may be linked to a smoother
more pliable fiber surface at the nanoscale. These findings
along with the presented metrological method may be of
importance in the process of controlling fiber assembly and
durability of fiber based materials.
CELL 207
Assessment of paper topography by confocal laser
scanning microscopy and image analysis
Rupert Kargl1, [email protected], Denis Horvat2, Andreja
Dobaj-Štiglic1, Andreas Kornherr3, Gerhard Drexler3, Domen
Mongus2, Borut Zalik2, Karin Stana-Kleinschek1. (1) Faculty of
Mechanical Engineering, Institute for Engineering Materials
and Design, University of Maribor, Smetanova ulica 17, 2000
Maribor, Slovenia (2) Faculty of Electrical Engineering and
Computer Science, University of Maribor, Smetanova ulica 17,
2000 Maribor, Slovenia (3) Mondi Uncoated Fine & Kraft Paper
GmbH, Marxergasse 4A, 1030 Vienna, Austria
The surface topography and morphology of high grade office
and print papers is of immense importance for high printing
performance and a constant product quality. As a result,
reliable analytical methods are necessary to assess the
influence of production parameters. In addition, it is of high
interest to analyze the influence of paper morphology on the
printability of the products. Several surface sensitive methods
have been used in the past to investigate and illustrate highresolution topography of paper. One of these methods is
confocal laser scanning microscopy (CLSM), which provides
nanometer depth precision. Even though CLSM is a very
powerful technique that is frequently used in life sciences,
sample preparation and data analysis are far from being trivial.
We therefore systematically study the potential of the
technique by developing fluorescence labeling and data
analysis methods. The morphology and roughness of paper
surfaces from CLSM data can be estimated with advanced
algorithms for the analysis of surface topographies. In this way,
detailed information on parameters of interest can be
extracted. Data obtained by this procedure is systematically
compared with other methods for determining surface
topography.
CELL 208
Agroindustrial residues
nanocellulose production
as
alternative
sources
for
Maria S. Peresin1, [email protected], Panu Lahtinen1,
Jari Vartiainen1, Tuomas Hänninen1, Sari Liukkonen1, Jaakko
J. Pere2, Tekla Tammelin3. (1) Technical Research Centre of
Finland, VTT, Espoo, Finland (2) Biotechnology, VTT
Technical Research Centre of Finland, Espoo, Finland (3) VTT,
Espoo, Finland
Properties of nanocellulose vary according their method of
production and composition of raw materials. Recently,
alternative raw materials such as sub-products of agroindustry
and industrial crops have gained significant attention for the
production of nanocellulose. This implies an important addition
to the biorefinary concept, increasing the value chain of
products
such
as
sugar
and
ethanol.
In this work, several raw materials like sugar cane, hemp and
banana fibers were used to produce nanofibrillated cellulose
(CNF). These CNF were characterized in terms of their
suspension behaviour, chemical composition, rheology,
morphology and structural behaviour and such properties
compared to the nanocellulose traditionally obtained from
bleached wood fibres. The suitability of the different materials
in application tests such as paper additives and nanocellulose
film production will be discussed.
CELL 209
Microwave-assisted synthesis of cellulose and alkali earth
metal fluorides (MF2, M=Ca, Mg, Sr, Ba) nanocomposites
fu deng, [email protected], Lian-Hua Fu, Ming-Guo Ma.
Beijing Key Laboratory of Lignocellulosic Chemistry, College of
Materials Science and Technology, Beijing Forestry University,
Beijing, China
In this study, cellulose/alkali earth metal fluorides (MF2, M=Ca,
Mg, Sr, Ba) nanocomposites were successfully synthesised via
microwave-assisted method. The different cellulose types
including microcrystalline cellulose and cellulose solution
pretreated with NaOH/urea and various kinds of alkali earth
metal fluorides were investigated. All samples were
investigated by X-ray powder diffraction (XRD), Fourier
transform infrared spectrometry (FTIR), scanning electron
microscopy (SEM), thermogravimetric analysis (TG), and
derivative thermogravimetric (DTG). In this research, we used
sodium fluoride (NaF) as the source of fluoride ion and the
alkali earth metal nitrate (Ca(NO3)2, Mg(NO3)2, Sr(NO3)2, and
Ba(NO3)2) as the reaction initiator. The results demonstrated
that the cellulose types played an important role in the
recombination of cellulose and alkali earth metal fluorides, and
the types of alkali earth metal fluorides also displayed different
compound abilities. What’s more, cytotoxicity experiments
revealed that the alkali earth metal fluorides on the cellulose
substrate had nice biocompatibility and could be candidates for
the potential applications of biomedical, drug loading and
releasing fields.
The pore size analyzed by BJH model ranged from 1.7 nm to
300 nm and the volume of pores was 0.41 cm³/g.
In order to improve the drug release profile of the produced
micro-meso silica tubes for model compound of asprin, amino
silane was employed to modified the surface of silica tubes.
After the grafting, the modified silica tubes demonstrated slow
drug release profile. TG method showed that the drug loading
was 7.92%. Drug release profile showed that its releasing rate
is slow, after 6 hours 99% of aspirin was released. This
investigation showed that the Micro-meso silica tubes
fabricated with the aid of electrospun cellulose acetate fibers
have promising application in the controllable drug release.
CELL 210
Electrospun cellulose acetate fibers used as templates of
fabrication of tubular micro-meso silica materials for
controllable drug release
Junlong Song1, [email protected], Chengying Jia3,
Yongcan Jin1, Qiang Cheng4, Yan Li2, [email protected].
(1) Dept of Paper Science, Nanjing Forestry University,
Nanjing Jiangsu, China (2) Colorado State University, Fort
Collins, Colorado, United States (3) Quzhou Branch, China
National Pulp and Paper Research Institute, Quzhou, Zhejiang
Province, China (4) Research Institute of Wood Industry,
Chinese Academy of Forestry, Beijing, Beijing, China
Micro-mesoporous materials have advantages in many
applications due to there are of large specific surface area,
large volume of channel, controllable size, narrow pore size
distribution, controllable and uniform morphology and hollow
inside. Template is one of the most commonly used methods
for the fabrication of hollow and mesoporous materials.
Electrospinning is a convenient, flexible and simple mean to
prepare micro/nano scale materials. In this investigation,
electrospun cellulose acetate (CA) fiber was used as templates
to produce tubular silica materials with micro-meso pores in the
walls, which demonstrate controllable drug release profile.
Electrospun CA fibers were used as templates, cetyltrimethyl
ammonium (CTAB) bromide as bridge, tetraethoxysilane
(TEOS) as silica source and the sol-gel method was employted
to prepare composites of silica and CA fibers. After
incineration, silica tubes with featured micro-mesoporous
structure were obtained. The prepared silica micromesoporous silica tubes with wall thickness about 100 nm,
inner diameter closed to 1 micrometer. BET measurement
demonstrated that it has specific surface area up to 765 m2/g.
CELL 211
Carbon fibers from
nanocrystals (CNCs)
polyacrylonitrile
(PAN)/cellulose
Huibin Chang1,2, [email protected], An-Ting Chien1,
Hsiang-Hao C. Liu1,2, Bradley A. Newcomb1, Po-Hsiang
Wang1, Satish Kumar1,2. (1) Materials Science and
Engineering, Georgia Institute of Technology, Atlanta, Georgia,
United States (2) Renewable Bioproducts Institute, Georgia
Institute of Technology, Atlanta, Georgia, United States
Carbon fibers are widely used in high-strength and low-density
composite
materials.
Among
different
precursors,
polyacrylonitrile (PAN) is the predominant precursor for carbon
fiber production. Cellulose nanocrystals (CNCs), which have a
near perfect crystal structure, possess high tensile strength (up
to 7.5 GPa) and high tensile modulus (110-220 GPa). By
comparison, the tensile strength and modulus of PAN
precursor is about 1 GPa and 20 GPa, respectively. It is
hypothesized that the incorporation of highly ordered, high
strength and high modulus CNCs will contribute to further
increase in PAN based carbon fiber strength and modulus. The
purpose of this research, therefore, is to process PAN/CNC
nanocomposite fibers and to convert them into carbon fiber.
PAN/CNC nanocomposite fibers are gel spun using dimethyl
formamide (DMF). Fibers have been stabilized in air and
carbonized in inert environment. Structure, processing, and
properties of the PAN/CNC precursor fibers, as well as their
stabilized and carbonized products will be presented and
discussed in this work.
CELL 212
CNT incorporated lignin/PAN composite carbon fibers
Hsiang-Hao C. Liu1,2, [email protected], An-Ting Chien1,
Bradley A. Newcomb1, Yaodong Liu1, Satish Kumar1,2. (1)
Materials Science and Engineering, Georgia Institute of
Technology, Atlanta, Georgia, United States (2) Renewable
Bioproducts Institute, Georgia Institute of Technology, Atlanta,
Georgia, United States
As the byproduct of the pulp and biorefinery industry and the
second most abundant biomacromolecules on earth, lignin is
an attractive cost-effective alternative for carbon fiber
precursor. However, the lignin derived carbon fibers have
relatively low mechanical properties. In this work, a novel
precursor polyacrylonitrile (PAN)/Hardwood Lignin/Carbon
nanotubes (CNT) system is proposed to balance production
cost and carbon fiber mechanical properties. Although lignin
fiber is mainly processed through melt-spinning, the authors in
this work utilize solution spinning for the composite fibers.
Composite fibers are then stabilized under oxidative conditions
and further carbonized under inert environment at different
temperatures. The effects of lignin and CNT on fiber structure
and properties will be discussed. The incorporation of lignin will
reduce cost and environmental impact from manufacturing.
CELL 213
Understanding lignin acidolysis with aryl-ether model
compounds: A combined DFT and microkinetic study
Adam Pelzer1, [email protected], Matthew Sturgeon2,3,
Abraham Yanez-McKay4, Gina Chupka6,2, Marykate O'Brien6,
Rui Katahira1, Gregg Beckham2, Linda J. Broadbelt4. (1)
Chemical and Biological Engineering, Northwestern University,
Chicago, Illinois, United States (1) 3323, National Renewable
Energy Laboratory, Golden, Colorado, United States (2)
National Renewable Energy Lab, National Advanced Biofuels
Consortium, Golden, Colorado, United States (3) National
Renewable Energy Lab, National Bioenergy Center, Golden,
Colorado, United States (4) Chemical and Biological
Engineering, Northwestern University, Evanston, Illinois,
United States
Lignocellulosic biomass offers a vast, renewable resource for
the sustainable production of fuels and chemicals. To date, a
commonly employed approach to depolymerize the
polysaccharides in plant cell walls employs acidic
environments, and upgrading strategies for the resulting
sugars are under intense development. While the behavior of
cellulose and hemicellulose are reasonably understood, a
more thorough understanding of lignin depolymerization
mechanisms in acidic environments is necessary to
understand the fate of lignin in acidic conditions and ultimately
to potentially make lignin a viable feedstock. To this end, dilute
acid hydrolysis experiments were performed on two lignin
model compounds containing the α-O-4 ether linkage over a
range of temperatures concomitant with dilute acid
pretreatment. Both primary and secondary products were
tracked over time, giving insight into the reaction kinetics. It
was found that methylation of the α-carbon increases the rate
of reaction by an order of magnitude. Density functional theory
calculations were performed on a proposed mechanism
initiated by a nucleophilic attack on the α-carbon by water with
a commensurate protonation of the ether oxygen. The values
for the thermodynamics and kinetics derived from these
calculations were used as the basis for a microkinetic model of
the reaction. Results from this model are in good agreement
with the experimental kinetic data for both lignin model
compounds and provide useful insight into the primary
pathways
of
α-O-4
scission
reactions
in
lignin
depolymerization. The reaction coordinate for the formation of
the major products (solid line) along with the ortho (---) and
para
(····)
condensation
products
for
the 1(phenoxyethyl)benzene acidolysis reaction.
CELL 214
Modifications to the structure and dynamics of lignin
under THF-water co-solvent systems
Micholas D. Smith3, [email protected], Xiaolin
Cheng2, Loukas Petridis2, Barmak Mostofian1, Jeremy C.
Smith3. (2) Center for Molecular Biophysics, Oak Ridge
National Laboratory, Oak Ridge, Tennessee, United States (3)
Center for Molecular Biophysics, UT/ORNL, Oak Ridge,
Tennessee, United States
Recent
experimental
work
has
demonstrated
that
tetrahydrofuran (THF) water co-solvent systems readily
enhance the saccharification of biofuel precursors from
lignocellulosic biomass; however, a detailed description of how
these systems alter the physical properties of lignin/cellulose
allowing for this enhancement is unknown. Here, using allatom molecular dynamics simulations, we examine the
behavior of a softwood-like lignin aggregate under two different
concentrations of THF-water co-solvent at three experimentally
relevant temperatures. The results of this examination are
summarized in terms of average unfolding time, radius of
gyration measures, co-solvent contacts with lignin, and
changes to the polymer's scaling exponent.
Acquiring a detailed understanding of how these geometric
features affect intra-particle transport phenomena during
various conversion processes will facilitate optimization of
reactor conditions for specific feedstocks. First, I will describe
methods by which microscopy data may incorporated into
computer aided design (CAD) algorithms for the construction of
3D models of biomass particles that reflect realistic particle
morphology and species-specific microstructure. Next, I will
present simulations of heat and mass transfer in the context of
these complex particle models and compare the results to
similar simulations using traditional particle geometries. Finally,
I will present simulations of conversion processes that couple
heat and mass transport to kinetic models for biomass
conversion processes to demonstrate how the size, shape, and
species of biomass feedstocks can impact simulation results.
Lignin in 0.4 THF to Water mass ratio at 445K
CELL 217
CELL 215
Catalyst support effects in the carbon-oxygen bond
cleavage of lignin degradation products
Modeling coupling reactions for upgrading biomass
pyrolysis vapor
Mark R. Nimlos, [email protected], Seonah Kim, Lintao
Bu, David Robichaud, Gregg Beckham, Glen A. Ferguson.
National Bioenergy Center, National Renewable Energy
Laboratory, Golden, Colorado, United States
The upgrading biomass pyrolysis vapors into hydrocarbons
presents a pathway to the production of renewable fuels and
chemical products, but a better understanding of the catalytic
processes is required for improving efficiency. Carbon coupling
reactions involving carbonyl compounds are an important class
of reactions that are necessary to produce molecules in the
diesel and jet fuel ranges and to reduce gas formation. In this
study we investigate the coupling of small carbonyl compounds
that are found in pyrolysis vapors and that are models for
classes of pyrolysis compounds. Quantum mechanical
calculations are used to examine adsorption of reactant
molecules in the micropores of zeolites, to identify the
transition states for reactions and to estimate the energies of
reactions and transition states. In this way the reactivity on
different zeolites is determined as a function of acidity and pore
structure. Finally, the results of these calculations are
compared to experimental measurements of the reactivity of
model compounds on the same catalysts. This effort will help
us better understand upgrading chemistry and select optimal
catalysts.
CELL 216
Mesoscale simulations of biomass conversion processes
using particle models with explicit, species-specific
microstructure
Glen A. Ferguson, [email protected], Michael Griffin,
Susan Habas, Dan Ruddy, Joshua A. Schaidle, Mary Biddy,
Gregg Beckham. National Bioenergy Center, National
Renewable Energy Laboratory, Golden , Colorado, United
States
Lignin degradation from catalytic fast pyrolysis results in a
variety of oxygen functionalized aromatic molecules. The
presence of oxygen in these products significantly reduces the
quality of the resulting bio-oil and must be removed prior to
processing these products into fuels. Previous experimental
results indicate the possibility of direct C–O bond breaking at
elevated temperatures and low hydrogen pressures. More
recent experimental results indicate that the support material is
critical in understanding the C–O bond breaking step in the
mechanism for oxygen removal. The proposed mechanism
requires the tautomerization of the aromatic lignin degradation
product to an oxygenated cyclic diene. The resulting diene is
more likely to undergo oxygen removal than the aromatic
species. To understand this mechanism we have explored the
tautomerization and subsequent deoxygenation steps using
DFT calculations. The mechanism for the model compounds of
catechol and phenol C–O bond breaking under a hydrogen
atmosphere is explored over the TiO2(101) and TiO2(001)
surfaces of anatase titania. The effect of oxygen vacancies, the
presence of absorbed hydroxyl groups, and surface adsorbed
hydrogen on titania are explored for both catechol and phenol.
These results are compared to the reactivity over the same
reactions on a Pt(111) surface. These results provide the basis
for understanding this complex mechanism and will be
compared to available experimental data.
CELL 218
Peter Ciesielski1, [email protected], Michael F.
Crowley1, Mark R. Nimlos2, Bryon Donohoe1, Thomas Foust1.
(1) National Renewable Energy Lab, Golden, Colorado, United
States (2) Natl Renewable Energy Lab, Golden, Colorado,
United States
Dissolution and reaction of lignin in ionic liquids: A
computational mechanistic study
Heat and mass transport play an important role in many
biomass conversion processes. These phenomena are be
impacted not only by particle size and shape, but also by the
complex, directional system of pores within biomass particles
which can vary substantially between biomass feedstocks.
Imidazolium-based ionic liquids can dissolve cellulose and the
lignocellulose composite, providing potential new routes to
synthesizing high-value chemical intermediates from
lignocellulose. Mechanistic details of lignin's dissolution and
reaction in ionic liquids are under active investigation. We
Benjamin G. Janesko, [email protected]. Chemistry,
Texas Christian University, Fort Worth, Texas, United States
report a computational study of these details, using density
functional theory calculations. DFT calculations elucidate the
noncovalent interactions between isolated molecules of lignin,
cellulose, and ionic liquid anions and cations; and point to a
possible role of imidazolium pi stacking in lignin dissolution.
Calculations in continuum model solvents illustrate solvent
effects on acid-catalyzed lignin hydrolysis, as well as the
possible mechanistic roles of acidic ionic liquids and metal
chloride additives. These results illustrate the potential role of
computational chemistry in testing proposed reaction
mechanisms in biomass chemistry.
CELL 219
Theoretical understanding of biomass dissolution and
dissociation in acidic and basic ionic liquids
Parthasarathi
Ramakrishnan,
[email protected].
Deconstruction, The Joint BioEnergy Institute , Sandia National
Laboratories and Lawrence Berkeley National Laboratory,
Fremont, California, United States
Effective dissolution of lignocellulosic biomass by ionic liquid
(IL) is an important technology that is readily applicable to
current biomass conversion into advanced fuels and
chemicals. It involves enhanced separation of lignin moieties
from cellulose and by influencing the predominant hydrogen
bonding and other non-covalent interactions (include stacking
and Vander Waals interactions) of resultant amorphous
cellulose that could be rapidly hydrolyzed into glucose by
commercial cellulase mixtures. Our recent efforts on the
development of designing novel ILs for improved economy and
biocompatibility are paved a way of discovering diverse set of
ILs with task specific dissolution capacity on lignocellulosic
biomass pretreatment and also enable unique catalytic routes
of biomass dissociation in aqueous conditions and lower
temperatures. Besides experimental work, quantum chemical
computations of acidic and basic ILs interactions with lignin
and cellulose have been conducted mainly focus on
understanding reaction mechanisms. Lignin dimer model
compounds comprising p-hydroxyphenyl (H), syringyl (S), and
guaiacyl (G) subunits linked through common β-O-4, β-1 and
β-5 inter-unit linkages are investigated to understand
physiochemical control on reaction mechanisms. The role of
hydrogen transfer elucidated in this work clearly differentiates
energy barrier involved the acidic and basic ILs process
conditions and molecular triggering factors affect dissociation
of low molecular weight fragments.
CELL 220
Molecular simulation of hydrolysis reactions to engineer
more efficient biomass conversion
Kelly Fleming, [email protected], Jim Pfaendtner. Chemical
Engineering, University of Washington, Seattle, Washington,
United States
Finding a more efficient way to derive fuel from cellulosic
material has been a priority in chemical research for decades.
Hydrolyzing the ether bond, the glycosidic linkage in biomass,
is the limiting factor in producing fuels from cellulosic biomass
due to the high cost of enzymes required for this step.
Recently, focus has shifted to ionic liquids (ILs) as a potential
alternative solvent to enhance product yield of the breakdown
of cellulosic biomass. By choosing the anion/cation
combination, ILs can be uniquely engineered for specific
applications based on preferred physiochemical properties
such as density, viscosity, hydrophobicity, and solubility, and
are more environmentally sustainable than traditional organic
solvents. However, atomistic details not well understood to
explain how ILs affect the enzymatic reaction mechanism to
improve yield. Given this information, the most efficient ion
combination can be chosen, improving the efficiency of the
reaction for each unique system.Dimethyl ether (DME) offers a
simplified representation of the ether bond in cellulose so the
system can be modeled at the atomic level. Using ab initio
molecular dynamics and Density Functional Theory (DFT) we
investigated how ILs affect energetic and geometric features of
DME hydrolysis at the atomic level to gain insight into how
reaction yield is improved. DFT was performed with Gaussian
09 in vacuum and water to obtain minimum energy geometries
for the reactants and products and to find the relevant
transition state steps for both the catalyzed and uncatalyzed
reactions. The transition state step occurs during the proton
transfer from water to the DME oxygen, agreeing with previous
findings. DME hydrolysis was modeled in vacuum, water, and
IL mixtures with parameters used in a study by Liang, et al.
that modeled catalyzed DME hydrolysis in water with CPMD
enhanced with metadynamics. Results show the solvent
significantly affects the geometric features, specifically the
torsional angle and bond lengths. The energy surface also
indicates direct dependence on solvent atoms. By constructing
free energy surfaces corresponding to specific geometric
features, we can match exactly which steps of the hydrolysis
reaction are made more favorable by ILs and why. Details
learned will assist in designing optimal reaction conditions for
biomass breakdown with solvents to enhance enzyme
degradation during processing, making biofuels a more
economic alternative form of energy.
CELL 221
Structural characteristics of industrial lignins in respect to
their valorization
Tiina Liitiä5, [email protected], Stella Rovio6, Riku Talja7, Tarja
Tamminen1, JORGE RENCORET2, Ana Gutiérrez8, José C.
del Río4, Bodo Saake3, Katrin Schwarz9, Janis Gravitis10,
Marco Orlandi11. (1) VTT Technical Research Centre of
Finlanf, Espoo, Finland (2) IRNAS, CSIC, Seville, Spain (3)
University Hamburg, Hamburg, Germany (5) VTT, Espoo,
Finland (8) IRNAS-CSIC, Seville, Spain (10) LSIWC, Riga,
Latvia (11) University Milan, Milan, Italy
Depending on the used biomass processing technology, lignin
by-products with distinct structural features are produced,
offering thus variable up-grading routes for the lignin residues.
In this paper, the effect of raw material (softwood, hardwood,
wheat straw, bagasse) and pretreatment procedure (kraft,
soda, soda-AQ, organosolv, steam explosion) on the structure
and properties of the lignin fractions was evaluated by detailed
chemical and physical characterization. The application
potential of studied lignins especially for resins (PU, PF),
composites and dispersants was considered based on those.
In addition to the purity and composition, the lignin structure
(S/G/H ratio, inter-unit linkages) was analyzed using both the
degradative (Py-CG/MS) and spectroscopic techniques (2D
1H-13C NMR). Lignin functionalities (aliphatic and aromatic
hydroxyl, and carboxylic acid groups) were analysed by 31P
NMR spectroscopy. Molar mass was determined by size
exclusion chromatography. Thermal properties were evaluated
by DSC.Lignin rich hydrolysis residue and steam exploded
(SE) lignins extracted by alkali after SE, had distinct
characteristics (high molar mass, low phenolic content)
compared to the spent liquor lignins. For the reactivity required
in PU resins, both aliphatic and phenolic hydroxyl groups are
essential. The highest total hydroxyl content was detected for
hydrolysis residue and SW kraft lignin. The SW kraft lignin also
had most C5 unsubstituted phenols, which is a prerequisite for
the reactivity in PF resins. Soda-AQ bagasse and soda wheat
straw lignins contained most non-methoxylated parahydroxyphenyl groups, which should improve reactivity for PF
resin applications. The SE lignins and the SW kraft lignin had
the highest molar mass, assumably providing better adsorption
properties for dispersants. Higher molar mass lignin could be
beneficial also for the mechanical properties of lignin based
composites. The soda wheat straw lignin had high inherent
content of acidic groups assumed to be beneficial for
dispersants or surfactants, although additional modification is
probably still needed for improved solubility. The LGF
organosolv lignin had clearly lowest Tg, being in that sense
most thermoplastic for composites as such. Also here chemical
modification is still needed to obtain moldable thermoplastic
lignin for thermal processing.
CELL 222
Features of different lignin sources for adhesives and
aromatic chemicals production
Denilson Da Silva Perez1, [email protected],
Valentina Rousseau-Popa3, Frédérique Ham-Pichavant3,
Stephane Grelier3, Audrey Guillemain1, Sandra Tapin-Lingua 1,
Claudia Crestini2. (1) New Materials DIvision, FCBA, Grenoble,
France (2) Chemical Sciences & Technologies, Tor Vergata
Univrsity, Roma, Italy (3) Laboratory of Organic Polymer
Chemistry, ENSCPB, Talence, France
The interest of using lignins as raw material for different
chemical applications has importantly increased in the last
years. The emergence of new processes allowing producing
lignin from pulp mills at industrial scale such as Lignoboost and
the green chemistry approaches explain this gain of interest.
However, depending on vegetal sources (softwoods,
hardwoods, annual plants or residues) and the extraction
processes (kraft, soda, bisulfite, organosolv), lignins structure
can be very different. Therefore, the initial step for considering
the use of different lignins as source of chemicals, either as a
macromolecule for green adhesives or as oligomers/monomers
the chemical industry, is a detailed characterization of their
chemical structures.To address such important topic, nine kraft
lignins issued from different vegetal materials (softwoods,
hardwoods, annual plants) isolated from alkaline black liquors
by two methods (addition of CO2 or H2SO4) were characterized
by different chemical and spectroscopic/spectrometric
methods.Lignins purity from 87 to 96 %, C content from 50.2 to
65.2 %, O content from 27.2 to 34.4 %, H content from 4.4 to
5.7 % and S content from 2.1 to 4.2 %. Phenolic OH content
was calculated using two methods: UV-vis difference spectra
(15-31 OH per 100 C9 units) and 31P NMR after phosphitilation
(16-45 OH groups per 100 C9 units). 31P NMR spectra also
allowed quantifying different phenolic units (S, G or H units),
condensed phenolic units, aliphatic OH groups, and carboxylic
acids. Generally, aliphatic OH groups content is lower for
hardwoods lignins (0.6-0.7 mmol/g) that the others (1-1.7
mmol/g). Important amounts of phenolic S units are logically
observed for hardwoods, especially for eucalyptus (1.9
mmol/g). Softwoods lignins contain considerable amount of
phenolic G (1.2-1.4 mmol/g) and condensed units (0.8-1.1
mmol/g). However, very surprisingly, annual plants lignins
contain few amounts of phenolic H units (0.2 mmol/g). SEC
analysis revealed the average molecular weight (Mw) ranges
between 980-2546 g/mol. Finally, a fine analysis of the lignins
units using a quantitative the QQ-HSQC 2D NMR sequence
was performed revealing an important variety of structures. A
synthesis of the results based on the analysis of the products
issues from the wet chemistry methods and 2D NMR analysis
will be presented as a guide for the users of lignin in adhesives
or chemicals production applications.
CELL 223
Methyl isobutyl ketone/ethanol organosolv
Characterization and conversion to carbon fiber
lignin:
Omid Hosseinaei2, [email protected], David P. Harper1,
Joseph J. Bozell3, Timothy G. Rials1. (1) The University of
Tennessee, Knoxville, Tennessee, United States (2) University
of Tennessee, Knoxville, Tennessee, United States
Lignin, the second most abundant natural polymer on the
planet and a by-product of biorefinery and paper industry, is
consider a renewable and sustainable source for making value
added products. One of the potential products from lignin is
carbon fiber because of its low price, high carbon content, and
renewability. Melt spinning seems to be the most cost-effective
way for making carbon fibers. However, the most common
technical lignin (kraft) does not possess suitable thermal
characteristics for the melt spinning process. Lignin from
organosolv
process
has
demonstrated
remarkable
characteristic such as high purity and stable rheology. Ethanol
organosolv is the most common organosolv process, but it
produces highly depolymerized lignin that requires very long
thermostabilization time. An organosolv solvent system of
methyl isobutyl ketone (MIBK), ethanol and water, with a 0.05
M sulfuric acid as catalyst was used to fractionate switchgrass
and hybrid poplar biomass in a flow-through and static reactor
conditions. Lignin was isolated through rotary evaporation of
the collected spent liquor. Ash content, elemental composition,
thermal properties and chemical structure of lignins (FTIR and
NMR spectroscopy) were investigated. Melt spinning was
performed using a Haake MiniLab twin screw extruder. Lignin
fibers were thermostabilized and then carbonized. Results
indicated switchgrass lignin had higher nitrogen and ash
content. Both lignin had comparable Tg and thermal
decomposition trend. Based on IR spectroscopy switchgrass
lignin had high intensity band related to carbonyl groups, which
is typical for Gramineae due to presence of hydroxycinnamic
acids. 2D NMR spectroscopy showed extensive cleavage of
ether linkages and condensed structures dominated,
phenylcoumaran (β-5') in switchgrass and resinol (β-β') in
poplar. There was no peak in the carbohydrate anomeric
region of poplar spectra; these peaks were observed in the
spectra of switchgrass lignin. Poplar lignin was spun
continuously exhibiting some fiber strength and extensional
flow. Switchgrass lignin resisting continuous fiber extrusion by
having little melt strength and virtually no ability to stretch. As a
result, carbon fibers from poplar had higher tensile strength
and better surface morphological properties. Differences in
processing and properties are attributed to lignin structure
rather than organic and inorganic impurities that were similar.
CELL 224
Macromolecular characterization of plastics with 85–100%
levels of methylated native softwood lignin
analysis, andthermogravimetric analysis. The mechanism of
laccasecatalyzedpolymerizationofanilinein
LGS
template
system was also discussed.
CELL 226
Yun-Yan
Wang,
Yi-ru
Chen,
Simo
Sarkanen,
[email protected].
Bioproducts
and
Biosystems
Engineering, University of Minnesota, Saint Paul, Minnesota,
United States
Significant value added to co-product lignins is essential for the
profitability of biorefineries that process lignocellulose. Over
the past 40 years, lignins and their derivatives have been
generally regarded as functionally rigid macromolecules that
require introduction of compliant polymer chains to reduce their
brittle behavior in the solid state. Unfortunately, such an
approach made it difficult to overcome a 40% incorporation
limit for lignins in polymeric materials. However, it is quite
possible to create plastics that are entirely composed of
methylated native softwood lignins. Such new nanobiomaterials exhibit tensile properties that are better than those
of polystyrene. Their strength and/or ductility are improved
substantially by blending with relatively low levels of many
different
components
like
the
flame
retardant,
tetrabromobisphenol-A, the triblock copolymer, poly(ethylene
oxide-b-1,2-butadiene-b-ethylene oxide), and poly(ethylene
glycol). The predominant macromolecular species in these
plastics are associated complexes of methylated lignin
components assembled as a result of strong noncovalent
forces between the interior cofacial aromatic rings. Continuity
between neighboring macromolecular complexes is achieved
through a greater incidence of edge-on orientations between
interacting aromatic rings among the peripheral chain
segments in these species. Indeed, it appears that the thermal
motions responsible for the glass transition detected by
differential scanning calorimetry are pre-eminently restricted to
the peripheral lignin components of the complexes which, in
the nano-biomaterials described here, exhibit average
diameters of 45 nm as a lower limit. A more complete
understanding of the macromolecular characteristics of these
new lignin-based plastics will hasten the arrival of economic
viability for lignocellulosic biorefinery operations.
CELL 225
Laccase-catalyzed synthesis of conducting polyanilinelignosulfonate
composite
qiang wang1, [email protected], Ya Zhang1, xuerong
fan1, Ping Wang2, Jiugang Yuan3. (1) Jiangnan university,
Wuxi, China (2) Jiangnan University, Wuxi, China (3) School of
textiles and clothing, Jiangnan University, Wuxi, Jiangsu,
China
The high-redox-potential catalyst laccase, isolated from
Aspergillus,wasfirstusedasabiocatalyst
in
the
oxidative
polymerization of water-soluble conductive polyaniline(PANI)/
lignosulfonate (LGS) complexin LGS template system with
atmospheric oxygen serving as the oxidizing agent. LGS
served as linear templates and do pants facilitated the head-totail coupling of the monomers, thus causing an increase in the
conductivity of the complex. Meanwhile, the thermal stability,
solubility and process ability of the polymer were enhanced.
The conditions for polyaniline synthesis were optimized.
Characterizations of the complex were carried out using UV–
vis spectroscopy, FT-IR, cyclic voltammetry, elemental
Preparation of water-soluble lignin polyoxyethylene ether
by epoxidation and etherification
Chang-Zhou Chen, [email protected], Xun Li, Ming-Fei
Li, [email protected], Runcang Sun. Beijing Key
Laboratory of Lignocellulosic Chemistry, Beijing Forestry
University, Beijing, China
In this study, water-soluble lignin polyoxyethylene ether 1000
(L-PEG1000) was synthesized from epoxy alkaline lignin (E-L)
and polyoxyethylene ether 1000 (PEG1000). The epoxidation
of alkaline lignin was conducted with epichlorohydrin using
tetrabutylammonium bromide as the catalyst and 48% sodium
hydroxide solution as the dechlorinating agent. L-PEG1000
was prepared by the reaction of PEG1000 hydroxyl groups and
E-L epoxy groups using potassium persulfate as the initiator.
The effect of different reaction time and temperature on the
reaction ratios of L-PEG1000 was also investigated. The
structure of the L-PEG1000 was analyzed by Fourier transform
infrared spectroscopy (FTIR), ultraviolet spectrophotometer
(UV), gel permeation chromatography (GPC), and nuclear
magnetic resonance spectroscopy (NMR). FTIR and NMR
results showed that the PEG1000 was successively introduced
into lignin. The surface activity of L-PEG1000 was evaluated
via the detection of surface tension of the synthesized lignin
derivative solution. Results indicated that the lignin derivatives
prepared in this study is a promising feedstock as detergent
and dispersant.
CELL 227
Utilization of biorefinery technical lignins on lignin-phenolformaldehyde resin adhesives
Sheng Yang1, [email protected], Tong-Qi Yuan2,
Runcang Sun3. (1) Beijing Key Laboratory of Lignocellulosic
Chemistry, Beijing Forestry University, Beijing, China (2)
Beijing Forestry University, Beijing, China (3) South China Univ
of Tech, Guangzhou Guangdon, China
With the development of the modern biorefinery industry and
the application of this concept in conventional biomass
utilization, large amounts of biorefinery technical lignins have
been generated. As phenolic polymers, lignins are considered
to be potential renewable sources for industrial applications.
Because of the structural similarity between lignin and phenolformaldehyde (PF) resin, phenolic resin is an attractive area for
the application of technical lignin. The final properties of the
lignin-phenol-formaldehyde (LPF) resin adhesive are
significantly dependent on the structural and chemical (active
sites) features of the lignin. Thus, a complete characterization
of the technical lignin is extremely necessary prior to the
synthesis of LPF resin adhesive. In the present study, the
structural features and active sites of four different biorefinery
technical lignins before and after phenolation treatment under
alkaline condition were determined using quantitative 2D
HSQC, 13C NMR and 31P NMR spectroscopies. Four LPF resin
adhesives were synthesized with a proposed formulation,
which was designed based on accurate analysis of the active
sites of the four lignins with 31P NMR. The properties of the
LPF resin adhesives and the plywoods prepared with them
were tested according to the corresponding Chinese National
Standard. The structural features and curing behavior of the
LPF resin adhesives, as well as a commercial phenolformaldehyde (CPF) resin adhesive, were investigated by
solution and solid state 13C NMR. The curing characteristic of
the uncured LPF and CPF resin adhesives was comparatively
analyzed with DSC.
CELL 229
CELL 228
Sugars and post-translational modifications are critical
biological markers that modulate the properties of Proteins.
Our work studies the interplay of proteins, sugars and
modifications. This lecture will cover emerging areas in our
group in: (a) biomolecule construction with an emphasis on
new bond-forming processes compatible with biology & (b) use
of chemical probes & modulators of carbohydrate & protein
processing events. (i) Synthetic biology’s development at the
start of this century may be compared with synthetic organic
chemistry’s expansion at the start of the last; after decades of
isolation, identification, analysis and functional confirmation the
future logical and free-ranging redesign of biomolecules offers
tantalizing opportunities. (ii) Synthetic biologics and their
applications: drug delivery; selective protein degradation;
nanomolar inhibitors of bacterial interactions; gene delivery
vehicles; probes of in vivo function; non-invasive presymptopmatic disease diagnosis; targeted high-intensity
radioprobes; designed glycoconjugate vaccines. (iii) Chemical
probes and modulators: Delineation of mechanisms of
carbohydrate- and protein-processing systems and their
ligands allows not only an understanding of their fundamental
role in biology and immunology but also the use of molecules
to modulate and manipulate such processes, with a strong
associated potential for diagnosis, therapy and intervention in
medicine.
Novel functional lignins as building blocks in preparation
of polyurethane materials
Jennifer Dietz1, [email protected], Markus
Biesalski2, Michael Duetsch3, Okko Ringena3, Sanna
Valkonen4. (1) Macromolecular Chemistry & Paper Chemistry,
TU
Darmstadt,
Darmstadt,
Hessen,
Germany
(2)
Macromolecular Chemistry & Paper Chemistry, TU Darmstadt,
Darmstadt, Germany (3) UPM, Augsburg, Germany (4) UPM,
Lappeenranta, Finland
There have been large efforts in utilizing lignin-polymers for
various materials applications in the past. However, due to the
heterogeneity of the crude polymeric material and due to often
non-trivial chemical transformation into reactive precursorspecies, lignin-polymers have yet not advanced into materials
applications to a large extend.[1,2] The transition into a material
of higher value is inherently coupled to understanding and
developing precise chemical modification routes of lignins as
well as processing of such reactive precursors, rather than
trying to adapt the crude polymer to existing technologies. With
respect to the latter, we here introduce novel routes to ligninbased polyurethanes, progressing from rigid as well as soft
lignin-polyurethane foams to polyurethane coatings, containing
adjustable
amounts
of
lignin.
The polyurethanes we prepare are two-component (polyol and
polyisocyanate component) systems meaning two different
parts, which are mixed to obtain polyurethane products.
Since lignin is also a (bio-)polyol it can be directly mixed into
the
polyol
component
of
polyurethanes.
Another way of using lignin for designing polyurethane
materials, is to first modify lignin, e.g. into a reactive isocyanate
species, and then polymerizing such reactive precursor
molecules using appropriate co-feeds. Such activated lignins
can be mixed into the polyisocyanate part of polyurethanes.
Another approach is the preparation of pre-polymers.
In conclusion, we will show that it is possible to use lignins
either as a filler and/or pigment in polyurethanes and even to
substitute parts of the two components used for polyurethane
preparation to produce novel bio-based materials.
1. Thakur, V.K., et al., Progress in Green Polymer Composites
from Lignin for Multifunctional Applications: A Review. Acs
Sustainable Chemistry & Engineering, 2014. 2(5): p. 10721092.
2. Laurichesse, S., C. Huillet, and L. Averous, Original polyols
based on organosolv lignin and fatty acids: new bio-based
building blocks for segmented polyurethane synthesis. Green
Chemistry, 2014. 16(8): p. 3958-3970.
Sugars and proteins: Exploring and exploiting sugar
chemical biology
Benjamin G. Davis, [email protected]. Univ of
Oxford Chem Rsrch Lab, Oxford, United Kingdom
CELL 230
Synthesis and properties of end-functionalized methyl
cellulose derivatives: Bridging the gap between oligo- and
polysaccharides
Hiroshi Kamitakahara, [email protected], Atsushi
Nakagawa, Ryo Suhara, Mao Yamagami, Haruko Kawano,
Toshiyuki Takano. Graduate School of Agriculture, Kyoto
University, Kyoto, Japan
Aqueous solution of methylcellulose shows thermo-reversible
gelation behavior at about 60°C. The industrial methylcellulose
has been said to be an alternating block copolymer, which
consists of densely substituted hydrophobic and less
substituted hydrophilic block sequences. To understand the
thermo-reversible gelation behavior, we have synthesized
model compounds for cross-linking loci in methylcellulose from
oligo- to polysaccharide derivatives. Consequently, substituent
patterns within the anhydro glucosyl residue of methylcellulose
and along the methylcellulose backbone strongly affected their
physical properties such as surface activities, thermoresponsive aggregation, and gelation properties. The diblock
structure consisting of cellobiosyl block and approx. ten 2,3,6tri-O-methyl-glucopyranosyl units was of crucial importance for
thermoreversible gelation of methylcellulose. Moreover, selfassembled nanostructures of diblock methylcellulose
derivatives in water varied with their molecular weights from
ellipsoidal nanoparticles to ribbon-like nanofibers. Recently, we
developed a general synthetic method to obtain endfunctionalized methylcellulose derivatives. Variable molecules
such as oligosaccharides of academic interest will be able to
be conjugated at the end of methylcellulose derivatives with
thermo-responsive property.
CELL 231
CELL 232
Synthesis and biological evaluation of carbohydratefunctionalized polymers
Hien M. Nguyen, [email protected]. Dept of Chemistry,
University of Iowa, Iowa City, Iowa, United States
Multivalent interactions play important roles in a variety of
biological processes. Major roles of multivalent interactions are
to enhance weak protein-carbohydrate interactions and change
protein receptor proximity. In many cases, a multivalent ligand
can bind to a number of protein receptors with enhanced
affinity. Extensions of this finding reveal that long polymers
result in enhanced multivalent binding (termed ‘avidity’)
compared to short polymers or monomers because of their
ability to span a greater number of binding sites. To take
advantage of the multivalent binding concept for achieving the
highest binding affinity between synthetic oligosaccharide
epitopes and proteins of interest, we have designed and
synthesized a number of oligosaccharide-derived bivalent
polymers. Their ability to bind to ConA, 2G12, and antithrombin
of interest has been determined using ITC techniques. The
synthesis and biological studies of oligosaccharides-derived
bivalent polymers will be presented at this conference.
CELL 233
Bioengineering of third generation chitosans
Regioselective synthesis of polysaccharide derivatives
Zheng3,
significant recent advances against this problem. We will report
new reactions, new protective groups, and new routes to
regioselectively substituted polysaccharide esters. We will also
describe versatile routes to a broad variety of aminosubstituted polysaccharides which have interesting potential in
biomedical applications.
Zhang2,
Pereira4,
Xueyan
Ruoran
Junia
Kevin J.
Edgar1, [email protected]. (1) Mail Code 0323, Virginia Tech,
Blacksburg, Virginia, United States (2) Macromolecular
Science and Engineering, Virginia Tech, Blacksburg, Virginia,
United States (3) Chemistry, Virginia Tech, Blacksburg,
Virginia, United States (4) Macromolecules & Interfaces
Institute, Virginia Tech, Blacksburg, Virginia, United States
Regioselective substitution of polysaccharides is a difficult
problem. Polysaccharides contain many nucleophilic groups,
including multiple hydroxyl groups and in some cases amine
groups. The hydroxyl groups are chemically nonequivalent, but
have low reactivity due to their close proximity to the polymer
backbone and their restricted approach angles. This requires
that rather strong conditions be used for reactions in which
these hydroxyls act as nucleophiles; powerful catalysts (e.g.
NaOH, H2SO4), high temperatures (often ≥ 80ºC), and long
reaction times (often 12-24 h). Such conditions are not
conducive to selectivity. Yet in the few cases where we are
able to achieve regioselective substitution of polysaccharides,
it is abundantly clear that regioselectivity has a powerful effect
on polymer properties. Regioselectively substituted derivatives
differ strongly from randomly substituted but otherwise
equivalent derivatives with regard to properties like solubility,
thermal behavior, crystallinity, colligative properties, and optical
characteristics. Thus control of regioselectivity of substitution is
one of the critical remaining unconquered problems in
polysaccharide chemistry. Our group has made several
Bruno M. Moerschbacher, [email protected].
Institute for Biology and Biotechnology of Plants, WWU
Münster University, Münster, Germany
Chitosans are among the most promising and most versatile
functional biopolymers, with superior material properties and
biological functionalities. Chitosans can form gels, films, and
fibers, nano-particles, nano-capsules, and nano-fibers, they
have antimicrobial and plant strengthening, wound healing and
drug delivering potential – but the best suited chitosan differs
for each application, necessitating a detailed molecular
understanding of structure/function relationships. The term
chitosan really refers to a family of oligo- and polysaccharides
differing in their degree of polymerisation (DP), degree of
acetylation (DA), and pattern of acetylation (PA), and initial
commercial chitosans were rather ill-defined mixtures with
large batch-to-batch differences. Using series of well-defined
chitosans with narrow ranges of DP and DA, and defined
random PA, we showed that chitosans with low DA and
intermediate DP exhibited the highest antimicrobial activities,
independent of the bacteria or fungi studied, while chitosans
with intermediate DA and high DP were best for plant
strengthening, but the optimal chitosan differed between plant
species and disease. These ‘second generation’ chitosans are
now available on industrial scale and allow for the first time the
development of reliable chitosan-based plant protectants with
good efficacies. However, biomedical activities of these
chitosans still tend to remain unreliable. We have argued that
biological activities of chitosans will crucially be determined by
their PA if the target tissue contains a sequence-specific
chitosan hydrolase – such as human chitotriosidase. However,
due to their chemical production processes from fully
acetylated chitin or fully de-acetylated polyglucosamine, the PA
of today’s chitosans is invariably random. We therefore aim to
develop enzymatic ways to produce chitosans with controlled,
non-random PA, and we have designed enzymatic/mass
spectrometric fingerprinting tools for their analysis. In addition,
we are developing biotechnological production ways for these
‘third generation’ bio-engineered chitosans using recombinant
chitin and chitosan synthesizing and modifying enzymes in a
cell factory approach.
Acknowledgement: This research has received funding from
the EU`s 5th, 6th, and 7th FP under grant agreements 00777,
013882, 222628, 613931, and EIB.10.042, as well as from the
German Federal Ministry of Education and Research, BMBF,
under grant agreements 03VWP0024, 0315935A and
0315543A.
CELL 234
Understanding and manipulating cellulase glycosylation
Zhongping Tan, [email protected]. Department of
Chemistry and Biochemistry, University of Colorado Boulder,
Boulder, Colorado, United States
Glycosylation is a powerful strategy for modulating properties
of enzymes. However, due to the heterogeneity and complexity
of glycans attached to enzymes, the quantitative analysis of
the relationships between glycosylation patterns and properties
of glycosylated enzymes has been seriously impeded. Using a
Family 1 carbohydrate-binding module (CBM) as a model
molecule, we demonstrated that chemical synthesis can serve
as a valuable tool to develop a deep understanding of enzyme
glycosylation. More importantly, by systematically comparing
the structurally well-defined glycoforms, our studies were able
to provide useful guidelines for cellulase glycoengineering.
CELL 235
Glycosynthase technology for enzymatic synthesis of
functional polysaccharides
Antoni Planas, [email protected]. Bioengineering
Department, Institut Quimic de Sarria, Universitat Ramon Llull,
Barcelona, Spain
Glycoside bond formation in the synthesis of oligosaccharides,
polysaccharides, and glycoconjugates requires accurate
control of the regio- and stereoselectivity of the condensation
reactions, imposing complex protection/deprotection itineraries
in chemical approaches. Nature uses glycosyltransferases and
transglycosidases for glycosylation reactions with exquisite
selectivity by direct glycosyl transfer. Glycosidases, acting in
reverse under kinetically controlled transglycosylation, have
been extensively used as biocatalysts for preparative in vitro
applications. More recently, engineered “glycosynthases”
became a step forward towards the preparative in vitro
synthesis
of
oligosaccharides
and
glycoconjugates.
Glycosynthases are mutant retaining glycoside hydrolases
(GH) in which the catalytic nucleophile has been removed
rendering an inactive hydrolase but able to catalyze
transglycosylation reactions from activated glycosyl donors
with opposite anomeric configuration to that of the natural
substrate of the parental hydrolase.1,2 The strategy has been
extended to other GH families including those acting by
substrate-assisted catalysis and inverting enzymes.3
We here report on the application of the glycosynthase
technology to the preparation of artificial polysaccharides by
enzymatic self-condensation of simple glycosyl donors leading
to polymers with defined structure.4 Key aspects to be
discussed are: 1) control of the degree of polymerization which
is dependent on the ratio between the rate of enzymecatalyzed polymerization and the rate of product precipitation,
and 2) introduction of modified glycosyl donors in the
glycosynthase-catalyzed polymerization which will lead to
functionalized polysaccharides with a regular pattern of
derivatization. Examples of engineered glycosynthases for the
preparation of mixed-linked β-glucans with regular distributions
of β-1,3 and β-1,4 linkages,6 and modified celluloses with a
regular pattern of functionalization4 will be described. A novel
HTS independent of enzyme specificity will assist further
directed evolution approaches for engineering improved
glycosynthases.6
(1) Mackenzie, et al. (1998) J.Am.Chem.Soc. 120, 5583–5584
(2) Malet, Planas (1998) FEBS Lett. 440, 208–212
(3) Wang, Huang (2009) Curr.Opin.Chem.Biol. 13,592–600
(4) Pérez, Faijes, Planas, (2011) Biomacromolecules 12, 494–
501
(5) Codera, Edgar, Faijes, Planas, in preparation
(6) Andrés, Aragunde, Planas (2014). Biochem.J. 458, 355363
CELL 236
Highly porous cellulose: Aerogels vs. cryogels
Nela Buchtova, Tatiana Budtova, [email protected]. CEMEF, Mines ParisTech, Sophia Antipolis,
France
Highly porous celluloses are very attractive for various
applications, from bio-medical (controlled release, scaffolds) to
engineering (thermal insulation) and electrochemical (when
pyrolised). In this work we compare two types of porous
cellulose II materials, both prepared via dissolution-coagulation
route but dried either via freeze-drying (cryogels) or with supercritical CO2 (aerogels). The influence of drying method and
cellulose concentration on the density, morphology, pore size
and specific surface area will be presented and discussed.
Acknowledgement: The work was performed in the frame of
“Aerowood” project financed by WoodWisdom Net+ EC
program.
CELL 237
Photoluminiscent
and
transparent
cellulose-based
aerogels and films carrying covalently immobilized coreshell quantum dots
Falk Wolfgang Liebner2, [email protected], Huiqing
Wang2,3, Sven Plappert2, Sakeena Quraishi1, Nicole Pircher2,
Thomas Rosenau2. (1) Boku University, Vienna, Austria (2)
Department of Chemistry, University of Natural Resources and
Life Sciences, Tulln, Austria (3) Hefei University of Technology,
Hefei, Anhui, China
The multifaceted response of quantum dots (QD) - mostly
semiconductor-based nanoparticles - towards photons of
different energy is an attractive feature for a wide range of
applications. Photoluminiscence as one of these phenomena
could be employed in bio-sensing of active compounds, tracing
of proteins and cells, or possibly true volumetric displays.
In this work we demonstrate that cellulose aerogels of tunable
photoluminiscence carrying covalently immobilized core-shell
QDs can be prepared either by 1) grafting of the QDs onto
cellulose in solution state or 2) loading and grafting of QDs
onto prefabricated aerogels. Furthermore we succeeded to
combine QDs with transparent aerogels that were obtained
from TEMPO-oxidized cellulose. This strongly encourages our
studies towards cellulose-based true volumetric displays. This
work on 3D structures has been complemented by synthesis of
highly transparent, mechanically strong flexible 2,3-dialdehyde
cellulose films and sheets which were also grafted with coreshell QDs.
CELL 238
Novel insights into the development of nanocomposites
based on cellulose nanofibers
Carmen Freire, [email protected], Armando Silvestre, Carlos
Pascoal Neto. CICECO/Department of Chemistry, University of
Aveiro, Aveiro, Portugal
In the later decades, nanocellulose fibers like bacterial
nanocellulose (BNC) and nanofibrillated (NFC) received
considerable attention as raw materials for the development of
innovative functional nanocomposites for application in several
fields such as in packaging, biomedical and electronic devices
and products, because of their unique properties. Bacterial
nanocellulose is generated, by several bacteria, as a
tridimensional network of nano- and micro-fibrils and has high
purity, water holding capacity, crystallinity, tensile strength and
Young modulus. Nanofibrillated cellulose is obtained by
disintegration of plant fibers from different sources, using highpressure homogenizers combined with enzymatic or chemical
treatments, and the obtained cellulose fibril suspensions bear
the appearance of highly viscous shear-thinning transparent
gels and have high aspect rations and specific surface areas
combined with remarkable strength and flexibility, low thermal
expansion, high optical transparency and specific barrier
properties.The preparation of (nano)composite materials based
on nanocellulose fibers (NFC and BNC) involves different
approaches, including compounding with thermoplastic
matrices, combination with other natural polymers (normally by
casting), blending with other materials such as inorganic
nanoparticles and in situ polymerization approaches. The
application of these strategies led to the preparation of a wide
range of promising functional materials, such as for example,
transparent nanocomposite materials, membranes with barrier
properties, membranes for controlled drug release, scaffolds
for tissue regeneration, conductive films and antimicrobial
materials, among many others. In this communication the most
recent research activities carried out in this field in our group
will be presented and discussed.
CELL 239
Honeycomb-patterned cellulose films as a promising tool
to investigate deformation of wood cross section and
wood cell wall formation
Yasumitsu Uraki1, [email protected], Qiang Li2,
Teuku B. Bardant3, Keiichi Koda2. (1) Research Faculty of
Agricuture, Hokkaido University, Sapporo, Japan (2) Hokkaido
University, Sapporo, Japan (3) Chemistry, LIPI, Serpong,
Indonesia
We have developed honeycomb-patterned cellulose films with
cellulose I and II polymorphisms, as a fundamental framework
for creating artificial wood cell wall. By using the films with
cellulose II polymorphism, which were prepared from cellulose
acetate, we evidently demonstrated high validity of a bendingstretching model theory, proposed by C. S. Moden and L. J.
Berglund, to elucidate deformation mechanism of wood crosssection. Especially, the deformation of xylan-adsorbed
honeycomb-patterned cellulose film was well consistent to the
predicted deformation using important factors for earlywood
and latewood proposed by the theory. Next, we attempted to
prepare laminated artificial wood cell wall, mimicking the
formation/deposition process of wood cell wall components in
tree. The honeycomb-patterned bacterial cellulose films with
cellulose I polymorphism were found to absorb much xylan
than normal pellicle of bacterial cellulose, suggesting that the
honeycomb-patterned film provided larger accessible area to
xylan than the pellicle. Polymerization of coniferyl alcohol as a
lignin precursor with a horse radish peroxidase and hydrogen
peroxide on the matrix of xylan-adsorbed honeycombpatterned bacterial cellulose gave much dehydrogenative
polymer (DHP) than that on xylan-adsorbed pellicle, and the
resulting DHP was rich in 8-O-4’ interunitary linkage. This
result suggests that xylan acts as a scaffold for DHP formation
and template for 8-O-4’ interunitary linkage.
CELL 240
High-added value materials with cellulose nanocrystals
Christoph Weder, [email protected]. University of
Fribourg, Adolphe Merkle Institut, Fribourg, Switzerland
Cellulose nanocrystals (CNCs) are attracting growing interest
as inexpensive and renewable components that are useful for
the creation of a broad variety of nanomaterials. This
presentation will discuss several new examples of advanced
materials systems for high-added-value applications. The
ability to switch the interactions between (surface-modified)
CNCs in polymer matrices has allowed the design of
mechanically adaptive nanocomposites, whose properties can
be influenced by external stimuli such as irradiation with light or
exposure to physiological conditions. The possibility to create
functional high surface area materials was utilized for
fluorescence-based sensing schemes; in this case, porous
CNC nanostructures were fixated with the help of a polymeric
binder and a portion of the scaffold’s hydroxyl surface groups
was reacted with fluorescent sensor motifs. The high surface
area and the possibility to chemically anchor a payload were
exploited for CNC-based pro-fragrances; here CNCs were
decorated with fragrance molecules using a short linker, which
serves to covalently connect the fragrance molecules with the
nanocarrier and promotes slow release of the payload via a
retro 1,4-Michael-type addition reaction.
CELL 241
Effects of structure of cellulose in solid state on functions
and properties of composite materials
results from different characterization methods in order to
make characterization more reliable and remove what is
generally referred to as “inconsistencies” in the literature.
CELL 243
Lina Zhang1, [email protected], qiyang wang2, Jinhua
Guo3, Ang Lu3. (1) Wuhan University, Wuhan Hubei, China (2)
Wuhan university, Wuhan, China (3) Department of Chemistry,
Wuhan University, Wuhan, Hubei, China
To understand the role of the structure of cellulose in solid
state, regenerated cellulose composite materials with different
functions and properties were fabricated directly from cellulose
solution dissolved in alkali hydroxide/urea aqueous system
with cooling. On the basis of the removability of cellulose
molecules in the hydrogel state, a new class of bioplastic was
constructed by hot-pressing the hydrogel prepared from the
cellulose solution by physical cross-linking to induce a
transition in the aggregated structure, leading to the plastic
deformation. The cellulose bioplastics exhibited much higher
tensile strength, the flexural strength and thermal stability as
well as lower coefficient of thermal expansion than the
common plastics. Moreover, regulated photoluminescence
bioplastics were constructed by hot-pressing the cellulose
hydrogel with lanthanide elements, which were fixed through
electrostatic adsorption, and the various colors could be
modulated by adjusting the three primary rare earth materials.
Furthermore, magnetic cellulose plastics were prepared by hotpressing cellulose/Fe3O4 hydrogel under strong uniform field,
leading to the orientation of the Fe3O4 nanoparticles.
CELL 242
Surface chemistry and characterisation of cellulose
nanocrystals
Samuel
Eyley,
[email protected].
Leuven, Kortrijk, Belgium
Wim
Chemical
Thielemans,
Engineering, KU
The surface modification of nanocrystalline cellulose is
receiving a large amount of attention to introduce different
surface functionalities and to vary their interaction with
solvents, polymers, surface and each other. To modify their
surface, it is possible to use their primary and secondary
hydroxyl groups. However, significant hydrogen bonding of
these groups on the nanowhisker surfaces alters their reactivity
when compared to homogeneous cellulose systems. Amongst
nanocelluloses, cellulose nanowhiskers are also single crystals
of cellulose, making the positioning of surface modifications
predictable when using selective modification routes as will be
shown in this talk. In addition to these effects, it is also
paramount to clean the nanowhisker surface as the normal
purification procedures used during nanocellulose preparation
(mostly aqueous and relative gentile) are not sufficient to
remove adsorbed impurities (lignin fragments, glucose
hydrolysis products). During this talk I will discuss a reliable
purification procedure to make surface modifications more
reproducible. This will be followed with a variety of surface
modifications developed in our group based on reactions such
as esterifications and thiole-ene and azide-alkyne-click
reactions to create cationized, polymer-modified or fluorescent
nanoparticles. In particular, a recent method to create highly
substituted cationic nanoparticles will be discussed in detail.
These examples will also be used to present improvements in
some characterization methods of nanocrystalline cellulose
(XRD and XPS) and to discuss possibilities to directly compare
Formation of chiral nematic films from cellulose
nanocrystal suspensions is a two-stage process
Xiaoyue Mu, Derek G. Gray, [email protected].
Chemistry, McGill University, Montreal, Quebec, Canada
The evaporation of aqueous suspensions of cellulose
nanocrystals (CNC) gives iridescent chiral nematic films with
reflection colors at visible wavelengths. Possible applications
as structural pigments, photonic materials and as templates for
other porous and inorganic chiral nematic materials have been
proposed. A key problem is controlling the chiral nematic pitch,
P, and hence the reflection colors of CNC films. By adding D(+)-glucose to the suspension, we show that the change in P
during evaporation occurs in two distinct stages. The first stage
is the decrease in P as the concentration of CNC in the chiral
nematic suspension increases due to evaporation; addition of
glucose causes a decrease in P in this stage. In a second
stage, a concentration of CNC is reached where formation of
ordered gels and glasses prevents further major changes in P.
The addition of glucose lowers the CNC concentration at which
this occurs, leading to an increase in P, and hence an overall
shift to the red end of the spectrum compared to the color of
the film formed without added glucose. In general, the final
reflection properties of chiral nematic films will depend on (i)
the equilibrium values of the chiral nematic phase, (ii) the
equilibrium and kinetic factors governing gelation and glass
formation and (iii) the orientational order and spatial distribution
of chiral nematic elements in the final film.
CELL 244
Advanced polysaccharide
applications
materials
for
biomedical
Manja Kurečič1, [email protected], Uroš Maver3,
Tamilselvan Mohan4, Rupert Kargl1, Stefan Spirk2, Volker
Ribitsch4, Karin Stana-Kleinschek1, [email protected].
(1) Faculty of Mechanical Engineering, Institute of Engineering
Materials and Design, University of Maribor, Smetanova ulica
17, 2000 Maribor, Slovenia (2) Institute for the Chemistry and
Technology of Materials, Graz University of Technology,
Stremayrgasse 9, 8010 Graz, Austria (3) Faculty of Medicine,
University of Maribor, Taborska ulica 8, 2000 Maribor, Slovenia
(4) Institute of Chemistry, University of Graz, Heinrichstraße
28, 8010 Graz, Austria
Polysaccharides (PS) have a huge potential to be applied in
advanced applications. For many of these functions surface
properties and the interactions at their interface are crucial. By
having
a
detailed
understanding
of
wetting,
adsorption/desorption, adhesion, morphology and internal and
surface structure, PS-materials with desired properties can be
created. Spin-coated thin films of PSs are one platform that
can be used to elucidate these surface phenomena.
Knowledge created in this way can be transferred to the
development of functional materials. For the characterization of
their composition and morphology, modern surface analytical
methods such as a quartz-crystal microbalance, surface
plasmon resonance, or X-ray photoelectron spectroscopy are
employed. These films can further be surface structured and
serve as a basis for functional layers in optical sensors for the
detection of DNA and proteins, which are examples for PS
used in biomedical applications.The biological efficacy of many
charged polysaccharides can also be exploited in the coating
of metal (nano-) particles which can be applied in modern
wound dressings leading to antimicrobial properties and
biocompatibility. Electrospinning of PSs and their derivatives
with incorporated functional substances for wound dressings
that are antimicrobial, super-absorbing and analgesic
represents another example where basic and applied knowhow on PS-materials are leading to innovative products.
Exploitation of naturally derived extracts with excellent
antimicrobial as well as antioxidant activities, and cross-linking
agents for structural tuning, can be used for preparation of
different spinning formulations and wound dressings. These
were studied for their surface properties, biocompatibility,
bioactivity, wettability and morphology. In this presentation an
overview on the current achievements in these fields of
research will be given.
CELL 245
Construction of functional biomaterials of hemicellulosechitosan
Yumin Du1, [email protected], Shuping Wu1, Xiaowen
Shi1, Hongbing Deng1, Ang Lu2, Lina Zhang3. (1) Center of
Research on Biomass Resource, Wuhan University, Wuhan
Hubei, China (2) Department of Chemistry, Wuhan University,
Wuhan, Hubei, China (3) Wuhan University, Wuhan Hubei,
China
The structure of hemicellulose extracted from corncob was
investigated to reveal that the lowest degree of branching and
lower molecular weight of hemicellulose led to low steric
hindrance, which was beneficial to Mailard reaction. Novel
functional biomaterials based on hemicellulose of corncob and
chitosan were constructed by the regulation of Maillard
reaction process. Meanwhile, the correlations between
structure and properties of the biomaterials were figured out.
Their structures and properties were studied with fluorescence
spectra, FT-IR, X-ray diffraction, antioxidant activity and
antimicrobial assessment. The results indicated that the lower
molecular weight of the reactants was, and the more easily
Maillard reaction occurred. The antioxidant capacity and
antibacterial activity of xylan-chitooligomer-zinc complex
obtained by optimizing the reaction conditions were 2.5 times
and 5 times higher than that of chitooligomer, respectively. On
the other hand, the novel biomaterials were constructed via
Schiff base reaction between the amino group of the chitosan
or carboxymethyl chitosan and the reductive carbonyl group of
the hemicellulose by incorporating TiO2 nanoparticles into the
network structure. The biomaterials exhibited excellent
antibacterial activity and hemostasis properties. Furthermore,
xylan-chitosan-nanoTiO2 hybrid with multiple structure and
abundant adsorption sites were also fabricated, showing an
outstanding candidate as a kind of recyclable, effective, and
selective bioadsorbent for the removal of heavy metal ions
from wastewater.
CELL 246
Thermal inducing self-assemble nanofibrils to construct
chitin microspheres for tissue engineering
Bo Duan, [email protected], Lina zhang. Chemistry, Wuhan
University, China, Wuhan, Hubei, China
Chitin was dissolved completely in 11 wt% NaOH/4 wt% urea
aqueous solution via the freezing/thawing method. The chitin
nanofibrous microspheres were fabricated through the selfassemble of the chitin chain in the aqueous system. In this
case, the sheath-like structure of inclusion complex associated
with chitin, NaOH and urea was broken via the heating way
and the stiff chitin chain arranged parallelly and self-assembled
into nanofibrils through the hydrogen bonding between the
chitin chains to form chitin microsphere consisted of
nanofibrils. The chitin microspheres with different size (5-150
mm) exhibited 3D-mesh nanofibrous structure and large
surface area, which can promote the transport of the oxygen
and protein. Furthermore, the homogeneous nanofribrous
structure could enhance the adhesion of the cells on the
microspheres, showing excellent biocompatibility, safety and
adhesion to cells. These versatile biomimetic microspheres
may provide a powerful tool to be used as an injectable system
for non-invasive tissue regeneration engineering applications.
CELL 247
Antibacterial wound dressing electrospun nanofibers from
chitosan - iodoacetamide
Abdelrahman M. Abdelgawad1, [email protected], Samuel
Hudson 2, Orlando J. Rojas1. (1) Forest Biomaterials, North
Carolina State University, Raleigh, North Carolina, United
States (2) Fiber and Polymer Science Program , North
Carolina State University, Raleigh, North Carolina, United
States
A new and effective antibacterial wound dressing nanofibers
based on chitosan iodo-acetamide was successfully prepared
via electrospinning. Chitosan derivative, chitosan iodoacetamide, was obtained by the introduction of Iodoacetic acid
moiety to the chains of chitosan polymer. The reaction was
mediated through carbondiimide intermediate using ethyl-3(3dimethylamminopropyl) carbondiimide hydrochloride (EDAC)
as a coupling agent. The chemical structure was verified by
FT-IR and 1H NMR spectra. Chitosan iodo-acetamide
derivative was found to react with th e cysteine residuals, of
the outer cellular membrane of the bacteria, faster than its
thiolated counterparts. Electrospun nanofiber mats were
obtained from PVA/CS, PVA/CS/thiol chitosan, and
PVA/CS/chitosan
Iodoacetamide
blended
solutions.
PVA/CS/chitosan Iodoacetamide blended solutions showed
superior morphological and antibacterial properties over that
obtained from PVA/CS/thiol-chitosan. The antimicrobial activity
of the nanofiber mats were performed against gram negative
bacteria E. coli. PVA/CS/chitosan Iodoacetamide showed
bactericidal activity after only 4h of treatment, whereas,
PVA/CS/thiol-chitosan after 24h.
CELL 248
Surface phthaloylation of chitin nanofiber in aqueous
media to improve dispersibility in and ultraviolet
protection properties
Shinsuke Ifuku, [email protected], Nana Suzuki.
Graduate School of Engineering, Tottori University, Tottori,
Japan
Phthaloylation of chitin nanofiber (NF) was achieved by
reaction with phthalic anhydride in aqueous media. The
phthaloyl group was quantitatively introduced into an amino
group of a surface-deacetylated chitin NF surface. The
characteristic nanofiber network structure was maintained after
phthaloylation. The NFs were dispersed homogeneously in
organic solvents, and even in several aromatic solvents, due to
the high solvation interactions with the phthaloyl group. In
addition, the homogeneous dispersions in aromatic solvents
had reversible thermo-responsive properties and exhibited a
dispersive-to-precipitate phase transition response at
approximately 25 C. Due to the presence of the phthaloyl
group, the NF dispersion and the nano-composite film cut
harmful ultraviolet light.
CELL 249
Chitosan
modification
via
polymerization
and
“grafting
homogeneous media
nitroxide-mediated
to”
approach
in
Omar García-Valdez2, Sean George2, Enrique Saldivar1,
Pascale
Champagne3,
Michael
F.
Cunningham2,
[email protected]. (1) Ctr Investigation Appl
Chem, Saltillo, Mexico (2) Dept of Chemical Engineering,
Queens University, Kingston, Ontario, Canada (3) Civil
Engineering/Chemical Engineering, Queens University,
Kingston, Ontario, Canada
A facile strategy to modify chitosan (CTS) with a wide
catalogue of well-defined molecular weight graft polymers and
copolymers via nitroxide-mediated polymerization (NMP) in
homogeneous media is presented. This strategy involves first
functionalizing CTS with glycidyl methacrylate (GMA) and
sodium dodecylbenzenesulfonate (SDBS) to yield CTS-SDBSg-GMA, which is soluble in organic media. The second step
involves grafting SG1-terminated polymers, previously
synthesized via NMP, to the CTS-SDBS-g-GMA. Several
different polymers (including both homopolymers, random
copolymers, and block copolymers) can be grafted, including
poly(styrene) (PS), poly(butyl acrylate) (PBA), poly(acrylic acid)
(PAA),
poly(styrene-b-acrylic
acid)
(PS-b-PAA),
and
poly(styrene-r-acrylic acid) (PS-r-PAA). NMR, TGA, and FT-IR
analyses were used to confirm the grafted CTS structure.
CELL 250
Synthesis of functional sponges from nanofibrillated
cellulose using a silylation process in water
Philippe
Tingaut1,
[email protected],
Tanja
Zimmermann1, Gilles Sèbe2. (1) Applied Wood Materials
Laboratory, EMPA, Swiss Federal Laboratories for Materials
Science and Technology, Dübendorf, Switzerland (2)
Laboratoire de Chimie des Polymères Organiques, University
of Bordeaux, Pessac, France
Nanofibrillated Cellulose (NFC) consists of long, flexible and
interconnected cellulose nanofibers, with diameters from 10 to
100 nm and aspect ratios from 50 to 100 (Figure 1a). NFC is
generally isolated from the cellulose pulp using a mechanical
disintegration process in water, which generates a suspension
containing entangled hydrophilic cellulose I nanofibers. The
subsequent replacement of water with air using freeze-drying
gives rise to a sponge, also called foam or aerogel, with an
architecture displaying long and entangled cellulose I
nanofibers. Nevertheless, the scope of applications of the
sponges is often restricted, due to the single functionality
present on the cellulosic nanofibers and the strong hydrophilic
character of the porous materials.1-4 Here, we present an
innovative silylation process in water to efficiently synthesize
NFC sponges with tailored properties and to further broaden
the application fields of the neat sponges. The highly porous (≥
99 %) sponges are engineered by freeze-drying water
suspensions of NFC in presence of alkoxysilane molecules
(Figure 1b). Two examples are presented using
methyltrimethoxysilane and 3-aminopropyltriethoxysilane as
modifying agents, leading to functional sponges with possible
applications in oil-water separation5 and CO2 capture6, 7,
respectively. The sponges have been systematically
characterized with Scanning Electron Microscopy (SEM),
elemental analysis, solid-state Nuclear Magnetic Resonance
(NMR) spectroscopy (CP-MAS 13C and 29Si) and X-Ray
Photoelectron spectroscopy (XPS).
1. Aulin et al., Soft Matter 2010, 6 (14), 3298.
2. Paakko et al., Soft Matter 2008, 4 (12), 2492.
3. Siro and Plackett, Cellulose 2010, 17 (3), 459
4. Tingaut et al., In Handbook of Green Materials: Processing
Technologies, Properties and Applications 2014; Vol. 1.
5. Zhang et al., Chem. Mater. 2014, 26 (8), 2659
6. Gebald et al., Env. Sci. Technol., 2013, 47 (17), 10063
7. Gebald et al., Env. Sci. Technol. 2011, 45, (20), 9101
CELL 251
Functionalization of nanofibrillated cellulose with
alkoxysilanes in water and reinforcing properties in PDMS
networks
Gilles Sèbe2, [email protected], Tanja Zimmermann1, Philippe
Tingaut1. (1) Applied Wood Materials Laboratory, EMPA, Swiss
Federal Laboratories for Materials Science and Technology,
Dübendorf, Switzerland (2) Laboratoire de Chimie des
Polymères Organiques, University of Bordeaux, Pessac,
France
Recent concerns about sustainable development and
petroleum resources depletion have led to look for alternative
polymer materials based on renewable resources. In this
context, nanofibrillated cellulose (NFC) displays attracting
properties related to its unique nanostructure, high aspect
ratio, excellent mechanical properties, biodegradability and
renewability. NFC consists of long, flexible and interconnected
cellulose nanofibers, which are isolated from wood or
agricultural by-products by mechanical disintegration. Although
it showed promise in a wide variety of applications (reinforcing
filler, porous scaffold, emulsifying agent, templating nanosubstrate…), its hydroxylated surface has been often pointed
out as a limiting factor. For instance, the hydrogen bonding
aggregation of NFC in low polarity environments rends it
difficult to efficiently reinforce many commercial hydrophobic
polymers. In this context, we developed a versatile method for
the functionalization of NFC in water, which allowed improving
its dispersive and interfacial properties when used as
reinforcing filler in hydrophobic matrices. NFC produced from
oat straw was silylated by a sol-gel process in water, using
methyltrimethoxysilane (MTMS) as a model alkoxysilane. The
silylated material was thoroughly characterized by elemental
analysis, Fourier transform infrared (FT-IR) spectroscopy, solid
state 13C and 29Si cross polarization-magic angle (CP-MAS)
nuclear magnetic resonance (NMR), Scanning Electron
Microscopy (SEM), Wavelength Dispersive X-Ray (WDX),
contact angle measurements and thermal gravimetric analysis
(TGA). The reinforcing properties of MTMS-treated NFC in
PDMS networks will be particularly discussed, through the
comparison of the static and dynamic mechanical properties of
model nanocomposites.
CELL 252
Tailoring barrier-properties of paper substrates using
fiber-immobilized polyvinyl acetate copolymer
Michael
Graf,
[email protected],
Markus
Biesalski. Macromolecular chemistry and paper chemistry, TU
Darmstadt, Darmstadt, Hessen, Germany
In recent years, Paper-based materials have witnessed
increasing interest, both from academia and industry, as a
renewable, low-cost and non-toxic ‘green’ material for the
design of “high-tech” devices, such as microfluidic papers or
paper-materials used in microelectronic applications. Despite
low-cost and well-established technologies to produce paper in
large scale, the material offers a number of interesting
features, such as high surface area, and tunable porosity. The
latter properties lay the foundation, in particular, for the use of
paper in microfluidic applications, where paper can achieve a
pump-less laminar fluid-flow in a channel. Often several
chemical steps are necessary to design such channels, which
can limit the control over channel-definition, and intrinsic
paper-properties (porosity etc.). In this paper, we introduce a
novel method in order to tailor the chemical properties of paper
sheets in a simple process, where only one polymer coat is
used to modify paper fibers, and by simple polymeranalogous
reactions, this polymer coating can be switched from
hydrophobic to hydrophilic surface properties. For this
instance, we focus on photo-reactive polyvinyl acetate as a
functional coating that can be applied onto various substrates
from solution by dip-coating or doctor blading. These
copolymers can easily be synthesized using free radical
copolymerization and offer uncomplicated photo-chemically
induced surface-attachment and network generation properties
by direct C-C bond formation via UV excitation of
benzophenone moieties, which have been incorporated into
the copolymer in desired ratios. Additionally, the hydrophobic
polyvinyl acetate can be converted into hydrophilic polyvinyl
alcohol by simple and fast ester hydrolysis in alkaline
methanolic sodium hydroxide solution. This change in surface
chemistry allows direct micro structuring of a substrate surface
into non-wetting and wetting domains and ultimately the
fabrication of microfluidic structures or channels on a substrate
by spatially resolved application of methanolic sodium
hydroxide solution via inkjet printing.
CELL 253
Photocatalytic papers with enhanced chemical stability in
wet conditions
Markus A. Biesalski1, [email protected], Florian
Loyal2. (1) Department of Chemistry, Technische Universität
Darmstadt, Darmstadt, Germany (2) Makromolekulare Chemie
und Papierchemie, Technische Universiaet Darmstadt,
Darmstadt, Germany
In this contribution, we will introduce a novel concept in the
design of photocatalytically active paper sheets with enhanced
wet-strength properties. Catechol-functionalized copolymers
are being prepared which consist of a non-toxic
Polyacrylamide matrix, a catechol function used for
coordinating photocatalytic active TiO2 to lignocellulosic fibers,
and a benzophenone function, which enhances the wet
strength of a paper sheet by photo-chemically crosslinking
adjacent fibers. The copolymers can be applied either prior to
the paper making process, by in situ confining the
macromolecules, fibers and the pigments in a slurry, or the
copolymers are surface-transferred to readily prepared paper
sheets, and subsequently loaded with the pigment. The
pigments are strongly coordinated to the catechol functions in
the copolymers, and the macromolecules are cross-linked to
the fibers by UV-light illumination. Model-studies on the
photocatalytic activity of so-prepared functional paper sheets
reveal that the rate constants at which organic substances are
degraded depend on the pigment used, as well as the volumeto-surface ratio of the pigments, and can therefore be tailored
to specific needs. Because the pigments are attached to the
copolymers, and the latter surround the lignocellulosic fibers as
a protective shell, a decrease in mechanical stability (i.e. wet
strength) can be largely avoided, and long term illumination
with UV light does not disintegrate the thin sheets. This is in
contrast to paper sheets, where the pigments are attached
directly to the fibers without (chemical) protection: here radicals
produced by the photocatalytic process also damage the fibers
and a loss of structural integrity may limit applications of such
papers.
CELL 254
Functionalization of nanofibrillated cellulose for improved
wet strength and biomedical applications
Henrikki Mertaniemi, [email protected], Olli T.
Ikkala. Dept of Applied Physics, Aalto University, Espoo,
Finland
Nanofibrillated cellulose is a promising biomaterial, being
capable of forming films and threads with good mechanical
strength. Recent studies have indicated that nanocellulose is
non-toxic and biocompatible, thus being suitable for biomedical
applications. However, the mechanical strength of
nanofibrillated cellulose is very limited after exposure to water;
the dry material has a tensile strength larger than 250 MPa,
decreasing to only a few MPa after soaking in water. In this
study, we have studied the effect of covalent cross-linking to
the wet strength of nanocellulose. The results show that after
being soaked in water, the functionalized nanocellulose has a
tensile strength of 100 MPa, retaining up to 40% of the tensile
strength of the dry material. The mechanical properties of
cross-linked nanocellulose will be discussed in detail,
comparing the performance of the functionalized nanofibrillated
cellulose in dry and wet state. Also, possible applications in the
biomedical field will be discussed.
CELL 255
Smart and responsive molecular ensembles from
renewable building blocks: Assemblies and properties
George John, [email protected]. City Colg of New York
Dpt Chem, New York, New York, United States
Adaptive response in functional systems of nature could be
best exemplified by the homeostasis (homeoviscous
alterations) or the tropism observed in flora and fauna. The
term “homeoviscous alteration” describes the process where,
the fluidity of the membrane is adjusted in response to a
perturbation such as temperature, pressure, etc. Most of the
naturally occurring lipid systems utilize their characteristic
unsaturations present in their lipid chains as a tool to execute
such elegant processes. Chilling sensitivity in plants are the
direct repercussion of the membrane dynamics in plants that
involve conformational changes and variations in unsaturation
component of the lipid membranes. Deciphering the stimuli
responsive character in such biological systems not only
provide information on the underlying mechanism in the race
for survival of the fittest, but also provide clues to generate
unique functional materials in the laboratory. Amphiphilic
molecules rich in unsaturations in their side chain are expected
to reminisce such interesting phenomenon and provide vistas
for newer soft materials. Taking cue from this, we designed an
amphiphile from a naturally available raw material – cardanol
that possess structural features akin to natural lipidic systems.
A reversible, micelle-vesicle transition, followed by vesicular
adhesion leading to sticky jelly phase was observed and
corroborated from cryo-electron microscopy and other physicochemical techniques.
CELL 256
Multiresponsive polymer-grafted cellulose nanocrystals
Firas Azzam1,2, Eder Siqueira1, Jean-Luc Putaux1, Frédéric
Pignon3, Bruno Jean1, [email protected]. (1)
CERMAV-CNRS, Grenoble Cedex 9, France (2) INRA ,
Nantes, France (3) Laboratoire Rhéologie et Procédés,
Grenoble, France
Despite their numerous properties such as renewability, high
specific surface area (~200-300 m2/g), excellent mechanical
properties (Young’s modulus ~150 GPa), liquid-crystalline selforganization ability, light weight, or non-toxicity, cellulose
nanocrystals (CNCs) still require a fine tuning of their surface
properties to be used as building blocks for materials with
advanced functionalities. In this framework, thermosensitive
polyetheramines were successfully grafted onto the surface of
CNCs using a peptidic coupling reaction after TEMPO
oxidation. This synthetic strategy combines several
advantages since it is carried out in aqueous medium under
ambient conditions and because the amide bond that form can
easily be characterized by spectroscopic techniques. The
properties of such thermosensitive polymer-grafted CNCs (TPCNCs) have been characterized by dynamic light scattering
(DLS), small angle neutron scattering, electron microscopy and
rheology. When dilute suspensions are considered, a highly
repeatable and reversible aggregation/redispersion behavior is
observed. Interestingly, results show that TP-CNCs assembly
upon temperature increase depends on the pH and ionic
strength of the suspensions. Actually, measurements reveal
that the electrosteric nature of the interaction forces make the
TP-CNCs temperature-, pH and salt-sensitive. When more
concentrated suspensions are used, a viscous liquid / elastic
solid transition is observed when the temperature is increased
beyond the polymer cloud point due to larger aggregates
formation and physical crosslinking. Such a multisensitive
behavior of polymer-grafted CNCs make them suitable for the
development of biobased materials with advanced functional
properties.
CELL 257
Structural response to humidity and property control in
cellulose nanocrystal-based films
Jairo A. Diaz1, [email protected], John W. Epling1,
Robert J. Moon2, Jeffrey P. Youngblood1. (1) School of
Materials Engineering, Purdue University, West Lafayette,
Indiana, United States (2) Forest Products Laboratory, US
Forest Service, Madison, Wisconsin, United States
Simultaneous
control
over
optical
properties
and
thermomechanical stability is highly desirable in the
manufacture of electronic devices. Cellulose nanocrystal
(CNC) films offer unique opportunities in this regard due to the
controlled optical reflection and low thermal expansion
achieved as response of CNC alignment within bulk films or
polymer composites. Based on the unmodified hydrophilic
nature of CNC films, relative humidity can modify the film
microstructure primarily in terms of optical reflection (e.g.
interlayer spacing modification) and thermomechanical
properties (e.g. coefficient of thermal expansion, stiffness). The
influence of factors governing the structural response to
humidity (e.g. CNC alignment, precursor suspension
conditions, sample morphology, etc.) is characterized in CNC
films with different structural features (e.g. iridescence,
orientation). The understanding of such interplay between
humidity, enhanced properties and structural performance
represents an essential element in advanced materials design.
CELL 258
CO2-switchable polysaccharide graft copolymers
Yong Huang2,1, [email protected], Ning Che1, Ruigang
Liu1, [email protected]. (1) State Key Laboratory of Polymer
Physics and Chemistry, Institute of Chemistry, Chinese
Academy of Sciences, Beijing, China (2) Chinese Academy of
Sciences, Technical Institute of Physics Chemistry, Beijing,
China
CO2 is a kind of nontoxic, cheap, abundant, and
environmentally friendly chemical reagent. In this paper, we
designed and synthesized CO2 stimulus responsive graft
copolymers based on polysaccharides. Dextran graft poly((Namidino)hexyl methacrylamide) (Dex-g-PAHMA) copolymers
were synthesized by free radical polymerization in aqueous
medium and characterized. Dex-g-PAHMA copolymers can
self-assemble into micelles with the PAHMA rich core and
dextran rich shell in aqueous media. The CO2 sensitivity of the
micelles was investigated by dynamic light scattering (DLS),
conductivity and Zeta potential. The results confirmed that the
Dex-g-PAHMA copolymer micelles have reversible CO2
sensitivity. Then, the CO2 sensitive properties of hydroxypropyl
cellulose graft poly(N,N-dimethyl aminoethyl methacrylate)
(HPC-g-PDMAEMA) were investigated. The correlation
between the structure and topology of the graft copolymer and
CO2 sensitive properties will be discussed. The CO2 sensitive
graft copolymers can be used for the drug carriers. In case of
loading doxorubicin (Dox), the Dox molecules mainly locate in
the core of the micelles. MTT assay indicated that the Dex-gPAHMA graft copolymers are non-toxic to cells in the
copolymer concentration range of 5-1000 μg mL–1. Whereas
the relative cell viability is greatly reduced with the increase of
copolymer concentration for Dox-loaded micelles. The Doxloaded micelles can be endocytosed by MCF-7 cells and the
Dox can release from micelles and diffuse into the cell nucleus.
The Dex-g-PAHMA copolymers have the promising
applications as drug carriers for cancer therapy.
CELL 259
High strength chitosan hydrogels fabricated from alkaline
aqueous solution
Jiangjiang
Duan,
[email protected].
University, Wuhan, Hubei, China, Wuhan, China
Wuhan
Commercial chitosan with high molecular weight and degree of
deacetylation were successfully dissolved in 7% KOH/8%
LiOH/8% urea aqueous solution via freezing-thawing process,
for the first time, and then novel chitosan hydrogels with
excellent mechanical properties and extremely pH-sensitive
properties were facilely constructed in the alkaline solvent
system. On the basis of their excellent performances, a robust
hydrogel reinforced by chitosan microgels were prepared,
which could be stretched to 20 times of original length, and
completely recovered after removing external force. Moreover,
a chitosan-based reversible bidirectional self-rolled bilayer
hydrogel triggered by pH changing was constructed via
combining chitosan and carboxymethyl cellulose to form a
janus hydrogel sheet. At low pH, rolling process of the hydrogel
was quickly, whereas a high pH, the hydrogel was rolled to the
opposite direction. These novel hydrogels would have
application potentials in the field of tissue engineering.
CELL 260
From a terminal olefin to functional groups: Olefin crossmetathesis and hydroboration-oxidation in the synthesis
of novel cellulose esters
Xiangtao Meng2,1, [email protected], Kevin J. Edgar2,1. (1)
Department of Sustainable Biomaterials, Virginia Tech,
Blacksburg, Virginia, United States (2) Macromolecules and
Interfaces Institute, Virginia Tech, Blacksburg, Virginia, United
States
Functionalization of cellulose and other polysaccharides has
relied extensively on conventional synthetic approaches such
as esterification and etherification. While such approaches
have indeed contributed to most of the commercially important
polysaccharide derivatives, the chemical structures and
available functionalities are somehow restricted by these
reactions. To this end, novel modification strategies that lead to
polysaccharide derivatives with new functionality and defined
structure in a mild and efficient manner would be of great
value. Herein, we report two such strategies: olefin crossmetathesis (CM) and hydroboration-oxidation reaction (HO),
towards novel functionalized cellulose esters. In general,
terminally olefinic side-chain modified cellulose esters (TOCE,
e.g. cellulose acetate undec-10-enoate) were used as
platforms, and the terminal olefin served as a handle for further
CM or HO reaction. By CM of TOCE with CM partners such as
acrylamides, cellulose esters with novel functionality such as
amide have been obtained. Organic acids, e.g. acetic acid,
were proven good solvents for the CM reaction in suppressing
coordination between CM catalyst (Hoveyda-Grubbs’ 2nd
generation) and amide-containing CM partners, and thus can
improve the conversion of the reaction. HO reaction, which can
transform terminal olefins to primary alcohols, is an alternative
approach to CM in the synthesis of hydroxyl-substituted
cellulose derivatives. Hydroboration of the terminal olefin on
TOCE was performed by 9-borabicyclo[3.3.1]nonane (9-BBN),
followed by oxidizing the intermediate to hydroxyl group by
H2O2. Instead of NaOH, weak base (e.g. NaOAc) was used to
catalyze the oxidation, which significantly minimized the
hydrolysis of ester linkages as well as chain-scission.
Moreover, this reaction was so mild that the ester functionality
was well preserved from being reduced by 9-BBN.
Characterization methods including FTIR and NMR proved the
success of this strategy in the synthesis of a family of novel
hydroxyl functionalized cellulose esters that cannot be
obtained by previous methods.
CELL 261
Softwood hemicelluloses promote the physical stability of
oil-in-water emulsions
Kirsi S. Mikkonen1, [email protected], Claire
Berton-Carabin2, Chunlin Xu3, Maija Tenkanen1, Karin
Schroën2. (1) University of Helsinki, Helsinki, Finland (2) Food
Process Engineering Group, Wageningen UR, Wageningen,
Netherlands (3) Laboratory of wood and paper chemistry, Abo
Akademi University, Turku, Finland
O-Acetyl-galactoglucomannans (GGM) are polysaccharides
abundantly available in softwoods and their mechanical pulp,
from which they dissolve in the process water of industrial mills
and can be isolated at high yield and purity. Recent efforts on
GGM research are focused on their recovery from modern
forestry biorefining processes and utilization in, e.g., material,
packaging, or biomedical applications. GGM are known to
stabilize the colloidal dispersions of wood-derived lipophilic
substances in pulp. We study the potential of GGM as
stabilizers in food systems, which could be suitable novel
applications for these plant-based polysaccharides. In the
present study, GGM and their carboxymethyl derivatives (CMGGM) were dissolved in aqueous buffer solution and used as
the continuous phase of rapeseed oil-in-water emulsions (1–5
wt.-% oil, 0.01–1 wt.-% GGM or CM-GGM), prepared by high
pressure homogenization using a microfluidizer. The oil particle
size distribution was followed during four weeks of storage at
room temperature, using static light scattering. In addition, the
zeta potential (ζ) of emulsion droplets was determined and the
morphology of emulsions was investigated by optical
microscopy. The partitioning of GGM and CM-GGM between
the continuous phase and on the oil-water interface was
investigated after separating the emulsions’ phases by
centrifugation. GGM and CM-GGM greatly enhanced the
emulsion formation compared to plain buffer solution, and
produced oil particles with average diameter (d3,2) below 1
µm. The visual appearance of the emulsions as well as the
particle size distribution over storage revealed that GGM and
CM-GGM efficiently stabilized the emulsions against physical
breakdown. The mechanisms of stabilization of the model food
emulsions by GGM and CM-GGM will be discussed.
CELL 262
Recycled thermoset waste/polypropylene composites with
enhanced stiffness and impact resistance
Oguzhan Oguz, [email protected], Eren Simsek, Kaan
Bilge, Yusuf Z. Menceloglu. Faculty of Engineering Natural
Sciences, Sabanci University, Istanbul, Turkey
Critical environmental and economic issues are stimulating
research in the mass production of sustainable materials for
markets that require low costs and high production rates.
Particularly attractive are the physical modification of
thermoplastics such as Polypropylene (PP) based on blending
with an elastomer and/or natural fibers in which an economical
way to produce sustainable materials, preventing further
stresses on the environment. However, PP finds use in many
industrial fields due to its intrinsic properties such as high
melting temperature, low density and high chemical resistance,
the poor impact resistance is a major problem for a wide range
of engineering applications. Furthermore, the wild use of
elastomers (synthetic wastes) and cellulose based short fibers,
which is not available is to reuse in textile industry because of
their length (natural wastes), is becoming a world-wide waste
disposal problem. To address these global concerns, this study
is an effort to create a new horizon for the mass production of
the advanced thermoplastic based materials by the processing
of the renewable sources and common thermoplastics in a
high-shear thermokinetic mixer. PP was chosen as a
thermoplastic matrix whereas cross-linked waste EDPM rubber
and cellulose based short fibers were used as renewable
reinforcing agents with various filler concentrations. Waste
EPDM rubber was employed up to %80 by weight as an impact
modifier. The reuse of cellulose based short fibers was
considered as an alternative reinforcement to the incorporation
of glass fibers into thermoplastics between 10-30% by weight
for many high performance applications. Briefly, 2-fold increase
in elastic modulus of PP was achieved by the addition of
cellulose based renewable fibers (natural wastes) whereas 5fold increase in impact resistance was acquired in PP/w-EPDM
master batches as advanced thermoplastic materials modified
by synthetic wastes. The main conclusion of the study is that
the extensive blending technology gives us the ability to
produce high performance thermoplastic materials as well as
managing the world-wide waste disposal problem by reusing of
synthetic wastes, which is a great opportunity to ensure
sustainability and reduce environmental and economic costs
for many industries. Furthermore, cellulose based renewable
fibers can be used as an alternative reinforcing agent to the
glass fibers that is also quite significant for engineering
applications.
CELL 263
Ionic liquid/molecular solvent mixtures as tailored media
for cellulose derivatization: Uncatalyzed- and imidazolecatalyzed acylation
Omar El Seoud1, [email protected], Thaís C. Teixeira1, Paulo
Augusto R. Pires1, Haq Nawaz2, Thaís A. Bioni1. (1) University
of Sao Paulo, Sao Paulo - SP, Brazil (2) Institute of ChemistryLab 0463, University of Sao Paulo, Sao Paulo, Brazil
The use of ionic liquids, ILs, as solvents for cellulose is
associated with problems of high cost and high biopolymer
solution viscosity. These are attenuated by using mixtures of
ILs and molecular solvents, MS. Understanding solventcellulose interactions is required. We probed these by
determination of the rate constants of the uncatalyzed- and
imidazole-catalyzed acylation of microcrystalline cellulose with
ethanoic- to hexanoic anhydride in mixtures of the IL 1-allyl-3methylimidazolium chloride with DMAC, DMSO and sulfolane.
For the diazole-catalyzed reaction, the acylating agent is Nacylimidazole. For the same anhydride, the order of reactivity
in all cases is DMSO > DMAC > sulfolane. This is explained by
differences in the reaction activation parameters, and
differences in solvent viscosity and microscopic properties
(polarity, acidity, basicity; determined by solvatochromic
probes). Acetylation in IL/DMAC is faster than that in
LiCl/DMAC due to differences in the activation parameters.
Acknowledgements: We thank FAPESP for a fellowship to TCT
and financial support; CNPq for fellowships to TAB and OAES.
CELL 264
Lignin-soy protein aerogels
Carlos L. Salas2, [email protected], Ingrid C. Hoeger2,
Mariko Ago1, Orlando J. Rojas3,2. (1) Tokushima Bunri
University, Tokushima, Japan (2) Forest Biomaterials, North
Carolina State University, Raleigh, North Carolina, United
States (3) Forest Products Technology, Aaalto University,
Espoo, Finland
Our quest to use lignin in applications beyond power cogeneration includes explorations in the synthesis of composite
fibers and multiphase materials. In this work we propose the
utilization of lignin in aerogels system combined with soy
protein and coadjutant polymers (polyethylene oxide and
polyvinyl alcohol). Relatively strong, low density, highly porous
aerogels were obtained after freeze drying. The effect of
freezing method (liquid N2, slow freezing), the content of coadjutant polymer and the effect of lignin content on the
morphology, porosity and mechanical properties of the
aerogels were determined. Crosslinking of the aerogel matrix
was also explored to improve the wet strength. The results
indicate the synergy between lignin and soy proteins in the
fabrication of aerogels and shows promise for the development
of low-cost functional materials.
CELL 265
CELL 267
Reinforcing capability of cellulose nanofibrils (NFC) on
nanopapers from soybean hulls forms: Study of the
synergetic effects on the mechanical and barrier
properties
Strategy
for
multidimensional
understanding
lignocellulose conversion processes
Ana Ferrer1, [email protected], Carlos L. Salas2, Thomas W.
Theyson3, Orlando J. Rojas1,4. (1) Forest Biomaterials, North
Carolina State University, Raleigh, North Carolina, United
States (2) Forest Biomaterials, NC State University, Raleigh,
North Carolina, United States (3) Tenstech Inc., Matthews,
North Carolina, United States (4) Forest Products Technology,
Aalto University, Espoo, Finland
of
Carlos Driemeier, [email protected], Maria T.
Pimenta. CTBE, CNPEM, Campinas, São Paulo, Brazil
Agricultural waste represents an abundant, low-cost source of
cellulosic materials that can be processed into value added
materials for industrial applications. In this work, microfibrils
and cellulose microparticles with interesting brick-like shape
were isolated from soybean hulls by combining chemical and
mechanical treatments. These materials were used to prepare
nanopapers which were characterized and compared against
nanopapers prepared from wood nanofibrillar cellulose (NFC).
Nanopapers with improved mechanical and barrier properties
were prepared by mixing the soy hulls derived fibrils with wood
fibrils which indicates that synergetic effects were achieved.
The dynamic mechanical analysis showed that addition of the
NFC improved Young ́s modulus and increased the stiffness of
these nanopapers, among other significant properties.
Conversion of lignocellulosic biomass into value-added
products comprises many phenomena taking place across
distinct
characteristic
length
scales.
Comprehensive
understanding of factors influencing biomass conversion
should consider potential roles of processing conditions as well
as biomass compositional and structural characteristics. Our
strategy to investigate the multidimensional character of
lignocellulose conversion includes precise characterization of
biomass nanostructure. Concretely, we have been employing
the following analytical techniques: X-ray diffraction to probe
cellulose crystals; infrared spectroscopy associated with
dynamics of deuterium exchange to probe biomass disordered
fractions; dynamic vapor sorption to probe water accessibility;
and calorimetric thermoporometry to probe wet-state
nanoscale pores. Importantly, information from compositional
and structural analytical techniques is integrated through
multivariate statistical analysis. To exemplify the applicability of
this data acquisition and analysis strategy, we present an
investigation
on
how
biomass
compositional
and
nanostructural properties influence enzymatic digestibility of
pretreated sugarcane bagasse.
CELL 266
CELL 268
Mill wood
cellulases
lignin
interactions
with
monocomponent
1,
Antonio Pereira Gonzalez [email protected], Ingrid C.
Hoeger6, Ana Ferrer2, JORGE RENCORET3, José C. del Río4,
Angel T. Martinez5, Ana Gutiérrez3, Orlando J. Rojas2. (1)
IRNAS, CSIC, Seville, Spain (2) Forest Biomaterials, North
Carolina State University, Raleigh, North Carolina, United
States (3) IRNAS, CSIC, Seville, Spain (4) IRNAS-CSIC,
Seville, Spain (5) Cib Csic, Madrid, Spain (6) Forest
Biomaterials, NCSU, Raleigh, North Carolina, United States
The recalcitrance nature of biomass is one of the main
obstacles in biorefineries operating under the bioconversion
platform to convert cellulose to sugars and other chemical
species. The presence of lignin hinders the enzymatic
hydrolysis of lignocellulosic materials, through hydrophobic and
electrostatic interactions. This study pertains a fundamental
study of these interactions. To this end, lignins from different
wood sources (Hardwood and Softwood) were isolated by the
Milled Wood Lignin (MWL) method. Compositional
spectroscopic analyses of the MWL was carried out and lignin
films were prepared by the spin coating technique. The films
were characterized by atomic force microscopy and contact
angle measurements. The interactions of cellulase enzymes
with the different lignins where monitored with Quarz Crystal
Microbalance (QCM) and Surface Plasmon Resonance (SPR)
and the main conclusions are presented.
Gelatin as renewable source for new material production
Cristina Peña-Rodriguez1, [email protected], Gurutz
Mondragon1, Aitor Arbelaiz1, Roxana Ruseckaite2, Arantxa
Eceiza1. (1) Chemical and Enviromental Engineering ,
University of the Basque Country, Donostia / San Sebastián,
Guipúzcoa, Spain (2) INTEMA, Research Institute of Material
Science and Technology , Mar de Plata, Argentina
The renewable origin of gelatin, high number of sources for
easily extraction and the relatively low prices result in a very
attractive biopolymer for application in food packaging. The
acceptance of gelatin as “Generally Recognized as Safe”
(GRAS) substance in the area of food additives by the U.S.
Food and Drug Administration (FDA) together with its excellent
film-forming ability, gel-forming properties around 35 °C,
excellent versatility due to its amino acid composition,
abundance, low cost and biodegradability, make gelatin an
attractive protein in the design and development of functional
films with potential application in the food and biomedical
sectors1. The tightly bounds (hydrogen bonds and hydrophobic
interactions) present in gelatin structure and the polar groups
of aminoacids result in brittle materials in dry state with high
moisture absorption2. Mechanical and barrier properties can be
improved using additives like polyols, carbohydrates of high
molecular weight such as starch and chitosan3,
oligosaccharides and some organic acids4. On the other hand,
plasticizers like sorbitol5, or chemical modification with
aldehydes6 are also used to modify some of the functional and
physical properties of the films. Phenolic compounds of
vegetable tannins are a good alternative for the development
of new gelatin-based materials which would not involve the use
of toxic components banned for food packaging and medical
applications. Tannic acid and tannin extracts have been
employed to improve mechanical properties and water
repellence of this hydrophilic protein7-8. The aim of this work is
to study the materials obtained by modification of gelatin matrix
with several contents of commercial tannin extracts. In figure 1
obtained gelatin films modified with several amounts of
chestnut (GC), oak (GO) and tara (GT) tannin extracts are
shown.
1. Peña-Rodriguez C., et al. Gelatin Films: Renewable
Resources for Food Packaging. In: Gelatin: Productions,
Applications and Helth Implications (pp 71-87). Nova Science
Publishers. (2013)
2. Karnnet S., et al. (2005) Polymer Degradation and Stability.
90, 106-110
3. Cao N., et al. (2009) Food Hydrocolloids 23, 729-735
4. Vanin F.M., et al. (2005) Food Hydrocolloids. 19, 899-907
5. De Carvalho et al. (2004) Food Hydrocolloids 18, 717-726
6. Peña-Rodriguez C., et al. (2010) Bioresource Technology
101, 6836-6842
7. Peña-Rodriguez C, et al. Food Science and Technology
International. Published online 15 May 2014
CELL 269
Lignin-additives-enzymes interactions studied by QCM-D
Consuelo Fritz1, [email protected], Ana Ferrer1, Carlos L.
Salas1, Hasan Jameel1, Orlando J. Rojas1,2. (1) Forest
Biomaterials, North Carolina State University, Raleigh, North
Carolina, United States (2) Forest Products Technology, Aalto
University, Helsinki, Finland
A critical step on the enzymatic hydrolysis of lignocellulosic
biomass involves the adsorption and desorption enzymes on
the substrate. These dynamic processes are affected by
temperature, pH, and other factors related to the substrate,
such as surface characteristics (chemical composition) and
bulk properties as affected by pretreatment steps, the surface
area and pore volume. Among these, the role of lignin is the
main focus in this work. As such, we used Quartz Crystal
Microbalance with Dissipation monitoring (QCM-D) to obtain
real time molecular-level information about the interactions of
enzymes with lignin model surfaces primed with nonionic
surfactants. The results indicate that non-ionic surfactants
were effective to reduce non-productive interaction between
lignin and cellulases. At concentrations below the surfactant
critical aggregation concentration, reduced adsorption onto
lignin model surfaces was observed. This low adsorption
promotes larger amount of sorbed enzymes. Phenolic and
aliphatic hydroxyl content, as well as the lignin surface charge
were determined and used to understand the mechanistic
aspect of the adsorption process involving both surfactants and
cellulases.
CELL 270
Industrial scale production of nanocellulose, based on
agroindustrial wastes
Melissa Camacho Elizondo, [email protected], Jose Vega
Baudrit. LANOTEC, Pavas, Costa Rica
Purpose of this study is to determine the feasibility of industrial
scale production of nanocellulose, as a reinforcing material for
plastic packaging from pineapple wastes (in specific peels).
Costa Rica has a big agricultural production, which generates
large amounts of agroindustrial waste, such as pineapple,
whose remnants have been traditionally linked with
environmental damage. The production procedure was based
on a method developed at the POLIUNA from the Universidad
Nacional,Costa Rica, and in acid hydrolysis techniques.
Results: TMAR = UTIL = 19,19% So, the project is accepted
VAN
>
0
so,
the
project
is
accepted
TIR = 46,42% > TMAR, so, the project is accepted.
Conclusions: This feasibility study showed a very positive level
of profitability, which could be beneficial for the country; in one
side, it transforms an environmental problem in a benefit that
can be extended to entire communities and in the other hand, it
creates a new technology that can pay dividends for the
country
CELL 271
Glycosylated proteins and glycan binding: Insight into
function using NMR
James H. Prestegard, [email protected], Qi Gao,
Cheng-Yu Chen. Univ of Georgia, Athens, Georgia, United
States
Many proteins at the surface of mammalian cells are not only
glycosylated themselves, but also interact with other glycans of
the glycocalyx. This makes an understanding of the mode of
interaction between protein and glycan of extreme importance
in attempts to modulate function in response to disease.
Reaching this understanding, particularly at a structural level,
has been challenging because of the heterogeneity of the
glycans involved and the necessity of preparing proteins with
homogeneous glycosylation. For NMR, the need for
enrichment with NMR active isotopes poses additional
challenges. We have approached this challenge with a
combination of sparse isotope labeling (single amino acid type
for proteins) and long range NMR constraints from
paramagnetic effects and residual dipolar coupling. We will
illustrate this approach with examples from a set of cell-surface
signaling molecules that interact with glycosaminoglycans in
modulating their function.
CELL 272
Photoregenerated cellulose: From 2D patterns to 3D
microfabrication
Archim Wolfberger2, Andreas Petritz4, Volker Schmidt4, Rupert
Kargl3, Barbara Stadlober4, Katrin Niegelhell1, Thomas
Griesser2, Stefan Spirk1, [email protected]. (1) Institute
for the Chemistry and Technology of Materials, Graz University
of Technology, Graz, Austria (2) University of Leoben, Leoben,
Austria (3) University of Maribor, Maribor, Slovenia (4)
Materials, Joanneum Research, Weiz, Austria
In many areas of science and technology, patterned films and
surfaces play a key role in the engineering and development of
advanced materials. However, cellulose based films have not
been widely used for such purposes due to the lack of efficient
and non-destructive patterning methods. In this contribution,
non-destructive photolithographic patterning strategies of
cellulose films for the realization of 2- and 3-dimensional
micropatterns are presented. The main idea is to employ
photo-acid induced reactions that convert an acid labile
cellulose derivative to pure cellulose upon exposure to UV light
by the aid of photoacid generators. When a mask aligner is
used, areas exposed to UV light are converted to cellulose
whereas protected areas remain unaffected leading to possible
feature sizes in the single-digit micron range. Depending on
the applied development procedure (either rinsing or enzymatic
treatment) negative or positive-type patterns are obtained.
Moreover, the use of 2-photon absorption lithography allows
for realizing 3-dimensional structures having feature sizes of ca
0.5 microns by using the same strategy.
and 3) « click » coupling of pre-formed blocks referred as «
grafting onto » method. The synthesis and self-assembly
properties will be described.
CELL 273
Glycan maps and quantitation of glycoproteins
Carlito B. Lebrilla, [email protected]. Chemistry,
University of California, Davis, Davis, California, United States
Proteins are modified by glycans that often play a key role to
their functions. It is estimated that 70% of all human proteins
are glycosylated, however less than 5% of the sites are
mapped with glycan heterogeneity. We are developing
methods for determining site-specific glycosylation and are in
the process of mapping the serum glycome. The glycan maps
enable the development of methods for site-specific
glycosylation. In this presentation, the glycan map of serum
glycoproteins will be described. The maps provide site-specific
glycosylation with microheterogeneity. The glycan maps are
used for developing methods for quantitative glycoproteomic.
In this site-specific glycans are monitored with high quantitative
precision. The methods are used for determining markers in
diseases and for identifying and monitoring glycosylation in the
production of glycoprotein drugs and therapeutics.
CELL 274
Well-defined sugar-based amphiphilic copolymers: From
controlled architectures to nanostructured materials
Sami HALILA, [email protected], Issei Otsuka,
Redouane BORSALI. Physical Chemistry of Glycopolymers,
CERMAV - CNRS, University Grenoble Alpes, Grenoble,
France
Amphiphilic copolymers, block or graft, have been extensively
explored due to their ability to self-assemble in solution or in
thin film giving rise to controlled nanostructured materials. The
applications areas are multiple including nanomedicine and
nanoelectronics.
For both applications, the introduction of biosourced poly/oligo-saccharides block is highly desirable in regards to their
high hydrophilicity, chemical functionalities, biocompatibility,
biodegradability and their relevant biological activities.
In aqueous solution, «hybrid» amphiphilic oligosaccharidebased copolymers self-assemble into micellar aggregates or
vesicles where the hydrophilic sugar blocks comprise the outer
corona while the hydrophobic blocks are trapped inside
through physical interactions. Recently, we have succeeded in
preparing nano-organized thin films made from hybrid
glycopolymers with size and domain spacing is approaching 10
nm while the today state-of-the-art is 20-30 nm. Such
breakthrough innovation is favored by the rigid nature of the
oligosaccharide and the strong incompatibility between the
blocks. From a synthetic point of view, "hybrid" glycopolymers
were obtained according to a three-step process consisting of:
1) preparation of scalable and size-homogeneous
oligosaccharides from biosourced materials by enzymatic or
chemical processes; 2) conjugation with “clickable” functions
Self-assembly of “hybrid” sugar-based block copolymer in solution
or in thin-film.
CELL 275
Wood hydrolysates: From fractions to products
Ann-Christine Albertsson, [email protected], Ulrica M.
Edlund. Fibre and Polymer Technology, Royal Inst of
Technology (KTH), Stockholm, Sweden
Hemicellulose-rich and lignin containing wood hydrolysates
can be recovered from the liquid process streams in wood
processing operations such as pulping. These fractions have
great utilization potential from a chemical and property
perspective. We have shown how and why wood hydrolysates
perform especially well when not highly purified or even in the
crude state. In particular, they perform with very low
permeabilities, also under challenging humidity conditions,
when converted to renewable oxygen barrier films and
coatings. [1-4] Taking product formulation from lab scale to
pilot scale and beyond represents a challenge. The process
must be technically and economically sound and process
parameters are being established that generate a hydrolysate
with properties robust toward inevitable fluctuations in wood
origin. Evaluating mass-energy balances and technoeconomical considerations are important steps along the way
of taking research to industrial scale.[5]
[1] O. Dahlman; M. Söderqvist Lindblad; J. Parkås, A.-C.
Albertsson; U. Edlund, Utilization of a wood hydrolysate, EP
2067793 / WO 2009068525 A1, 2009.
[2] A.-C. Albertsson; U. Edlund, Barrier layers for packaging
laminates and packaging laminates comprising such barrier
layers, WO 2011005181 A1, 2011.
[3] Y. Zhu Ryberg; U. Edlund; A.-C. Albertsson,
Biomacromolecules, 2011, 12, 1355-1362.
[4] A. Ibn Yaich, U. Edlund, A.-C. Albertsson,
Biomacromolecules, 2012, 13, 466-473.
[5] M. Jansson, S. Danielsson, S. Saadatmand; U. Edlund, A.C. Albertsson, Cellulose 2014, 21(3), 2045-2062.
CELL 276
Proteomics analysis of sialylated glycoproteins identifies
substrates for sialyltransferases and sialidases
Yibing Wang, Janet McCombs, Jennifer J. Kohler,
[email protected]. University of Texas
Southwestern Medical Center, Dallas, Texas, United States
The presence or absence of sialic acid can dramatically alter
the activity of glycoproteins, affecting both extracellular binding
and intracellular signaling events. The sialylation status of
glycoproteins is regulated by two key classes of enzymes:
sialyltransferases, which add sialic acid, and sialidases, which
remove sialic acid. Glycoproteomics methods are beginning to
inventory the glycoproteins that may be sialylated, but these
efforts have not yet linked sialylation to the activity of specific
sialyltransferases and sialidases. We report the integration of
the periodate oxidation and aniline- catalyzed oxime ligation
(PAL) reaction for specific biotinylation of sialylated molecules
with quantitative proteomics methods, and show that this type
of glycoproteomics analysis can be used to identify
sialyltransferase and sialidase substrates. First, we used PAL
in combination with stable isotope labeling by amino acids in
cell culture (SILAC) to identify substrates for the human
sialyltransferase ST6GAL1 in a breast cancer cell line. We
confirmed that the pro-metastatic protein CDCP1 (also known
as Trask) is an ST6GAL1 substrate and showed that signaling
through CDCP1 is activated by ST6GAL1 expression. In
addition, we show that both ST6GAL1 and CDCP1 are
involved in promoting a mesenchymal phenotype in a breast
cancer cell line. Thus, the PAL-SILAC approach provides new
mechanistic insight into the role of sialylation in cancer cell
behavior. In a second application, we used PAL in combination
with label-free SINQ normalized spectral index quantitation to
identify glycoprotein substrates for three pneumococcal
sialidases. Sialidase substrates were identified from a cell line
that models the human endothelial blood-brain barrier, yielding
insights into possible mechanisms by which pneumococcus
crosses the blood-brain barrier in meningitis.
CELL 277
Aligned cellulose nanowhisker-based high-performance
polymeric proton conductors
Mohammad
M.
Hasani-Sadrabadi1,2,
[email protected], Erfan Dashtimoghadam3, Fatemah
S. Majedi2, Philippe Renaud2, Karl I. Jacob1,4. (1) G.W.
Woodruff School of Mechanical Engineering, Georgia Institute
of Technology, Atlanta, Georgia, United States (2) Laboratoire
de Microsystemes (LMIS4), Institute of Microengineering and
Institute of Bioengineering, École Polytechnique Fédérale de
Lausanne (EPFL), Lausanne, Switzerland (3) Department of
Polymer Engineering, Amirkabir University of Technology,
Tehran, Iran (the Islamic Republic of) (4) School of Materials
Science and Engineering, Georgia Institute of Technology,
Atlanta, Georgia, United States
Proton exchange membrane (PEM) fuel cells are among the
most promising electrochemical devices for transport energy
conversion due to their high energy density at medium
operating temperatures. PEM is a central component, acting as
the fuel barrier and providing proton conduction. The
amphiphilic nature of polyelectrolytes leads to nanoscale
phase separation resulting in the presence of parallel
hydrophilic nanochannels randomly distributed throughout the
matrix. Considering the model for ionic phase separation of
Nafion as a state-of-the-art polyelectrolyte membrane, it could
be speculated that phase separation and nanochannel
formation could be less disturbed in the presence of 1D
nanoadditives compared to spherical nanoparticles. We
studied the potential of cellulose nanowhiskers (CNWs) as
promising rod-like nanomaterials to regulate microstructure of
Nafion. We exploit aligning capability of CNWs induced
through an applied external electric field and design
polyelectrolyte matrices with improved anisotropic proton
conductivity and as a results superior electrochemical
performance.
CELL 278
Cellulose carbontes – a platform for novel cellulose
derivatives
Thomas J. Heinze, [email protected]. Friedrich
Schiller University of Jena, Jena, Germany
Cellulose aryl carbonates could be synthesized efficiently
under
homogeneous
conditions
(DMA/LiCl,
Ionic
Liquids/covalent) with degree of substitution (DS) up to 3
applying p-NO2-phenyl chloroformate, phenyl chloroformate,
and phenyl fluoroformate. The aminolysis of the reactive
cellulose aryl carbonates using aliphatic amines or benzyl
amines, yield soluble polysaccharide carbamates. Even a
novel class of polyzwitterions possessing weak ionic groups
could be efficiently synthesized from cellulose phenyl
carbonate. Polyanions, polycations, and polyzwitterions are
accessible by orthogonal removal of protecting groups. The
molecular structure was proofed by means of FTIR- and NMR
spectroscopy. Characteristic properties of the cellulose
derivatives, e. g., acid dissociation constants, isoelectric point,
and self-complexation were investigated by potentiometric
titration (pH), nephelometry, rheologys and dynamic lightscattering. The formation of pH-responsive interpolyelectrolyte
complexes applying polydiallyldimethylammonium chloride was
studied. The particles obtained are switchable in a
physiological relevant range of pH values and are promising
nanocarriers in field of drug delivery, cell targeting, and
immobilization of biocatalyst.
CELL 279
Synthesis, characterization, and properties of cellulose
derivatives having an annular structure in the side chains
Chunyu Chang1, Yoshikuni Teramoto1,2, Yoshiyuki Nishio1,
[email protected]. (1) Div. of Forest & Biomaterials
Sci., Kyoto University, Kyoto, Japan (2) Faculty of Applied
Biological Sci., Gifu University, Gifu, Japan
We designed a pathway to synthesize novel cellulose
derivatives having a necklace-like annular structure in the side
chains. First, native cellulose was modified with glycidol (GLY)
in NaOH/urea aqueous solution to obtain O-(2,3dihydroxypropyl) cellulose (DHPC) having more than two
hydroxyl groups in the side chains. Then, butyralization of
DHPC with butyraldehyde (BuA) was conducted in acidic
aqueous solution, so as to produce cellulose butyral (CB)
involving a cyclic acetal formation in the side chains. The CB
products were characterized through rigorous analysis of the
molecular structure including the type of ring formation as well
as the substituent content. Following examination of the
processibility of the CBs as dimensional material, our major
concern was directed to optical, adhesive, and mechanical
properties of hot-pressed CB films. It is demonstrated that
those CB films exhibit a well-balanced performance in ductility
and toughness and possess a potential applicability as
interlayer for laminated glasses.
CELL 280
Preparation and properties of photosensitizer-bounded
cellulose derivatives
Toshiyuki Takano, [email protected], Yasuko
Saito, Hiroshi Kamitakahara. Graduate School of Agriculture,
Kyoto University, Kyoto, Kyoto, Japan
Cellulose is the most abundant renewable biopolymer in
nature. Cellulose and cellulose derivatives are widely used in
our daily life. However, much attention has been still paid to
the development of new functional cellulose derivatives for
high-value-added utilization of cellulose. Highly regioselectively substituted cellulose derivative is expected to be a
scaffold of photosensitizers because of its well-defined and
regular structure. Indeed, we have reported that LangumirBlodgett (LB) film of porphyrin-containing cellulose derivative
exhibited high photon-electron conversion performance in the
wavelength range from 400 to 450nm. However, the target
wavelength range for a solar cell should be considered from
400 to 920 nm. Then, new several photosensitizer-bounded
cellulose derivatives such as (metal phthalocyanine)-containing
cellulose derivatives, squaraine-containing cellulose derivative
were newly prepared and subjected to the evaluation of
photon-electron conversion performances. As the results,
(palladium phthalocyanine)-containing cellulose derivative has
the highest photon-electron-conversion performance as a
photoactive species in the red wavelength ranged from 600 to
700 nm.
Cellulose triacetate-block-oligoamide-15 and cellulose acetateblock-poly(gamma-benzyl-L-glutamate)
were
prepared
according to a stepwise elongation of a non-cellulosic
repeating unit and a covalent bond formation between two
polymeric residues via click chemistry, respectively. Diblock
methylcellulose derivatives and the analogs were prepared
according to a glycosylation, ring-opening polymerization of
glucose 1,2,4-orthopivalate derivatives, and CuAAC reaction.
Those well-defined cellulosic diblock copolymers exhibited
nanostructures of academic interests such as first-ever
cellulosic micro- or nano-phase separated film, ellipsoidal
nanoparticles, and thermo-responsive ribbon-like nanofibers.
Structure-property
relationships
of
cellulosic
diblock
cooligomers and copolymers will be also discussed.
CELL 282
Topochemical considerations controlling the dynamics of
cellulose nanocrystal brush polymerization
Chen TIAN2, Shiyu FU2, Youssef Habibi4, Lucian A. Lucia3,1,
[email protected]. (1) Departments of Forest Biomaterials and
Chemistry, North Carolina State University, Raleigh, North
Carolina, United States (2) State Key Laboratory of Pulp &
Paper Engineering, South China University of Technology,
Guangzhou, 关东, China (3) Key Laboratory of Pulp & Paper
Science & Technology, Qilu University of Technology, Jinan,
山东, China (4) Department of Advanced Materials and
Structures, Public Research Centre Henri Tudor, Hautcharage,
Luxembourg
We have determined that the facility of installing polymer
brushes onto the surface of cellulose nanocrystals is governed
by the immediacy of the dehydration protocol. Typically, either
solvent exchange or freeze-drying are the penultimate steps
necessary to allow any polymerization (grafting from or grafting
to)strategy to be successful; however, the distinction between
the two approaches has never been fully challenged nor
critically analyzed. We provide a sequential and logical
chemical accounting of the fundamental differences that
ultimately distinguish the two protocols for brush
polymerization schemes. The work described should have
special significance to the natural polymer chemistry
community who wish to incorporate celluose nanocrystal
species within hydrophobic matrices.
CELL 283
Cellulose in solid state and solution: Structure, chemistry,
and reaction mechanisms
Thomas Rosenau, [email protected]. Dept of
Chemistry, University for Agr Sciences, Vienna, Austria
Anselme Payen Award address by Dr. Thomas Rosenau
CELL 281
CELL 284
Synthetic strategies for cellulosic diblock copolymers
From biological
development
Hiroshi Kamitakahara, [email protected]. Kyoto
Univ Grad Sch Agri, Sakyo Ku Kyoto, Japan
Our research focuses on development of synthetic strategy for
diblock copolymers with cellulose acetate and methylcellulose.
glycosylation
to
universal
Chi-Huey Wong, [email protected].
Sinica, Taipei, Taiwan
vaccine
Academia
Biological glycosylation is one of the most complex biological
processes and is known to modulate the structure and activity
of proteins, lipids and natural products. Glycosylation of
proteins would affect protein folding, stabilization, trafficking,
signaling and many intercellular recognition events associated
with bacterial and viral infection, cancer progression and
immune response. Development of new tools and methods for
use to understand the roles of carbohydrates in biology may
provide new solutions to many of the unsolved disease
problems. This lecture will describe our efforts in this regard
with focus on the development of universal vaccines to combat
the problems of influenza and cancer.
broadly-neutralizing antibody. These glycoclusters are of
interest as HIV vaccine candidates.
CELL 285
Entirely carbohydrate-based cancer vaccines for disease
prevention and treatment
Peter R. Andreana, [email protected]. MS 602,
The University of Toledo, Toledo, Ohio, United States
Cancer is the second leading cause of death in the US.
Various pharmaceutical-based chemotherapeutic and cancer
immunotherapeutic agents are cell specific and therefore many
types of tumors are not affected by treatment. A new approach
to cancer vaccines utilizing a bacterial, capsular zwitterionic
polysaccharide PS A1 and tumor associated carbohydrate
antigens has rendered murine immune responses showing
tumor selectivity, tumor specificity and tumor killing function.
This talk will focus on cancer vaccines of an entirely
carbohydrate semi-synthetic construct, namely Tn-PS A1 and
TF-PS B will be discussed. Processes for evaluating
immunogenicity, specificity, and mechanistics insights will
include isolation, purification, chemical modification of PS A1
and subsequent in vivo mouse studies. ELISA, and FACS
studies reveal that an immune response is specific for the
conjugated Thomsen nouveau (Tn) and Thomsen-Friedenrich
antigens. Our results argue for a novel carbohydrate vaccine
construct highlighting cellular immune activation based on
cytokine profiling.
CELL 286
SELMA and glycopeptide mRNA display: Directed
evolution of multivalent glycoclusters in HIV vaccine
design
Isaac J. Krauss, [email protected]. Kalman Stockroom,
Brandeis University Chemistry Dept MS 015, Waltham,
Massachusetts, United States
Tight recognition of monosaccharides or even oligosaccharides
by carbohydrate binding proteins usually requires multivalent
presentation of the carbohydrates (i.e., several copies of the
carbohydrate clustered together). Although chemical synthesis
enables us to cluster carbohydrates on a scaffold molecule of
choice, the optimization of this scaffold to produce extremely
tight binders has not previously been possible in a highthroughput fashion. In this lecture, we will discuss two methods
developed in our lab for selection of optimal multivalent
presentations from among libraries of trillions of genetically
encoded multivalent glycostructures. These methods merge
the tools of chemical synthesis, click chemistry and
aptamer/peptide selection and have afforded glycoclusters with
low nanomolar to high picomolar recognition by an HIV
Multivalent Glycocluster Selection by SELMA or Glycopeptide
mRNA Display
CELL 287
Site-specific
chemoenzymatic
therapeutic antibodies
glycoengineering
of
Lai-Xi Wang, [email protected]. Department of
Biochemistry and Molecular Biology, University of Maryland
School of Medicine, Baltimore, Maryland, United States
Monoclonal antibodies (mAbs) are an important class of
therapeutic glycoproteins widely used for the treatment of
cancer, inflammation, and infectious diseases. Recent studies
have demonstrated that the structures of Fc glycans can
dictate the immunological functions, e.g., pro-inflammatory
(activation) vs. anti-inflammatory activity, of a given antibody.
Therefore, controlling glycosylation of a therapeutic
monoclonal antibody to a desired glycosylation status is critical
for maximizing its therapeutic efficacy. However, most
monoclonal antibodies are produced as mixtures of glycoforms
that are not optimal for efficacy, and preparation of
homogeneously glycosylated mAbs has been a challenging
task. In this presentation, we describe a chemoenzymatic
method that enables site-specific glycosylation remodeling of
both Fc and Fab glycans in a monoclonal antibody. Using
cetuximab, an mAb that carries both Fab and Fc glycans, as
an example, we have shown that a remarkable site-specific
glycosylation remodeling of both Fc and Fab glycans can be
achieved by taking advantage of the substrate specificity of the
deglycosylation and transglycosylation enzymes. The
glycoengineered rituximab, with a fully sialylated glycan at the
Fab domain, and a non-fucosylated N-glycan at the Fc domain,
showed comparable antigen binding affinity as the commercial
mAb, but its antibody-dependent cellular cytotoxicity was
significantly enhanced. The scope and limitation of the
chemoenzymatic approach to glycoengineering of mAbs will be
discussed.
CELL 288
Fighting cancer with a sweet bullet: The development of
carbohydrate based anticancer vaccines
Xuefei Huang, [email protected]. Michigan State
University, East Lansing, Michigan, United States
There are many antigenic carbohydrate structures on cancer
cell surfaces. The development of an effective vaccine
construct against these tumor associated carbohydrate
antigens (TACAs) is an attractive approach towards cancer
treatment. However, a serious challenge is that the TACAs are
only weakly immunogenic and direct administration of TACAs
cannot elicit a powerful immune response to protect the host
from cancer development. In this talk, we will present our
results on the development of virus-like particles such as
bacteriophage Qbeta (Qβ) as a novel platform to significantly
enhance the immunogenicity of TACAs. The Tn glycan, which
is overexpressed on numerous cancer cell surfaces, was
selected as the antigen for our study. Previously it has been
shown to be difficult to induce a strong T cell-dependent
immune response against the monomeric form of Tn. We first
synthesized Tn antigens that were conjugated regioselectively
to Qb. The Qb-glycoconjugates were then injected into mice
and pre- and post-immune antibody levels in the mice sera
were established. High total antibody titers and, more
importantly, high IgG titers specific for Tn were obtained in the
post-immunization, suggesting the induction of T celldependent antibody isotype switching by the glycoconjugate.
The antibodies generated were able to recognize Tn antigens
presented in their native conformations on the surfaces of
cancer cells. Importantly, we discovered that the local density
rather than the total amount of the Tn antigen was critical for
high antibody responses once the amount of Tn passed a
threshold level. Moreover, the vaccine construct provided
significant protection against the development of an aggressive
tumor model in mice. These results suggest that virus-like
particle Qβ can greatly enhance the immunogenicity of weak
antigens such as Tn and this provides a promising tool for the
development of carbohydrate based anti-cancer vaccines.
Scripps Research Institute, San Diego, California, United
States
The sialic acid binding immunoglobulin lectin family of cell
adhesion receptors, called siglecs, comprises 14 members in
humans and 9 members in mice. The majority of the siglecs
exhibit highly restricted expression on one or more types of
white blood cells that confer play critical roles in both innate
and adaptive immune responses. Because they recognize
sialic acid containing glycans expressed on all mammalian
cells, and contain regulatory motifs that regulate cell surface
signaling receptors, siglecs are increasingly recognized as coreceptors that help the immune system distinguish between
self and non-self. To study the functions of siglecs in immune
cells, we have sought to develop glycan ligands of high avidity
affinity and selectivity for each siglec, which can then be used
as tools to probe siglec function and target siglec expressing
cells in vivo. To date, siglec-targeting ligands suitable for in
vivo targeting of various white blood cells have been identified
for nine different human and murine siglecs. Using these
ligands we have demonstrated the utility of siglec ligand
decorated nanoparticles to probe the functions of B cell
siglecs, and for in vivo targeting of various siglec expressing
cells in applications that include delivery of chemo-therapeutic
agents to B lymphoma cells, delivery of antigens to
macrophages, and induction of B cell tolerance. (NIH grants
AI050143, AI099141, CA013889 and HFSP Fellowship
LT001099/2010-L).
CELL 291
Synthesis of cellulosic bottlebrushes with regioselectively
substituted side chains and their self-assembly
CELL 289
Mapping the glycome with systems-based analysis
Lara K. Mahal, [email protected]. Chemistry, New York
University, South Orange, New Jersey, United States
Carbohydrates play crucial roles in a diverse array of biological
processes from viral pathogenesis to tumor cell metastasis.
Glycosylation is an inherently complex system due to both
dendrimeric and epimeric structures and an intricate
biosynthetic pathway whose regulation is poorly understood.
Systems-based approaches, in which large datasets are
analyzed using bioinformatic algorithms, provide an important
avenue for exploring the mechanics of complex systems that
cannot be predicted a priori. Applying such approaches to the
glycome using our lectin microarray technology we have
recently identified microRNA as important regulators of
glycosylation, discovered new associations between the
glycome and microbiome and defined new cellular trafficking
pathways. Our work has opened new avenues for mapping the
glycome by examining and integrating large datasets.
CELL 290
Targeting immune cells with glycan ligands of siglecs
James C. Paulson, [email protected], Matthew S.
Macauley, Ryan McBride, Corwin Nycholat, Fabian Pfrengle,
Wenjie Peng, Sampat L. Ingale, Christoph Rademacher, Cory
Rillahan. Departments of Cell and Molecular Biology, Chemical
Physiology and Immunology and Microbial Sciences, The
Keita Sakakibara, [email protected], Yuji Kinose,
Yoshinobu Tsujii. Institute for Chemical Research, Kyoto
University, Kyoto, Japan
A graft copolymer with dense side chains, a molecular
bottlebrush, is known to form lyotropic liquid crystals because
of the considerably stretched formation of the backbone.
Furthermore, introduction of different kind of side chains into a
bottlebrush, called a Janus-type bottlebrush, can lead to
periodic nanostructures driven by the self-assembly of the side
chains. In our current study, novel bottlebrushes with semiflexible and helical cellulose backbones are synthesized and
their self-assembly toward mesoscopic hierarchical structure
are established. Polyethylene glycol and poly(methyl
methacrylate) or poly(styrene) covalently linked to cellulose
regioselectively were used to convey periodic nanostructures.
Synthesis, analytical and physicochemical characterization will
be presented and critically discussed.
CELL 292
Cosmetic active agent release from regenerated cellulose
matrices
Frank Meister, [email protected]. Thuringian Institute for Textile
and Plastics, Rudolstadt, Germany
Long-tern embedding and release of active ingredients from
textile structures is already wanted for couple of years. For that
reason fibre-film laminates has been developed including
depot structures made of polymer films which are now state of
the art. The complexity of such laminates, however, only
permits the use for pharmaceutical application, so far.
Physical modification of Lyocell fibres that are spun from direct
dissolved and dry-jet-wet shaped cellulose made it possible to
include such kind of active agents directly into the man-made
fibre matrix. High amounts of active agents, up to 20 per cent,
couldbeembed
dedusing
this
approach.While
solid
components like magnesia or zinc white could be directly
incorporated - liquid, soluble or meltable lipophilic components
could be added as composites embedded in liquid or meltable
paraffin wax. Independent of the used approach the
concentration of the active agents could be adapted to the
textile fabric lifetime and the reasonable active agent
effectiveness.The lecture will present experiences in
formulation of lipophilic components composites and theirs
incorporation into the direct dissolution technology. Moreover,
the morphological requirements for the release of cosmetic
active agents from the resulting shapes will be discussed. The
lecture will also discuss bio functionality as well as the
compatibility of the fabrics against human skin. Finally, the talk
will demonstrate in selected application studies the availability
of the active ingredients over the textile fabric lifetime.
CELL 293
Preparation of cross-linked cellulose nanofibril aerogel
with water absorbency and shape recovery
Chae Hoon Kim, [email protected], Hak Lae Lee, Hye
Jung Youn. Department of Forest Sciences, College of
Agriculture and Life Sciences, Seoul National University,
Seoul, Korea (the Republic of)
Current theories about fiber-fiber bonding in wet paper webs
leave room for various concepts and interpretations. Up to
now, it has not been possible to prove any of them by images
showing the actual condition of the web. The reason for this is
the preparation of samples, which tends to impair the bonding
structure of fibers but has been necessary to achieve the
desired resolution so far.To solve this problem, handsheets of
different moisture levels were formed from unrefined and
refined pulps. Specimens were prepared by cryofixation and
subsequent freeze-drying to image the convergence of fibers
by means of high-resolution Field Emission-Scanning Electron
Microscopy (FE-SEM) technology. The images show the
behavior of microfibrils in the fiber-water gel. Partly detached
microfibrils protrude from fibers into the surrounding water and
interact with neighboring fibrils and fibers. In the specimens
made from refined pulp, the interaction is not limited to single
microfibrils – portions of the S1 and S2 wall layers are capable
of moving freely in the fiber-water gel to form contact areas
with the surrounding fibrous material as well. We can therefore
assume that van der Waals forces exist between fibers already
in the wet mat. Acting like hook and loop fasteners, they create
strong cohesive bonds within the fiber structure.
The images reveal the processes involved in the convergence
of fibers and microfibrils even when acquired at high moisture
levels, thus confirming a number of models that had previously
been merely suppositional.
CELL 295
Zinc nitrate influences for promoting the dissolution of
cellulose in NaOH based aqueous solvent at low
temperature
Aerogels made of nanocellulosic materials are interesting new
materials with highly porous and flexible structure. In addition,
its surface properties can be easily modified for diverse
applications due to the abundant hydroxyl groups in cellulose
chain. However, typical nanocellulosic aerogels are formed by
interfibrillar hydrogen bonds and these fiber networks are
easily destroyed by water. This weakness in wet strength is a
limitation for the various applications of nanocelllosic aerogels.
In this research, we treated cellulose nanofibrils (CNF) with
maleic acid and hypophosphite. Firstly, maleic acid was
reacted with water dispersed CNF to form ester linkage. Then,
hypophosphite was added into the maleic acid-modifiedCNF
suspension and the suspension was quickly frozen using liquid
nitrogen. After freeze drying, CNF aerogel was prepared,
where cross-linkage of cellulose chain was formed by the
reaction between hypophosphite and maleic acid attached to
cellulose. With these two-step cross-linking reactions, covalent
cross-linked CNF aerogel with water absorbency was
produced. Moreover, cross-linked CNF aerogel showed shape
recovery characteristics after compressive deformation in wet
state. Shape recovery of cross-linked CNF aerogel was
evaluated by two-cycle compressive test and it was shown that
the performance of the cross-linked CNF was about 2.5 times
higher than that of untreated CNF aerogel.
Zinc nitrate was employed to promote the dissolution of
cellulose in NaOH/urea aqueous solution at low temperature
for the first time. The cellulose solubility in 6 wt% NaOH/ 4 wt%
urea aqueous solvent increased with the addition of zinc
nitrate, and the maximum solubility of cellulose was reached
with 4 wt% zinc nitrate. The resultant cellulose solution was
characterized by 13C NMR spectroscopy, dynamic and static
light scattering, relative viscosity, as well as rheology behavior.
The results demonstrated that cellulose was dissolved in
NaOH/urea/zinc nitrate aqueous solution without derivatization
as a physical process. The new additive could facilitate the
dispersion of cellulose chains in the dissolution at low
temperature, promote the stability of the concentrated cellulose
solution even at higher temperatures. Cellulose membranes
regenerated from the solution with and without additive were
compared, and the results showed that membranes fabricated
from NaOH/urea/zinc nitrate solution exhibited higher
mechanical properties and light transmittance. Furthermore,
the zinc nitrate was found to be capable of substituting the role
of urea for cellulose dissolution at low temperature.
CELL 294
CELL 296
Making fiber-fiber bonds visible
Requirements for successful cellulose fiber spinning from
ionic liquid solutions
Juergen Belle1, [email protected], Stephan Kleemann1, Juergen
Odermatt2, Andrea Olbrich3. (1) Chemical Engineering, Munich
University of Applied Science, Munich, Bavaria, Germany (2)
Chemical Wood Technology, University of Hamburg, Hamburg,
Germany (3) Thuenen-Institut fuer Holzforschung, Hamburg,
Germany
Sen Wang, Ang Lu, [email protected], Lina zhang. Department
of Chemistry, Wuhan University, Wuhan, Hubei, China
Michael Hummel1, [email protected], Anne Michud1,
Shirin Asaadi2, Yibo Ma1, Lauri K. Hauru3, Herbert Sixta1. (1)
Forest Products Technology, Aalto University, Espoo, Finland
(2) Forest product Technology, Aalto university, Espoo-02650,
Finland (3) Aalto University, Helsinki, Finland
During the last decade, cellulose fiber spinning from ionic liquid
solutions has been promoted intensively by several research
groups as possible alternative to the existing viscose and
Lyocell processes. A number of ionic liquids has been
identified as cellulose solvents and were suggested to be also
suitable for cellulose processing. However, the shaping of
polymer solutions to produce value added bio-based products
requires distinct properties of the solutions. In particular during
fiber spinning, pronounced shear and elongational stress is
exerted on the thin liquid filaments and has to be balanced by
the visco-elastic properties of the polymer solutions. Those
properties do not only depend on the cellulosic solute but also
on the ionic liquid used as solvent. Distinct differences were
observed in the spinning performance of ionic liquids. In
particular, solutions of the most promoted cellulose dissolving
ionic liquid, 1-ethyl-3-methylimidazolium acetate, lacked the
necessary visco-elastic properties to produce high tenacity
fibers. In this study several ionic liquids are compared in
respect to their performance in dry-jet wet fiber spinning, with
N-methylmorpholine N-oxide as benchmark solvent. The
rheological properties of the to date superior IL 1,5diazabicyclo[4.3.0]non-5-enium acetate were evaluated upon
dissolution of a wide range of cellulosic solutes. Oscillatory
shear-rheology provided a comprehensive set of information.
The spinnability and spin stability was tested at different scales
via a dry-jet wet piston spinning device. Thus, rheological
requirements to allow for successful fiber spinning could be
identified and are reported herein.
CELL 297
Degree of acetylation in biopolymers: a novel analytical
method
Thomas Zweckmair1, [email protected], Manuel
Becker1, Kyujin Ahn1, Hubert Hettegger1, Paul Kosma2,
Thomas Rosenau1, Antje Potthast1. (1) Chemistry / renewable
resources, BOKU Vienna, Vienna, Austria (2) Organic
Chemistry, University of natural resouces and life sciences
Vienna, Vienna, Austria
Zemplén deacetylation by sodium methanolate and
subsequent analysis of methyl acetate formed by GC-MS is
used as a novel approach to measure the degree of acetylation
in biopolymers. Only the covalently bound acetate is
transesterified upon the catalytic action of anhydrous sodium
methanolate in methanol. Free acetic acid or the
corresponding salts are not monitored, which renders the
method specific for ester functionalities (organic acetates). The
development focused on the accurate determination of the
degree of acetylation also at very low detection limits. Such
samples
hitherto
eluded
reliable
determination.
Straightforward liquid phase injection and a SPME-based
approach were compared for methyl acetate measurement
generated by the Zemplén reaction, the latter being superior
with regard to sensitivity. In order to eliminate discrimination
effects by varying moisture content or adsorptive interactions
of the analyte in the gas phase with the materials present in
the vial (i.e. cellulose) Isotope Dilution Mass Spectrometry is
the preferred method. By introducing isotopically labeled
methyl acetate, released from 4-O-(13C2-acetyl)-vanillin as the
internal standard, the overall reliability of the SPME method is
improved to a large extent.The Zemplén release of acetyl
groups as methyl acetate combined with its quantification by
SPME-GC-MS, revealed to be the method of choice for
routine, yet very precise and accurate analysis of a wide range
of acetyl-containing biopolymers, with easy handling and
widest applicability as additional positive features.
CELL 298
Reaction mechanisms in pulp bleaching: H2O2 degradation
of
2,5-dihydroxy-[1,4]-benzoquinone
as
a
key
chromophore in aged cellulosics
Takashi Hosoya, [email protected], Ute Henniges,
Antje Potthast, Thomas Rosenau. Chemistry / renewable
resources, BOKU Vienna, Vienna, Austria
2,5-Dihydroxy-[1,4]-benzoquinone (DHBQ) is one of the key
chromophores occurring in all types of aged cellulosics.1,2 This
work presents molecular mechanisms in H2O2 degradation of
DHBQ by a combination of experimental and computational
approaches, to provide a solid knowledge base for optimization
of bleaching sequences aiming at DHBQ removal.
Experimental investigation under neutral conditions (3.0 %
H2O2) showed that DHBQ degraded into malonic acid, acetic
acid, and carbon dioxide with the activation energy (Ea) being
20.4 kcal/mol. Theoretical calculations presented a plausible
mechanism for the degradation of DHBQ (Figure 1A). The
mechanism involves an intermediate IOH having an
intramolecular O-O bridge. IOH then undergoes the homolysis
of the O-O bond followed by b-fragmentation of the resulting
biradical BROH, giving ketene and oxaloacetic acid. While
ketene yields acetic acid, oxaloacetic acid eventually gives
malonic
acid
and
carbon
dioxide.3a
Under conditions more relevant to pulp bleaching (3.0% H2O2,
NaOH, pH 10), DHBQ degraded quantitatively into malonic
acid with an Ea of 16.1 kcal/mol. The theoretical computation
indicated that this degradation formed a dianionic intermediate
IO- (Figure 1B). The intermediate IO- undergoes O-O homolysis
to form a biradical BRO-, which is fragmented into malonate
anions. The O-O bond homolysis of the dianionic intermediate
IO-, under alkaline conditions, is favored over that of the neutral
counterpart IOH, with the unpaired electrons of BRO- being
stabilized by the geminal anionic oxygens. This difference in
the stability of the intermediates translates into significant
variations in the reaction rate and the product distribution
between
pH
10
and
neutral
conditions.3b
1. Rosenau, T.; Potthast, A.; Krainz, K.; Yoneda, Y.; Dietz, T.;
Shields, Z. P.; French, A. D. Cellulose 2011, 18, 1623–1633.
2. Hosoya, T.; French, A. D.; Rosenau, T. Mini Rev. Org.
Chem. 2013, 10, 309–315.
(3. a) Hosoya, T.; Rosenau, T. J. Org. Chem. 2013, 78, 3176–
3182. (b)Hosoya, T.; Rosenau, T. J. Org. Chem. 2013, 78,
11194–11203.
Figure 1. Degradation mechanisms under the neutral conditions (A)
and the alkaline pH 10 conditions (B).
CELL 299
One-pot synthesis of levulinic acid from cellulose in SO3Hfunctionalized ionic liquids
Shen1,
Sun1,
Wang1,
Yue
[email protected], Jian K.
Bo
Feng Xu2, Runcang Sun3,1. (1) Beijing Forestry University,
Beijing, China (2) Coll of Material Sci Tech, Beijing Forestry
Univ, Beijing, China (3) South China Univ of Tech, Guangzhou
Guangdon, China
A simple and effective route for the production of levulinic acid
(LA) from cellulose has been developed in SO3H-functionalized
ionic liquids. The effects of reaction conditions and ionic liquid
structures on the yield of LA were investigated, where the
highest yield of 39.4% was obtained for 120 min in the
presence of [BSMim]HSO4. A small amount of glucose and 5hydroxylmethylfurfural (HMF) (2.3% and 4.3%, respectively)
were also generated. The catalytic activities of ionic liquids
depended on the anions and decreased in the order: CF3SO3> HSO4- > OAc-, which was in good agreement with their
acidity order. The SO3H-functionalized ionic liquids were
efficient catalysts for cellulose conversion into LA and exhibited
favorable catalytic activity over four repeated runs.
Effect of [BSMim]HSO4 dosage on the hydrolysis of cellulose to the
main products (0.05 g cellulose; 0.3 g H2O; T = 120 oC; t = 120 min)
Recycling of IL for the hydrolysis of cellulose to LA (0.05 g
cellulose; 1.5 g IL; 0.3 g H2O; T = 120 oC; t = 120 min)
CELL 300
Affibody functionalized bacterial cellulose tubes for
biofiltration applications
Hannes Orelma1, [email protected], Luis O. Morales2,
Leena-Sisko Johansson3, Ingrid C. Hoeger4, Ilari Filpponen1,
Cristina Castro5, Janne Laine1, Orlando J. Rojas6. (1)
Department of Forest Products Technology, Aalto University,
Espoo, Finland (2) Helsinki University, Helsinki, Finland (3)
Aalto University, Espoo, Finland (4) North Carolina State
University, Raleigh, North Carolina, United States (5)
Universidad Pontificia Bolivariana, Medellín, Colombia
The objective of this study was to develop a tubular
nanocellulosic biofilter by using affibodies to selectively catch
proteins. Affibodies are engineered proteins, grown with E.coli,
which mimic the antigen binding properties of native
antibodies. They have also a wide availability to industrial
applications due to their bacterial origin. Tubular nanocellulosic
matrices
were
achieved
by
growing
them
with
Gluconacetobacter medellinensis in the presence of
carboxymethyl cellulose (CMC) to in-situ modify grown BC
fibrils. The properties of BC tubes were characterized with
SEM, WRV, charge, and XPS measurements. The concept
was demonstrated with anti-human serum albumin (anti-HSA)
affibodies, which bind specifically HSA. Affibodies were
covalently conjugated onto CMC modified BC tubes with the
aqueous EDC/NHS conjugation chemistry. The conjugation of
affibody and its affinity reactions on CMC modified cellulose
were verified by Surface Plasmon Resonance (SPR) with
cellulose thin films. The specific binding of HSA on an affibody
functionalized BC tube was demonstrated with fluorescence
stained HSA and the fluorescence microscopy. The presence
of CMC in the culture medium within BC grow has a significant
effect on the WRV of never-dried and air-dried BC tubes. This
subsequently reduces the irreversible structural changes of
frown BC within drying. Altogether, the covalent conjugation of
affibodies onto the surface of BC tubes and subsequent
detection of HSA was demonstrated. The fluorescence
intensity of bound HSA on affibody functionalized BC tubes
increased linearly as a function of HSA concentration. It is
expected that the developed mild and generic methodology
can be effortlessly transformed and utilized for the specific
detection and separation of other target proteins.
CELL 301
Triggering protein
cellulose surfaces
adsorption
on
tailored
cationic
Katrin
Niegelhell2,
[email protected],
Tamilselvan Mohan3, Cintia Salomão Pinto Zarth4, Rupert
Kargl5, Stefan Köstler6, Volker Ribitsch7, Thomas J. Heinze1,
Karin
Stana-Kleinschek5,
Stefan
Spirk2,
[email protected]. (1) Friedrich Schiller University of
Jena, Jena, Germany (2) Institute for Chemistry and
Technology of Materials, Graz University of Technology, Graz,
Austria (3) Institute for Chemistry, University of Graz, Graz,
Austria (4) Institute for Organic Chemistry and Macromolecular
Chemistry, Centre of Excellence for Polysaccharide Research,
Friedrich Schiller University of Jena, Jena, Germany (5)
Institute for the Engineering and Design of Materials, University
of Maribor, Maribor, Slovenia (6) Institute for Surface
Technologies and Photonics, Joanneum Research Materials,
Weiz, Austria
NFC surface while the POEGMA block provided surface
passivating properties.
CELL 303
In this contribution we present the creation of matrices for
controlled protein deposition whereas cellulose ultrathin films
are equipped with BSA (Bovine Serum Albumin) via
cationization of the surface by tailor made cationic celluloses.
The extent of protein affinity to these surfaces is controlled by
the solubility and charge density of the cationic cellulose
derivative. This effect is investigated at the example of
fluorescently labeled BSA at different concentrations and pH
values. The total amount of deposited protein on the surfaces
is quantified by means of QCM-D (Quartz Crystal Microbalance
with Dissipation Monitoring, wet mass) and MP-SPR (MultiParameter Surface Plasmon Resonance, dry mass).
Furthermore the amount of coupled water is obtained by
combination of QCM-D and MP-SPR data. It can be shown
that the tuning of protein adsorption is realizable over a wide
range (0.6-3.9 mg dry mass m-2) by varying the type of used
cationic cellulose derivative and the applied adsorption
conditions. Additionally, patterned cellulose thin films have
been prepared and cationic celluloses were adsorbed in a
similar fashion as in the QCM-D and MP-SPR experiments.
These cationic surfaces have been loaded with fluorescently
labeled BSA in different concentrations by an automatized
spotting apparatus. A correlation between the amount of
deposited protein and the fluorescence intensity is established.
CELL 302
Modification of cellulose with PDMAEMA-block-POEGMA
copolymers to control protein affinity for detection and
separation
Maija Vuoriluoto1, [email protected], Hannes Orelma1,
Mikko Poutanen1, Andreas Walther2, Janne Laine1, Orlando J.
Rojas1. (1) Aalto Univ, Espoo, Finland (2) DWI - Leibniz
Institute for Interactive Materials , Aachen, Germany
Cellulosic materials exhibit many desirable characteristics, e.g.
biodegradability and hydrophilicity, which make it an appealing
substrate for various biomedical applications. Modification of
cellulosic surfaces to create anti-fouling properties as well as to
control protein adsorption is paramount to the functionality in
these applications. Poly(ethylene glycol) or its derivatives
incorporated in multifunctional polymers have been found to
effectively prevent non-specific surface protein adsorption. In
this work we present a method to prepare a low-fouling
TEMPO-oxidized nanofibrillar cellulose (NFC) towards human
immunoglobulin G (hIgG) utilizing block copolymers of poly(2(dimethylamino)ethyl
methacrylate)
(PDMAEMA)
and
poly(oligo(ethylene glycol) methyl ether methacrylate)
(POEGMA) . POEGMA-b-POEGMA copolymer adsorption on
regenerated cellulose, NFC and TEMPO-oxidized NFC films
was investigated with quartz crystal microbalance with
dissipation (QCM-D) and surface plasmon resonance (SPR).
Atomic force microscopy (AFM) and X-ray photoelectron
spectroscopy (XPS) were applied to further verify that the
adsorption of the block-copolymers was mainly electrostatically
driven. The POEGMA-block-POEGMA copolymer adsorbed on
TEMPO-NFC surfaces could be partially regenerated in low pH
media and this effect was utilized to control bovine serum
albumin (BSA) adsorption and desorption. The blockcopolymers were observed to be good in preventing nonspecific hIgG binding. The cationic PDMAEMA block of the
copolymer functioned as an anchor to the anionic TEMPO-
Detection of human neutrophil elastase with fluorescent
peptide sensors conjugated to nanocellulosic solid
supports targeting wound care diagnostics
Krystal R. Fontenot1, [email protected], J.
Vincent Edwards2, Nicolette T. Prevost3, David Haldane4. (1)
USDA-SRRC, New Orleans, Louisiana, United States (4)
Innovatech Engineering, Tallahassee, Florida, United States
Human neutrophil elastase (HNE) is a biomarker for chronic
wounds and a therapeutic target for certain diseases. An
unchecked influx of neutrophils, which contain about one
pictogram of elastase per neutrophil, is responsible for
degrading growth factors and collagen formation, indefinitely
delaying the healing of chronic wounds. Nanocellulose when
conjugated with HNE peptide substrates has the potential to
improve point of care diagnostics used to assess the status of
chronic wounds, by offering a higher transducer surface area
for protease detection sensitivity. Over the years the use of
cellulose and other polysaccharides as a solid support for
peptides applicable to wound care has grown. Here cellulose
nanocrystals and mirofibrillated cellulose (CNC) derived from
cotton and wood respectively were compared as support
surfaces, and were produced with varying material forms for
attachment of elastase peptide substrates. Print cloth fabric,
wood/cotton cellulose nanocrystals and microfibrillated
cellulosic films were compared as putative transducer surfaces
to host-peptide fluorescent sensors of HNE. Analytical
approaches including attenuated total reflectance infrared
spectroscopy (ATR-IR), ultraviolet visible spectroscopy (UVVIS), mass spectrometry (MS), X-ray crystallography and
elemental analysis (EA) were utilized to characterize the
peptide-cellulose conjugates. The cellulose and nanocellulosepeptide conjugates were evaluated for their elastase detection
activities using a microtiter enzyme assay to monitor
fluorescence. Results of the relative sensitivity of HNE
detection, surface area differences, degree of peptide
substitution, and potential for applications to protease detection
will be discussed.
CELL 304
Interaction
of
biomolecules
with
nanostructured polysaccharide interfaces
micro-
and
Rupert Kargl2, [email protected], Matej Hribar4, Mitja Kolar4,
Christoph Cerny1, Tamilselvan Mohan1, Stefan Spirk3, Volker
Ribitsch1, Karin Stana-Kleinschek2. (1) Institute of Chemistry,
University of Graz, Heinrichstraße 28, 8010 Graz, Austria (2)
Faculty of Mechanical Engineering, Institute for Engineering
Materials and Design, University of Maribor, Smetanova ulica
17, 2000 Maribor, Slovenia (3) Institute for the Chemistry and
Technology of Materials, Graz University of Technology,
Stremayrgasse 9, 8010 Graz, Austria (4) Faculty of Chemistry
and Chemical Engineering, University of Maribor, Smetanova
ulica 17, 2000 Maribor, Slovenia
The design and properties of solid liquid interfaces are
essential for the applicability of renewable materials in the field
of life sciences. Biosensors and cell growth scaffolds are two of
the areas where understanding of wettability, morphology,
composition and adsorption play a key role for the
development of new products. In many of these cases
polysaccharides are used, owing to their compatibility with
biological materials. For such substrates the said phenomena
can be preferably studied on smooth, thin polysaccharide films
by state-of-the-art surface analytical methods. Detailed
knowledge obtained by these methods can further lead to the
manufacturing of tailored polysaccharide interfaces by polymer
blending, adsorption, and micro- and nano- structuring
methods. The interfaces designed in this way give spatially
resolved wettability, charges and chemical compositions, which
subsequently allow targeted protein and cell adhesion, leading
to highly functional polysaccharide materials. Results on the
structuring and surface properties of polysaccharide interfaces
and their interaction with biological matter will be presented.
CELL 305
Lignin esters in cellulose bicomponent thin films
Simone Strasser1,2, [email protected], Stefan Spirk1,
Christian Slugovc2, Manuel Kaschowitz4, Katrin Niegelhell2,
Tamilselvan Mohan3. (1) Institute for the Chemistry and
Technology of Materials, Graz University of Technology, Graz,
Austria (2) Graz University of Technology, Graz, Austria (3)
Institute of Chemsitry, University of Graz, Graz, Austria (4)
Institute for Chemistry and Technology of Materials, Graz
University of Technology, Graz, Styria, Austria
Lignin esters were synthesized by reacting lignin with various
carboxylic acid chlorides as well as by grafting/ring opening
polymerization of DL-lactide and e-lactone. The obtained
organosoluble lignin derivatives were used to fabricate blend
films with cellulose on silica supports by spin coating. Film
morphology, surface chemical composition and wettability of
the bicomponent thin films were determined by atomic force
microscopy, water contact angle and IR measurements.
Furthermore, the interaction of proteins with the bicomponent
surface was investigated by adsorption of BSA under various
conditions.
CELL 306
Valorization of lignins with applications in nanostructured
films
Bianca M. Cerrutti1, [email protected], Samarah V. Harb1,
Marli L. Moraes2, Peter Hammer1, Sandra H. Pulcinelli1, Celso
V. Santilli1. (1) Physical Chemistry of materials, Instituto de
Química -IQ-UNESP, Araraquara, São Paulo, Brazil (2)
Instituto de Ciência e Tecnologia, Universidade Federal de
São Paulo , São José dos Campos, SP, Brazil
Valorization of lignins is strategic for countries that produce a
lot of biomass, such as Brazil where large amounts of sugar
cane bagasse are generated in the alcohol and sugar cane
industry. Rather than being burnt to generate energy, lignin
can be used in nanotech applications in which its
biocompatibility can be exploited. In this work, we produced
three types of film with lignin serving as matrix for
immobilization of biomolecules and for reinforcing organicinorganic hybrids with anti-corrosion properties. Lignin was
found suitable as matrix in layer-by-layer (LbL) films containing
an antigenic peptide whose activity was preserved to be
capable of recognizing anti-HIV antibodies. Two-bilayer LbL
films of the lignin/peptide pair were deposited onto
interdigitated gold electrodes to form selective immunosensors
based on impedance spectroscopy which could detect anti-HIV
antibodies at concentrations as low as 0.1 ng/mL. This concept
of controlled supramolecular structures with lignin was
extended to produce phytase/lignin LbL films where
fluorescence from phytase was entirely quenched.
Fluorescence could be recovered if spacing bilayers of
polyelectrolytes were inserted between the lignin and phytase
layers, and therefore one may conceive sensors based on
Förster resonant energy transfer (FRET) containing lignin,
which is unprecedented in the literature. In the third
application, lignin was homogeneously dispersed into organicinorganic hybrid coatings made with siloxane-poly(methyl
methacrylate) (PMMA) synthesized with the sol-gel process.
Incorporation of lignin improved the mechanical properties and
thermal stability of the hybrids, which acted as efficient
diffusion barriers in anti-corrosion coatings for steel in a highly
saline environment. Taken together these results indicate that
lignins can be incorporated into nanostructured films as matrix
to immobilize biomolecules and as reinforcement for coatings
and functionalized surfaces.
CELL 307
Flexibility of cellulose nanocrystal networks in response
to water vapor
Elina Niinivaara3, [email protected], Marco Faustini 4,
Tekla Tammelin2, Heike M. A. Ehmann1, Stefan Spirk1, Eero
Kontturi3. (1) Institute for Chemistry and Technology of
Materials, Graz University of Technology, Graz, Austria (2)
High Performance Fibre Products, VTT - Technical Research
Center of Finland, Espoo, Finland (3) Department of Forest
Products Technology, School of Chemical Technology, Aalto
University, Espoo, Finland (4) Laboratorie Chimie de la Matiere
Condensée – Collège de France, Université Pierre et Marie
Curie, Paris, France
Ultrathin films made from renewable resources have become
an area of increasing interest for materials scientists as they
provide an interesting platform for technological advancements
in areas including biosensors, transmitters and optoelectronic
materials. For all these types of applications, the stability of the
matrix to atmospheric conditions is critical to ensure
predictablein-serviceperformance.In this study, the swelling
behavior of cellulose nanocrystal (CNC) thin films has been
investigated using several analytical techniques; ellipsometric
porosimetry, quartz crystal microbalance with dissipation
(QCM-D), x-ray reflectivity (XRR) and infrared reflection
absorptionspectroscopy(IRRAS).In contrast to what was
expected, the results demonstrated that CNC networks
supported on a silica substrate showed significant swelling
upon the uptake of water vapor. CNCs in themselves are not
able to swell upon exposure to water vapor as it is unable to
penetrate into the crystalline structure thus has no effect on
crystal dimensions.Our measurements clearly establish that
thin film CNC networks are responsive to water vapor as they
exhibit extensive swelling as a function of relative humidity.
Hypothetically, swelling of these films results from flexibility
within the nanocrystal network as water vapor is believed to
condense in the voids between the CNCs generating capillary
pressure that is significant enough to allow movement of the
individual CNCs, resulting in the observed swelling.
CELL 308
CELL 310
Deuterated cellulose thin films - challenges and surprises
Model wound dressing
electrospun fibers
David Reishofer1, [email protected], Rupert Kargl5,
Heike M. A. Ehmann2, Robert Schennach4, Silvo Hribernik5,
Andreas Kornherr6, Karin Stana-Kleinschek5, Stefan Spirk3,
[email protected]. (1) Graz University of Technology,
Graz, Austria (2) Institute for Chemistry and Technology of
Materials, Graz University of Technology, Graz, Austria (3)
Institute for the Chemistry and Technology of Materials, Graz
University of Technology, Graz, Austria (4) Tech Univ Graz Inst
Solid St, Graz, Austria (5) University of Maribor, Maribor,
Slovenia (6) Mondigroup, Ulmerfeld-Hausmening, Austria
In this contribution, amorphous deuterated cellulose thin films
are prepared by regeneration of trimethylsilyl cellulose thin
films in a DCl/D2O atmosphere or by exposing the films to
either liquid or gaseous D2O. Besides standard analytical
techniques to characterize the films, extensive IR
spectroscopic investigations are performed in order to track
changes in the supramolecular structure of the films upon
different physical treatments (e.g. drying, hornification).
CELL 309
Cellulose thin films meet a synchrotron beam: In situ
observation of rearrangement during regeneration and
drying using grazing incidence small angle X-ray
scattering
Heike M. A. Ehmann1, [email protected], Oliver
Werzer2, Tamilselvan Mohan3, Andreas Kornherr4, Karin
Stana-Kleinschek5, Heinz Amenitsch6, Roland Resel7, Eero
Kontturi8,9, Stefan Spirk1, [email protected]. (1) Institute
for Chemistry and Technology of Materials, Graz University of
Technology, Graz, Austria (2) Institute of Pharmaceutical
Technology, Karl-Franzens University of Graz, Graz, Austria
(3) Institute of Physical and Theoretical Chemistry, KarlFranzens University of Graz, Graz, Austria (4) Mondi Uncoated
Fine Paper Europe & International Mondi, UlmerfeldHausmening, Austria (5) Faculty of mechanical engineering,
University of Maribor, Maribor, Slovenia (6) Institute of
Inorganic Chemistry, Graz University of Technology, Graz,
Austria (7) Institute of Solid State Physics, Graz University of
Technology, Graz, Austria (8) Department of Forest Products
Technology, Aalto University, Aalto, Finland (9) Department of
Chemical Engineering, Imperial College London, London ,
United Kingdom
The rearrangements of cellulose, the most abundant
biopolymer on earth, are still not fully understood despite its
importance in many large scale industrial processes. Here, we
present a versatile approach that allows for an in-situ
investigation of two major types of rearrangements typically
observed in paper and fiber industries, namely regeneration
and drying of cellulose. For this purpose, model systems have
been employed (cellulose thin films) to study pore size
changes using grazing incidence small angle X-Ray scattering
at a synchrotron facility during regeneration and drying of the
films.
materials
–
thin
films
vs.
Uroš Maver1, Manja Kurečič2, [email protected], Tina
Maver2, Tanja Pivec2, Zdenka Peršin2, Lidija Gradišnik1, Karin
Stana-Kleinschek2, [email protected]. (1) Faculty of
Medicine, University of Maribor, Taborska ulica 8, 2000
Maribor, Slovenia (2) Faculty of Mechanical Engineering,
Institute of Engineering Materials and Design, University of
Maribor, Smetanova ulica 17, 2000 Maribor, Slovenia
Wound care is one of the fastest growing markets for medical
materials worldwide. Novel approaches in wound dressing
design are therefore explored with a high frequency.
Considering the present socio-economic situation, a lot of effort
is put into development of methods with high benefits, but low
costs. Model wound dressings are lately often referred to as
one of the possible platforms for cheap, yet precise
development of novel wound dressing materials. Their
combination with drugs, followed by thorough characterization,
enabled by their controlled synthesis, make them ideal for
testing of novel advanced wound dressing approaches.
Electrospinning has in the last decade evolved to one of the
main techniques for preparation of nanofibers from versatile
precursor solutions and for coating of fibers and other
materials. Its main advantages are exceptionally large
nanofiber active surface area per mass unit, possible fibers’
morphology control, a high benefit/cost ratio and relative easy
transfer to the industrial scale.In this study, electrospun fibers
were compared with thin films in relation to their application
potential in design of novel advanced wound dressing
materials. For this purpose, both systems, combined with
synthetic drugs (pain reducing agents) or natural antioxidants,
were
characterized
for
their
surface
properties,
biocompatibility, bioactivity, wettability and morphology. Final in
vitro testing was performed on Franz diffusion cells, while their
safety and efficacy was shown on skin-based cell cultures.
CELL 311
Nanocelluloses as versatile platform of interactions for
smart and tunable thin films
Bernard Cathala1, [email protected], Céline
Moreau1, Firas Azzam1, Patricia Bertoncini2, Olivier Chauvet2.
(1) BIA, INRA, Nantes, France (2) Institut des Matériaux de
Nantes, Nantes, France
Nanocelluloses are stiff nanorods or nanofibers that offer a
variety of interactions capabilities. They can interact with other
components through Hydrogen bonds or van der Walls
interactions thank to the hydroxyl or aliphatic groups of glucose
monomers, they can also establish electrostatic interactions
due the occurrence of ionic moieties on the crystal surface
arising usually from preparation procedures (sulfuric acid
hydrolysis or TEMPO oxidation for instance). Furthermore the
high level of organization of the cellulose chains within the
crystal structure induces uneven exposure of chemical
functions on the crystal faces resulting in hydrophobic or
hydrophilic character of the faces. In this talk, three examples
of thin film elaboration displaying smart or tunable functions will
be presented. All elaboration processes take advantage of
specific interactions capability of nanocelluloses. The first
example will describe the formation of structurally colored thin
films composed by cellulose nanocrystals and xyloglucan
interacting through Hydrogen and van der Walls interactions1.
The second will address the dispersion of single wall carbon
nanotubes by cellulose nanocrystals through self-assembly for
the elaboration of conductive films2. Finally, films with tunable
porosity and antireflective properties can be constructed
through the control of electrostatic interactions between a
polycation
and
cellulose
nanofibrils3.
1 Coloured Semi-reflective Thin Films for Biomass-hydrolyzing
Enzyme Detection. Cerclier C., Lack-Guyomard A., Moreau C.,
Cousin F., Beury N., Bonnin E, Jean B., Cathala B. Advanced
Materials 23: 3791–3795, 2011
2 Cellulose Nanocrystals assisted Dispersion of Luminescent
Single Wall Carbon Nanotube for Layer-by-Layer Assembled
Hybrid Thin Films. Olivier C., Moreau C., Bertoncini P., Bizot
H., Chauvet O., and Cathala B., Langmuir, 28 : 12463–12471,
2012
3 Cellulose-based multilayered thin films: ionic strength effect
on porosity, swelling and optical properties. Azzam F., Moreau
C., Cousin F., Menelle A., Bizot H. and Cathala B. Langmuir 30
: 8091-8100, 2014
CELL 312
Synergistic
templated
self-assembly
of
cellulose
nanocrystals (CNCs) in thin block copolymer films
Danielle Grolman2, [email protected], Jeffrey Gilman1,
Alamgir Karim2. (1) Materials Science and Engineering
Division, National Institute of Standards and Technology,
Gaithersburg, Maryland, United States (2) Department of
Polymer Engineering, The University of Akron, Akron, Ohio,
United States
Nanofillers in thin polymer films offer unique advantage to
potentially modify the film's thermal, optical, electrical and
mechanical properties due to the high surface area to volume
ratio and intrinsic property change at the nanoscale. Nanofilled
polymer films have been shown to exhibit unusual film stability
to dewetting with a non-monotonic behavior with nanofiller
loading, potentially arising from a number of factors like
competitive phase behavior, substrate wetting, and filler
aggregation, particularly in the high nanofiller concentration
limit. In this regard, block copolymer films can act as ideal
nanoscale phase separated structured templates due to the
feasibility of tuning parameters for directed self-assembly. In
conjunction with incorporated cellulose nanocrystals (CNCs),
we seek to understand how individual anisotropic nanofillers
can provide synergistic reinforcement to inherently anisotropic
nanostructured block copolymer films. Current preliminary work
displays a clear enhancement in the Young's Modulus with
increased CNC loading using strain-induced elastic buckling
instability for mechanical measurements (SIEBIMM) for thin
films. To this end, we examine the nanoscale to microscale
morphology of the blend film through atomic force microscopy
(AFM), grazing incidence small angle x-ray scattering
(GISAXS) and optical microscopy, and CNC dispersion and
percolation through high-intensity grazing incidence wide angle
x-ray scattering (GIWAXS) analysis, coupled with SIEBIMM
nanomechanical techniques.
ELL 313
New concepts for molecular engineering of macroscopic
adhesion between cellulose surfaces
Andrea Trager3, [email protected], Samuel Pendergraph3, Anna
Carlmark2, Lars Wagberg1. (1) KTH Fibre Polymer Techn,
Stockholm, Sweden (2) Fibre and Polymer Technology, KTH
Royal Institute of Technology, Stockholm, Sweden (3) Royal
Institute of Technology, Stockholm, Sweden
Layer-by-Layer (LbL) films, where oppositely charged
polyelectrolytes are deposited consecutively on top of each
other, provide excellent means to control the adhesive
interactions between solid materials. Nano-meter thin layers
can be formed and fine tuning of the molecular components as
well as the deposition conditions enables us to tailor the
adhesive properties of the thin films. In this study, triblock
copolymers containing either anionically or cationically charged
outer blocks, together with middle blocks possessing different
chemical and physical properties, such as ductility or stiffness,
are synthesized and characterized. Hereafter their behavior as
micelle dispersions is evaluated followed by adsorption studies
where the polymers are adsorbed in layer by layer assemblies
onto model surfaces of silica and cellulose. The adhesive
properties of the LbL films are characterized with colloidal
probe AFM and a contact adhesion testing apparatus designed
specifically for this purpose. These films could potentially find
numerous applications where thin, adhesive joints are desired,
yielding a material with a tailored combination of properties
such as both ductility and stiffness.
CELL 314
Improved interfacial bonding in cellulosic biocomposites
with humins-based furanic resins
Nathanael Guigo2, [email protected], Jean-Mathieu Pin2, Alice
Mija2, Luc Vincent2, Nicolas Sbirrazzuoli2, Jan C. van der
Waals1, Ed de Jong1. (1) Avantium Technologies, Amsterdam,
North Holland, Netherlands (2) Laboratory of Condensed
Matter Physic, University Nice Sophia Antipolis, Nice Alpes
Maritmes, France
Humins are side-stream products generated during acid
catalyzed sugar (carbohydrate) conversion processes, such as
in the production of furan-dicarboxylic acid (FDCA) the key
building block for Poly(ethylene 2,5-furandicarboxylate) (PEF).
Valorization of the humins into value-added materials is
necessary to increase the sustainability as well as the
economics of these kind of bio-refinery operations.
Interestingly, the present communication demonstrates that
large quantities of humins can be incorporated into a
thermosetting polyfuranic network. Homogeneous and fully
biobased systems comprising polyfurfuryl alcohol (PFA) and
humins were prepared via acid-induced polymerizations.[1] It
was shown by means of FT-IR measurements that new
chemical interconnections were created between the side
chain oxygen groups of the humins and the PFA network.
Humins-based thermosetting furanic composites were
prepared with cellulosic fibers. Comparisons were made with
composites generated with polyfurfuryl alcohol (PFA) and with
PFA/lignin resins. SEM observations reveal that the
PFA/humins composites present more fiber fractures than the
other composites which attest for higher interfacial bonding
and more efficient stress transfer between the matrix and the
fibers in presence of humins. The higher ductility of the
humins-based matrix allows to reach a two-fold higher tensile
strength in comparison with other composites tested.
Incorporation of humins increases the interfacial bonding with
cellulose and decreases the brittleness of the furanic
composites which is one major drawback of the pure PFA
composites. From a conceptual point of view, the humins
opens quite interesting perspectives in the development of new
wood adhesives and wood composites.
[1] Pin, J.-M.; Guigo, N.; Mija, A.; Vincent, L.; Sbirrazzuoli, N.;
van der Waal, J. C.; de Jong, E. ACS Sustainable Chemistry &
Engineering 2014, 2, 2182.
in detail. The results showed that the oxidation process
successfully introduced the aldehyde group into the BC, and
also improved the stability of the immobilized laccase. AFM
and SEM results showed that both TiO2 and laccase were well
immobilized on the surface of the BC. Compared with free
laccase, the optimum pH of the immobilized laccase shifted to
lower pH, and optimum temperature were decreased from 55
ºC to 50 ºC. The dye degradation experiments showed that the
optimum pH for dye degradation was pH 5.0-6.0, and optimum
temperature was about 40 ºC. Under UV illumination, the dye
degradation efficiency improved significantly. Therefore, this
method proves very effective and can find its application in
waste water remediation.
CELL 315
Spray-dried microencapsulation of tea tree oil with a
complex of methyl cellulose/chitosan/alginate
Juan Chen1, Xueqiong Yin1,2, [email protected], Xuyu
Wang1, Junhua Chen1, Li Zhu1, Lucian A. Lucia2. (1) Hainan
Provincial Fine Chemical Engineering Research Center,
Hainan university, Haikou, Hainan , China (2) Departments of
Forest Biomaterials and Chemistry, North Carolina State
University, Raleigh, North Carolina, United States
In this paper, methyl cellulose (MC) was used to increase the
compatibility of the tea tree oil and chitosan (CTS)/alginate
(ALG) during spray-dried microencapsulation. The best spray
drying conditions was: air inlet temperature 210oC, needling
frequency 2s each time, pump flow 60 r/min. The highest oil
content 20.7% was obtained with the ratio of methyl cellulose,
chitosan, alginate and oil 2:3:15:4. The microcapsules in
solvent were characterized with polarized light microscopy
(PLM), which indicated that the microcapsules from
MC/CTS/ALG expressed good spherical shape, while the other
systems with one component, or bicomponents of MC, CTS, or
ALG, or three components MC/ALG/CTS resulted in no good
spherical microcapsules. Scanning Electron Microscopes of
the dried samples revealed spheres with little deformed
surface owing to the fast evaporation of water during drying.
After one month storage, the oil loss was 1.02%, indicating that
the
microcapsules
were
stable
during
storage.
Key words: tea tree Oil, microencapsulation, characterization,
methyl cellulose, chitosan, alginate
CELL 316
Photocatalytic and biocatalytic degradation of dye
solution using laccase and titanium dioxide loaded on
bacterial cellulose
Avinav Nandgaonkar2, [email protected], Qingqing
Wang1, Wendy Krause2, Qufu Wei3, Lucian Lucia4. (1) Key
Laboratory of Eco-Textiles , Jiangnan University, Wuxi,
Jiangsu, China (2) College of Textiles, North Carolina State
University, Raleigh, North Carolina, United States (4) Forest
Bio-materials , North Carolina State University, Raleigh, North
Carolina, United States
In this work, TiO2 and laccase (Lac) were co-immobilized on
the surface of oxidized bacterial cellulose (OBC) [See Figure 1]
and the dye degradation process was carried out under certain
conditions. FTIR, SEM, and AFM were used to analyze the
oxidation of BC, TiO2 coating, and laccase immobilization. The
optimum pH, temperature, temperature stability, operational
stability of the OBC/Lac and OBC/TiO2-Lac were also studied
Graphical presentation of the immobilization of laccase and TiO2 on
the surface of bacterial cellulose
CELL 317
Enzymatic bio-fuel cells based on bacterial cellulose
(BC)/MWCNT/laccase (Lac) and bacterial cellulose
/MWCNT/ glucose oxidase (GOD) electrodes
[email protected],
Avinav
Qingqing
Wang1,
Nandgaonkar2, Lucian Lucia3, Qufu Wei1. (1) Key Laboratory of
Eco-Textiles , Jiangnan Univerisy, Wuxi, Jiangsu, China (2)
College of Textiles, North Carolina State University, Raleigh,
North Carolina, United States (3) Forest Bio-materials , North
Carolina State University, Raleigh, North Carolina, United
States
A novel hydrogel enzymatic bio-fuel cell composed of a biocathode (BC/MWCNT/Lac) and an enzymatic bio-anode
(BC/MWCNT/GOD) were developed and tested. The biocathode and bio-anode were prepared by deposition of
MWCNT and Lac/GOD onto BC, which act as conductive layer,
catalyst, and carrier; respectively. The BC/MWCNT composite
material was characterized by Scanning Electron Microscopy
(SEM), Fourier Transform Infrared Spectroscopy (FTIR) as well
as Thermogravimetric Analysis (TGA). The SEM, FTIR and
TGA results confirmed the attachment of MWCNT on BC.
BC/MWCNT/Lac bio-cathode was characterized by cyclic
voltammetry. An enzymatic biological fuel cell was
characterized by linear sweep voltammetry (LSV). The
enzymatic bio-fuel cell exhibited excellent performance with the
largest open circuit voltage (0.76 V) and with a maximum
power density value (24 μWcm-3). The biofuel cell also
exhibited acceptable stability over the course of 30 days.
CELL 318
epoxy polymeric systems display interesting properties that are
close to their commercial counterparts.
Improved antibacterial noatings with Nanotitania and
cyclic N-halamine
Xuehong Ren1, [email protected], Jing Li1, Lin Li1,
Tung-Shi Huang2. (1) College of Textile and Clothing, Jiangnan
University, Wuxi Jiangsu, China (2) Department of of Poultry
Science, Auburn University, Auburn, Alabama, United States
N-halamine compounds have a great potential value in
theoretical research and applications in the field of antibacterial
materials. A series of N-halamine precursors, including cyclic
N-halamine siloxane precursors and cyclic N-halamine
precursors with double hydroxy groups were synthesized. The
synthesized compounds were applied to cellulosic fibers with
nano-titania particles and bounded to the cellulose by covalent
bonds. Simple pad-dry-cure technique was used in the
coatings. The produced organic−inorganic hybrid N-halamine
antimicrobial materials were characterized and evaluated. The
results show that these N-halamine antimicrobial coated
fabrics have great biocidal efficacy, durability, UV stability, and
regenerability. The stability of N−Cl bond and antimicrobial
materials themselves have been improved under UV light
irradiation with the addition of nano-titania in the coatings. The
antimicrobial materials have potential applications in the field of
biomedical and healthcare industry.
CELL 319
Renewable resources
thermosetting resins
as
precursors
of
biobased
Maria L. Auad, [email protected], Bernal Sibaja. Polymer
and Fiber Engineering Department, Auburn University, Auburn,
Alabama, United States
The macromolecular chemistry based on vegetable feedstock
represents the answer to the quest for polymeric materials
capable of replacing their fossil-based counterparts. The use of
petroleum in chemical industry has proved to be
disadvantageous in terms of costs, shortage supply and it is a
nonrenewable source. Triglycerides or vegetable oils have a
three-armed star structure in which three fatty acids are joined
at a glycerol junction. Their competitive cost, worldwide
availability and built-in functionality (esters functions and
unsaturations) have catapulted the use of triglycerides as a
source of macromonomers for polymer applications. The
development of oleo-chemicals has been carried out mainly
through the functionalization of the double bonds to insert more
reactive groups, usually epoxy, amine or hydroxyl, etc. The
mechanical properties of these oil-based epoxy resins can be
enhanced by the addition of materials bearing aromatic
structures. Phenolic compounds exist in most plant tissues as
secondary metabolites. Their structure consists of an aromatic
ring carrying one (phenol) or more hydroxyl (polyphenol)
moieties. These hydroxyl groups are prompted to be
chemically modified. Thus, by employing triglyceride and
phenolic monomers functionalized with epoxy and amine
groups, via oxidation and nucleophilic addition respectively, the
main purpose of this project is to cover the major aspects
related to the chemical synthesis, physical-chemical
characterization and study of thermo-mechanical properties of
a bio-based epoxy resin, where highly functionalized
components are synthetized by chemical modification of oils
and phenolic acids. Results showed that this new biobased
CELL 320
Sisal pulp as raw material for magnetic hybrid films and
sugars
Elisabete Frollini3, [email protected], Laudemir C.
Varanda1, Adilson J. A. de Oliveira2, Ângelo D. Faceto2, Bruno
M. Rodrigues3, Daiana M. Furlan3, Daniel A. de Moraes1, Joice
J. Kaschuk3. (1) Institute of Chemistry of Sao Carlos, Colloidal
Materials Group, Center for Research on Science and
Technology of BioResources, University of Sao Paulo, Sao
Carlos , Sao Paulo, Brazil (2) Superconductivity and
Magnetism Group, Physics Department, Federal University of
São Carlos, Sao Carlos, Sao Paulo, Brazil (3) Macromolecular
Materials and Lignocellulosic Fibers Group, Center for
Research on Science and Technology of BioResources,
Institute of Chemistry of São Carlos, University of Sao Paulo,
Sao Carlos, Sao Paulo, Brazil
The sisal pulp was chosen in the present study due to the fact
that the plant has rapid growth and fibers with a high cellulose
content. One of the aims was to contribute to studies on the
incorporation of magnetite nanoparticles (NPs) (Fe3O4) in films
produced from sisal pulp or acetates from this pulp Magnetite
was chosen due to its low toxicity when compared with metallic
NPs and its potential application in several areas, including the
medical area. Films from sisal cellulose and its acetates were
obtained in the absence and presence of prior prepared NPs
(3.0 g L-1). The composite films based on cellulose and its
acetates showed superparamagnetic behavior at room
temperature (SQUID magnetometry) with good saturation
magnetization (27- 46 emu.g-1). No correlation between DS
and the magnetic properties of the acetates films was
observed, which showed some dependence on the presence
of microspheres(films from acetates of DS≥2.0).The sisal pulp
(previously mercerized) was also enzymatically hydrolyzed
using varied amount of commercial enzymes. Aliquots
constituted of unreacted pulp and liquor were taken from the
medium during the reaction. The unreacted pulps were
characterized with respect to Ic, MMvis, length and thickness
and scanning electron microscopy (SEM). In general the
analysis of unreacted pulps showed different behaviors with
respect to Ic and MMvis, depending on the time interval
elapsed during the reaction. Considering the peak density of
greater length and thickness the variation during the reaction
was [129-215] µm for [77-129] µm (length), and from [18-30]
µm to [14-18] µm (thickness). The liquors were analyzed by
HPLC and high yields of glucose were obtained (over 90%).
The enzymatic hydrolysis of cellulosic pulps with features
similar to the pulp used in the present study, has great
potential for the production of sugars via enzymatic catalysis
aiming at the production of bioethanol.
CELL 321
Biopolymers from tomato agro-industrial residual wastes
Mayra B. Gómez-Patiño3,2, [email protected], Juan
Vicente Méndez-Méndez2, María Eugenia Jaramillo-Flores4,
José Campos-Terán1, [email protected], Daniel
Arrieta-Baez2, [email protected]. (1) Departamento
de Procesos y Tecnología, Universidad Autónoma
Metropolitana-Cuajimalpa, México, D.F., Mexico (2) Centro de
Nanociencias y Micro y Nanotecnologías, Instituto Politécnico
Nacional, México, D.F., Mexico (3) Posgrado en Ciencias
Naturales e Ingeniería, Universidad Autónoma MetropolitanaCuajimalpa, México, D.F., Mexico (4) Departamento de
Ingeniería Bioquímica, Escuela Nacional de Ciencias
Biológicas, Instituto Politécnico Nacional, México, D.F., Mexico
Recently, polyester syntheses through enzymatic catalysis by
various monomer combinations have been extensively
investigated. By utilizing specific enzymatic catalysis,
enantioselective,
regioselective,
and
chemoselective
polymerizations have been developed. Worldwide potential
demands for replacing petroleum derived raw materials with
renewable plant-based ones in production of polymeric
materials are quite significant in the social and environmental
viewpoints. Tomato is one of the fruits of increased production
in Mexico. However, it is still a highly perishable fruit that
requires fast and efficient transportation; otherwise this factor
may become a financial problem due large losses (10 to 20%
of the production). Cutin is the most abundant polyester in
nature and constitutes the framework of the protective cuticle
of stems and leaves of higher plants. Recently, we have
reported an efficient isolation of 10,16-dihydroxyhexadecanoic
acid (10,16-DHPA), the main monomer of the tomato cuticle,
and the preparation of some derivatives from this important
cuticular component [1]. Our interest in the synthesis of
aliphatic polyesters is focused on the possibility to produce
linear, hydroxyl functionalizable polyesters through a
polymerization method that must be versatile enough to allow
for the facile preparation of a variety of different materials.
Thus, we are reporting the polymerization of 10,16-DHPA, and
its methylated ester (methyl-10,16-dihydroxyhexadecanoate,
methyl-10,16-DHHD) mediated by six different lipases. For
10,16-DHPA, optimum yields were obtained at 60⁰C using
toluene and 2-methyl-2-butanol as solvent, while for methyl10,16-DHHD the bests yields were obtained in toluene and
acetonitrile. Both reactions leaded to linear polyesters
according with the NMR analysis, and there was no data
indicating the presence of branched polymers. Functional
linear oligomers obtained from tomato agro-residual wastes,
could be potentially used in the field of pharmaceutical and
food
industry
as
drug
or
nutraceutical
carriers.
[1] Arrieta-Baez, D.; Cruz-Carrillo, M.; Gómez-Patiño, M.B.;
Zepeda-Vallejo,
L.G.
Derivatives
of
10,16Dihydroxyhexadecanoic Acid Isolated from Tomato (Solanum
lycopersicum) as Potential Material for Aliphatic Polyesters.
Molecules 2011, 16, 4923-4936.
CELL 322
Formation
and
characterization
of
10,16dihydroxyhexadecanoic acid thin films extracted from
tomato residues
José Vicente Hernández-Ortíz3, Mayra B. Gómez-Patiño3,2,
Claudia Jazmín Ramos-Torres2, Daniel Arrieta-Baez2, José
[email protected].
(1)
Campos-Terán1,
Departamento de Procesos y Tecnología, Universidad
Autónoma Metropolitana-Cuajimalpa, México, D.F., Mexico (2)
Centro de Nanociencias y Micro y Nanotecnologías, Instituto
Politécnico Nacional, Mexico, D.F., Mexico (3) Posgrado en
Ciencias Naturales e Ingeniería, Universidad Autónoma
Metropolitana-Cuajimalpa, México, D.F., Mexico
The use of agricultural residues to obtain products of higher
added value is becoming a green alternative within the
industrial sustainable processes. Processing of fruits and
vegetables for commodities such as juices or sauces results in
the accumulation of large amounts of byproducts of little or no
commercial value. However, there are components of these
waste products that are of potential value if they could be
recovered economically. For example, cutin is the most
abundant polyester in nature and constitutes the framework of
the protective cuticle of stems and leaves of higher plants.
Chemically, the cutin is an amorphous polymeric network of
polyhydroxylated C16 and C18 fatty acids monomers crosslinked by ester bonds. The main monomer of tomato cuticle,
10,16-dihydroxy-hexadecanoic acid (10,16-DHPA) and its
methyl ester derivative (methyl-10,16-dihydroxyhexadecanote;
methyl-10,16-DHHD) were used to enzymatically produced
linear functionalized polyesters [1]. All the compounds,
characterized by NMR, MALDI-TOF and ESI-MS analysis,
have potential application in the food, pharmacy and
cosmetology areas. In this regard, a study of their capacity to
form interfacial films at the air-water and air-solid interfaces
was performed using Langmuir and Langmuir-Blodgett thin
films, respectively. Langmuir films were also observed and
characterized with Brewster Angle Microscopy (BAM).
Langmuir-Blodgett films of the polyesters were analyzed by
contact angle measurements, atomic force microscopy and
spectroscopic ellipsometry. In this work, our latest results will
be presented.
[1] Gómez-Patiño, B.; Cassani, J.; Jaramillo-Flores, E.;
Zepeda-Vallejo, G.; Sandoval, G.; Jimenez-Estrada, M. and
Arrieta-Baez, D., (2013). Molecules (18):9317-9333.
CELL 323
Functional lignins used as curing agent in fiber-reinforced
epoxy-materials
Markus A. Biesalski1, [email protected], Matthias
Baaske2, Sabrina Mehlhase3, Roland Klein5, Sanna Valkonen4,
Michael Duetsch6. (1) Department of Chemistry, Technische
Universität Darmstadt, Darmstadt, Germany (2) AK Rehahn,
TU Darmstadt, Darmstadt, Germany (3) Technische Universitat
Darmstadt, Darmstadt, Germany (4) UPM GmbH, Augsburg,
Germany (5) Fraunhofer Institute LBF, Darmstadt, Germany
Lignin obtained as a by-product in biorefinery processes has
been used in past decades mostly as a source of energy, and
very few lignin is currently used as a chemical commodity
material. Here we introduce recent efforts spend in the design
of novel composite materials, where amine-functional lignin
has been used as a curing agent in Epoxy-based material.
Potential benefits for a given thermosetting protocol will be
discussed, such as the reduction of the amount of conventional
hardeners by addition of amine-functional lignin. In addition, we
will discuss curing kinetics in more detail, in particular,
observed differences of amine-functional lignin vs. nonmodified lignins in the epoxy-curing process. Finally, we will
show that it is possible to introduce such functional lignins as
substitutes in fiber-reinforced epoxy materials, and we
compare mechanical properties of such lignin-based
composites to conventional fiber-reinforced materials.
CELL 324
Deconstructing a natural fiber: Physicochemical and
structural properties of cellulose nanofribils and
nanocrystals from Colombian fique plants
Sergio A. Ovalle-Serrano1, Lina F. Jaimes-Cote1, Claudia P.
García-Villamizar1, Franci N. Gómez-Jaimes2, Cristian BlancoTirado1, Marianny Y. Combariza1, [email protected]. (1)
Escuela de Química, Universidad Industrial de Santander,
Bucaramanga, Santander, Colombia (2) Escuela de Ingeniería
Metalúrgica,
Universidad
Industrial
de
Santander,
Bucaramanga, Santander, Colombia
Hard or leaf fibers are natural biocomposites where cellulose
microfibrils are bundled together by hemicellulose and lignin
forming complex superstructures known as macrofibers. Most
hard fibers are vascular in origin and serve as mechanical
strength components helping the leave to maintain an upward
position; such is the case of Fique plants (Furcraea spp.)
native to the Colombian Andean region. Fique macrofibers are
extracted and widely used in Colombia as raw materials for
manufacturing cordage, rope, crafts and coffee sacks. The
length of the macrofibers, so far the only material from the
Fique plant with any application, ranges from 0.8 to 1.0 m after
extraction from the leave, and their weight only amounts up to
4 - 5% of the total leave weight. However, during the extraction
process shorter fibers and other cellulosic materials,
comprising up to 6% of the leave weight, are not recovered
and instead disposed of as residue. We investigated the
physicochemical and structural properties of cellulose
nanofribils and nanocrystals extracted from long and short
Colombian Fique fibers, via hydrolysis or TEMPO/mediated
reactions. We correlate cellulose crystallinity indexes, thermal
properties, z potential, aspect ratio, and number of
sulfate/carboxylate groups on the surface, among others, with
extraction experimental parameters. Our results indicate that
Fique by-products could be an additional source of cellulosic
materials with outstanding properties and wide range of
applications.
polypropylene.
CELL 326
Surface active materials from functionalized fique's
nanocrystalline cellulose
Franci N. Gómez-Jaimes2, Maria M. Gonzáles-Bernal1, Camila
F. Medina-Sandoval1, Jeferson Valencia1, Marianny Y.
Combariza1,
Cristian
Blanco-Tirado1,
[email protected]. (1) Escuela de Química,
Universidad
Industrial
de
Santander,
Bucaramanga,
Santander, Colombia (2) Escuela de Ingeniería Metalúrgica,
Universidad
Industrial
de
Santander,
Bucaramanga,
Santander, Colombia
Functionalized Nanocrystalline Cellulose (NCC) can lead to
several materials of industrial importance. In this work we
report on the surface modification of nanocrystalline cellulose,
obtained from a byproduct of fique fibers, by incorporation of
non polar moieties. NCC is produced from Fique fibers by acid
hydrolysis or TEMPO mediated reactions. Suspensions are
centrifuged and cleaned thoroughly to obtain pure NCCs. We
used different synthetic strategies to modify the NCC’s surface.
For example, direct transesterification with triacylglycerols is
achieved when NCC is mixed with palm oil in acetone, dried
and heated to 120 ˚C for 60 minutes in a oven. The modified
NCC exhibits surface activity and can be used as non ionic
surfactant in a variety of applications. For instance, when this
new material is redispersed in an organic solvent, it can be
used to inhibit the formation of water in oil emulsions, a
desirable trait in some industrial applications where forming
emulsion could lead to increasing viscosity and lowering flux.
CELL 325
CELL 327
Collection and evaluation of blended polypropylene
banana tree rachis fibers (Musa AAA)
Roy Zamora, [email protected]. Laboratory, INA
(National Institute of Learning), La Uruca, San Jose, Costa
Rica
The use of natural fibers (such as a thermoplastic filler) to
replace traditional synthetic fibers, presents interesting
alternative low-cost production, ecological and environmental
advantages. Through an extrusion process were developed
composite materials (MC) fibrous material from banana rachis
smaller than a millimeter in different percentages and virgin
polypropylene. The composites materials were evaluated with
virgin polypropylene (PP). The composites were tested by
analysis of melt flow index (FI), thermogravimetric analysis
(TGA), tensile and flexural, differential scanning calorimetry
(DSC), X -ray diffraction (RX) and Scanning Electronic
Microscopy (SEM). TGA revealed that the incorporation of
banana rachis fibers within the matrix causes a reduction in
thermal stability. The tensile strength and elongation at break
decreases with increasing fiber content and are minor
compared to the virgin polypropylene, but its modules
increases. By DSC analysis and RX determined that the
crystallinity of composites decreases with increasing fiber
content. By SEM analysis showed a decrease in stress transfer
between the fiber and matrix. The use of the rachis to obtain
new composite materials could be an important alternative for
new applications from a biowaste and a synthetic resin such as
QCM/SPR to study the oxidation and removal of
unsaturated fatty acids from NFC and PET surfaces by
lipooxygenase treatment
Ali H M.Tayeb1, [email protected], Orlando J. Rojas1,2,
Carlos L. Salas1, Keith D. Wing3. (1) Forest Biomaterials, North
Carolina State University, Raleigh, North Carolina, United
States (2) Forest Products Technology, Aalto University School
of Chemical Technology, Espoo, Finland (3) Consulting LLC,
Wilmington, Delaware, United States
A quartz crystal microbalance (QCM) used to investigate the
oxidation and removal of two unsaturated fatty acids, linoleic
acid and glycerol trioleate as well as wood extractives from a
soft surface (nanofibrilated cellulose, NFC) and a hard surface
(polyethylene terephthalate, PET). The effect of temperature,
thickness of the soiling lipid layer, soaking conditions, enzyme
concentration and available oxygen was elucidated as far as
the enzyme activity. The results indicate that lipophilic lipids
that have been oxidized have less affinity to NFC and PET.
Also, the rate of oxidation depends on the type of soil and the
aqueous medium pH. Surface plasmon resonance (SPR) was
used to confirm the oxidation effect of enzyme in aqueous
solution. Finally FTIR was employed to monitor the changes in
lipid structure and number of carbon double bonds upon
enzyme treatment. The obtained results can be used for
applications in papermaking, as a viable solution to deposit
problems and for fiber surface modification.
CELL 328
Recent developments in solvents for cellulose
Thomas J. Heinze, [email protected]. Friedrich
Schiller University of Jena, Jena, Germany
Today’s most widely used solvent in lab-scale applications is
N,N-dimethylacetamide (DMA)/LiCl established in the
pioneering work of C. L. McCormick et al. (e.g., J. Polym. Sci.,
Polym. Lett. Ed., 1979, 17, 479). Moreover, dimethyl sulfoxide
(DMSO) in combination with fluoride ions and ionic liquids (ILs)
such as 1-butyl-3-methylimidazolium chloride (BMIMCl) and 1ethyl-3-methylimidazolium acetate (EMIMAc) find considerable
interest. Very recently, it was found that quaternary
tetraalkylammonium halides with one long alkyl chain dissolved
in various organic media constitute a new class of cellulose
solvents. Contrary to the well-established solvent DMA/LiCl,
cellulose dissolves in DMA/quaternary ammonium halides
without any pretreatment. Thus, use of the new solvent avoids
some disadvantages of DMA/LiCl and ionic liquids, the most
extensively employed solvents for homogeneous cellulose
chemistry. Even acetone containing tetraalkylammonium
chloride was found to be an efficient solvent for cellulose.
Cellulose solutions in acetone/tetraalkylammonium chloride
have the lowest viscosity reported for comparable aprotic
solutions making it a promising system for shaping processes
and homogenous chemical modification of the biopolymer.
CELL 329
Interactions between cellulose and small molecules
Ruigang Liu1, [email protected], Chao Zhang1, Zhijing Liu1,
Zhiwei Jiang1, Yong Huang1,2, [email protected]. (1)
Sate Key Laboratory of Polymer Physics and Chemistry,
Beijing National Laboratory of Molecular Sciences, Institute of
Chemistry, Chinese Academy of Sciences, Beijing, China (2)
Chinese Academy of Sciences, Technical Institute of Physics
Chemistry, Beijing, China
The finding of new cellulose solvents is the key issue for using
cellulose, the most abundant natural polymers. The finding of
new cellulose was mainly based on the “try and error” method.
In this work, the mechanism of dissolution of cellulose will be
discussed by the consideration of the interactions between
cellulose and small molecules of the solvent systems. Firstly,
we revisited the classic DMAc/LiCl system by using FTIR,
NMR, etc. We find thatcomplex can be formed between DMAc
and LiCl. The molar ratio of LiCl to DMAc is about 1:6, which is
accordance with the content LiCl (about 8wt%) that have been
used for dissolving cellulose in the DMAc/LiCl. During the
dissolution, Cl– anions directly interact with –OH groups on
cellulose chains by which to break the hydrogen bonding
network of cellulose and the cellulose chains can be further
stabilized by the DMAc-Li+ complex through the charge
interaction, by which cellulose can be dissolved in the system.
For the solvent systems of NaOH, we investigated the
interactions between the different ions in the system and the
effects of additives, such as urea, ZnO, etc. on the interactions
of between cellulose and the small molecules in the system by
using NMR, calorimetry, FTIR, and so on, by which we can
answer why 7wt% NaOH should be used to dissolve cellulose
in the NaOH/urea aqueous system and why the low
temperature is favorite for the dissolution of cellulose in the
system. Our purpose is to understanding the interactions
between cellulose and small molecules in the solvent systems,
by which we can understanding the mysterious of the
dissolution of cellulose and could point out the key points for
the design and regulation of cellulose solvent systems in the
future.
CELL 330
Mechanism and kinetics of advantaged biofuels synthesis
from D-fructose
Thomas Flannelly, [email protected], Stephen Dooley,
JJ Leahy. Department of Chemical and Environmental
Sciences, The University of Limerick, Limerick, Ireland
The advanced lignocellulose derived biofuel candidates, ethyl
levulinate and 5-ethoxy methyl furfural, are synthesised from
α/β-d-fructopyranose (d-fructose) in a condensed phase
homogeneous ethanol system catalysed by hydrogen cations.
The detailed study of the d-fructose hydrolysis mechanism is
important as it is a recognised bottle-neck species, connecting
lignocellulose derived glucose to the feasible production of
biofuels. A mechanistic comprehension is pursued by detailed
measurements of the reactant, intermediate and product
species evolved with time, as a function of H2SO4 (0.09 M,
0.22 M, 0.32 M) and d-fructose concentration (0.14 M, 0.29 M,
0.43 M), also considering the addition of water to the ethanol
media (0/100, 12/88, 24/76 weight %). d-fructose, 5-hydroxy
methyl furfural, 5-ethoxy methyl furfural, ethyl levulinate, and
ethyl fructoside species, are quantified as major species
fractions, summing to (45-85 % of the initial d-fructose mass).
This information and pertinent findings from the literature are
utilised to assemble incremental mechanistic propositions, to
account for the synthetic system. Ten empirical reactions are
considered, assuming a first order relationship to the hydrogen
cation concentration for each. To test each mechanistic
proposition, these reactions are assembled into massconserved chemically authentic kinetic models and empirical
rate constants are derived for each of the chemical reactions
considered. The model indicates that d-fructose is unlikely to
undergo direct hydrolysis to 5-hydroxy methyl furfural and that
the reaction pathway likely proceeds through a stable
(fructofuranose or anhydro fructofuranose) intermediate. This
study notes that detailed investigations of the initial fate of dfructose reaction in ethanol limits further mechanistic
comprehension.
Using the reaction mechanism, for the optimal condition
studied, the synthesised fractions of ethyl levulinate, 5-ethoxy
methyl furfural and 5-hydroxy methyl furfural, considered as
fuel components, achieve an energy valorisation (ΔHCombustion,
kj/ml) of 312 % with respect to the ethanol consumed,
indicating the technical viability of the process.
CELL 331
Biphasic process using molten salt hydrates for chemical
transformation of lignocellulosic biomass into furan-based
chemicals
Chang Geun Yoo1, [email protected], Shuting Zhang1,
Xuejun Pan2. (1) Biological Systems Engineering, University of
Wisconsin at Madison, Madison, Wisconsin, United States (2)
Biological Systems Engineering, University of WisconsinMadison, Madison, Wisconsin, United States
The
furan-based
chemicals
such
as
furfural,
hydroxymethylfurfural (HMF), chloromethylfurfural (CMF), and
bromomethylfurfural (BMF) from biomass are important
building blocks in the production of fuels, plastics,
pharmaceuticals, and fine chemicals to replace petrochemical
products. In this study, we report a biphasic process for
conversion of carbohydrates in the biomass to the furan
derivatives. The biphasic system consists of an aqueous phase
of molten salt hydrate, in which biomass cellulose and
hemicellulose are converted to the furan-based chemicals, and
an organic phase of extraction solvent, into which the formed
furan products are immediately extracted to avoid the
formation of undesirable byproducts such as humins from the
condensation of the furan products. Meanwhile, lignin in the
biomass is extensively depolymerized during the reaction and
separated as a residue for co-product development. Different
carbohydrates and biomass were evaluated as starting
feedstock. The process parameters including organic solvent
loading, halide salt concentration, types of acids, temperature,
and reaction time were optimized for efficient furans
production. The reaction mechanism and process mass
balance were also investigated. In addition, the resultant lignin
was preliminarily characterized and evaluated.
CELL 332
Homogeneous saccharification of lignocellulosic biomass
in molten salt hydrates
Ning Li, [email protected], Xuejun Pan. Biological Systems
Engineering, University of Wisconsin-Madison, Madison,
Wisconsin, United States
The abundant lignocellulosic biomass is a renewable resource
for sustainable production of biofuels and chemicals. Biomassderived sugars are generally deemed as essential
intermediates of the efficient conversion of the biomass to the
biofuels and chemicals. However, efficient sugar extraction
from the biomass at low cost is still challenging.
Heterogeneous saccharification of the biomass by enzymes
proves to be low-efficiency without the energy- and costintensive pretreatment because of the poor accessibility of the
inter- and intra-molecule bonded cellulose to the catalysts. In
this work, a homogeneous hydrolysis of cellulose in molten salt
hydrate with high sugar yield and short reaction time was
reported. Cellulose could be dissolved in the molten salt
hydrate (LiBr) in 5 min at 110 ºC. In the presence of small
amount of HCl, unpretreated aspen was saccharified in the
medium in 60 min with 82.5% sugar yield. The residual solid
after the aspen saccharification was almost pure lignin, which
has good potential for co-products. A clear sugar-salt
separation was realized by the ion exclusion chromatography,
enabling the downstream sugar utilization and salt
regeneration and reuse.
Combination of X-ray and neutron diffraction techniques has
demonstrated the hydrogen bond disorder in highly crystalline
native cellulose, yielding two possible hydrogen bond
networks. Nevertheless, based on the same experimental
techniques, no similar disorder was found in cellulose II and IIII.
MD simulations, using four carbohydrate force fields
(GROMOS, CHARMM, GLYCAM, OPLS), together with
dispersion-corrected DFT calculations favor an alternative,
energetically more stable hydrogen bonding network, for both
cellulose II and IIII, different from the current model based on
neutron fiber diffraction data. Energy analysis shows that the
alternative model was stabilized by intramolecular factors
rather than hydrogen bonds in agreement with the population
analysis in the crystal structure database. Diffraction patterns
calculated from the DFT optimized models were compared with
the experimental ones, to directly estimate the reliability of the
models. We found that for cellulose II the current experimental
model reproduced better the experimental diffraction pattern,
while a subtle difference was in support of the energetically
determined cellulose IIII model.
CELL 334
Probing particle – particle interactions in swollen cellulose
nanocrystal thin films by surface plasmon resonance
spectroscopy
Michael S. Reid1, [email protected], Marco Villalobos2,
Emily D. Cranston1. (1) Chemical Engineering, McMaster
University, Hamilton, Ontario, Canada (2) Cabot Corporation,
Billerica, Massachusetts, United States
Cellulose nanocrystals (CNCs) are abundant, sustainable and
exhibit a high elastic modulus making them an ideal material
for
reinforcing
polymer
nanocomposites.
Controlling
dispersibility
and
mechanical
performance
within
nanocomposites requires a firm understanding of both particleparticle and particle-polymer interactions. This work explores
CNC particle-particle interactions by swelling thin CNC films in
water and various non-polar solvents. CNC film thickness and
porosity were monitored continuously throughout swelling via
surface plasmon resonance spectroscopy. Increased film
thickness was observed to be dependent on solvent molecular
volume indicating that solvation forces are responsible for
swelling in CNC films. Moreover, CNC films remain stable
throughout the swelling measurements demonstrating that
particle-particle van der Waals forces are sufficient to
overcome solvation forces.
CELL 335
CELL 333
Energetically favored alternative
cellulose II and cellulose IIII
Technology, Royal Institute of Technology, 10044 Stockholm,
Sweden (4) AICES Graduate School, RWTH Aachen
University, Schinkelstraße 2 , 52062 Aachen, Germany (5)
Univ. Grenoble Alpes, CERMAV, F-38000 Grenoble, France
hydrogen
bond
of
Pan Chen4, [email protected], Yu Ogawa2,1,
Yoshiharu Nishiyama1,5, Malin Bergenstråhle-Wohlert3, karim
Mazeau1,5. (1) CNRS, CERMAV, F 38000 Grenoble, France (2)
Department of Biomaterials Science, Graduate School of
Agricultural and Life Sciences, The University of Tokyo, Yayoi
1-1-1, Bunkyo-ku, 113-8657 Tokyo, Japan (3) Wallenberg
Wood Science Center, Department of Fiber and Polymer
On the combination of NaOH activation and DMAc/ LiCl
dissolution of cellulose from cotton fibers during different
stages of fiber development
Sumedha
P.
Liyanage,
[email protected],
Noureddine Abidi. Fiber and Biopolymer Research Institute,
Texas Tech University, Lubbock, Texas, United States
Cotton fibers, elongated epidermal cells of a cotton seed with
well-developed secondary cell wall, go through five major
overlapping development phases from fiber initiation to
maturity. There is a continuous change in cell wall composition
and organization throughout the development of cotton fibers,
leading to cellulose macromolecules formation and deposition.
The molecular weight and molecular weight distribution of
cellulose as well as the organization of cellulose chains within
the secondary cell wall are linked to the fiber strength. Those
parameters could vary between cultivars and different stages
of fiber development. Mature cotton fibers with more than 80%
of crystallinity are difficult to dissolve in most of the common
solvent systems. In this study, cotton fibers were subjected to a
pre-activation step using 23% NaOH before dissolution in
DMAc/ LiCl solvent system. Fibers were harvested from two
cotton cultivars of Gossypium hirsutum L., (Texas Marker-I and
TX 55) during different phases of fiber development. The
results of the characterization of these fibers using Gel
Permeation
Chromatography,
FTIR
microspectroscopy
imaging, and X-Ray diffraction will be discussed.
Isomerization of glucose (aldose) to fructose (ketose) is a key
step for the biochemical conversion of lignocellulose to liquid
fuels and chemicals through the sugar platform. Inorganic
bases, metal salts and enzymes have been widely tested as
catalysts for glucose isomerization; however, these
homogenous catalysts still have some drawbacks such as
unsatisfactory fructose yield and issues of separation and
recycle. This study demonstrated a novel strategy for
designing and synthesizing magnetic organic basic catalysts
for the isomerization of glucose to fructose in aqueous media.
Specifically, three commonly used organic bases including
imidazole,
tetramethylguanidine,
and
1,5,7triazabicyclo[4.4.0]dec-5-ene were chemically immobilized onto
the surfaces of magnetic iron (III) oxide nanoparticles for the
synthesis of magnetic organic basic catalysts. These
synthesized magnetic organic basic catalysts could achieve
approximately 25% glucose-to-fructose yields in water under
mild conditions, and also showed good stability and
recyclability.
CELL 336
CELL 338
Chemical functionalization and characterization of
crystalline cellulose derived from agricultural waste
products
Chemar J. Huntley2, [email protected], Kristy D.
Crews2, Michael L. Curry2,1. (1) Department of Chemistry,
Tuskegee University, Tuskegee, Alabama, United States (2)
Materials Science and Engineering, Tuskegee University,
Tuskegee, Alabama, United States
Due to the abundance of agricultural waste products interest
has intensified in its use as a biomass source for the extraction
of cellulose applicable as reinforcement fillers in thermoplastic
composites. The issue is the non-uniform distribution of
cellulose into the polymer matrix creating composite voids, due
to its hydrophilic nature. However, the extraction of cellulose
from different biomasses is a rigorous process and, often,
modification of its structure is needed to obtain the desired
chemical and physical structural properties. In this research
report, we have extracted cellulose from the agricultural waste
products—wheat straw and peanut shells—via hydrochloric,
nitric, and sulfuric acid hydrolyses and, subsequently,
subjected its structure to chemical functionalization using the
Albright-Goldman reaction. Furthermore, the thermal stability
based on the agricultural waste products’ mass (6 grams
versus 18 grams) and sonication solvent (acetone versus
water) was explored. Apparently, x-ray diffraction and scanning
electron
microscopy
analyses
reveal
a
structural
rearrangement – conversion from CI to CII – for the modified
cellulose. Thermal analyses indicate a significant improvement
in the thermal stability for the modified cellulose when
compared to its unmodified counterpart. Additionally, smaller
sample sizes and acetone-sonicated cellulose demonstrated
greater thermal stabilities.
CELL 337
Isomerization of glucose to fructose by magnetic organic
basic catalysts in aqueous media
Qiang Yang, [email protected], Troy Runge. Biological
Systems Engineering, University of Wisconsin-Madison,
Madison, Wisconsin, United States
Direct thermal processing of cellulose plasticized with
ionic liquids and its composites as polymer electrolytes
Jun Wu1, Yonggui Liao1, Yunsheng Ye1, XingPing Zhou1,
Bogumil Brycki2, Xiaolin Xie1, [email protected]. (1) Key
Laboratory for Large-Format Battery Materials and Systems,
Ministry of Education, School of Chemistry and Chemical
Engineering, Huazhong University of Science and Technology,
Wuhan, China (2) Faculty of Chemistry, Adam Mickiewicz
University, Poznań, Poland
Cellulose is the most abundant sustainable natural polymer
with fascinating properties, and the development of efficient
solvent systems has brought breakthrough progresses in wetprocessing[1-4]. However, only limited progresses have been
achieved
in
thermal
processing
of
cellulose[5,6].
Recently, ionic liquid plasticized celluloses are prepared with
microcrystalline cellulose (MCC) and 25 ~ 70 wt% 1-butyl-3methylimidazolium chloride (BmimCl) by direct thermal
processing. Based on the free volume transition and the
percolation of continuous hydrogen bonding networks, the
effects of free volume and H-bonding interactions on the glass
transition are differentiated, and the phase diagram has been
plotted with four regions, i.e. (I) rubber state with sufficient free
volume and without H-bonding networks, (II) glass state
without sufficient free volume and H-bonding networks, (III)
glass state with insufficient free volume and continuous Hbonding networks, and (IV) glass state with sufficient free
volume and continuous H-bonding networks[7]. Furthermore,
the ionic liquid plasticized celluloses are blended with
polyethylene glycol, and compounded with carbon nanotube
and meso-porous silica respectively. The resulted cellulose
composites exhibit excellent mechanical and electrochemical
properties, and have the potential applications as polymer
electrolytes.
Acknowledgment: The authors acknowledge the National Basic
Research Program of China (973 Program, 2012CB025903)
and Major International Joint Research Project (No. 51210004)
of National Natural Science Foundation of China for support of
this work.
[1]
Johnson
DL.
US
Patent
3,447,939
(1969)
[2]
Dupont
AL.
Polymer
2003,
44:4117-4126
[3] Swatloski RP, Spear SK, Holbrey JD, Rogers RD. J Am
Chem Soc 2002, 124:4974-4975
[4] Zhou JP, Zhang LN, Polym J 2000, 32: 866-870
[5] Schroeter J, Felix F. Cellulose 2005, 12:159-165
[6] Zhang XQ, Wu XL, Gao DC, Xia KN. Carbohydr Polym
2012. 87: 2470-2476
[7] Wu J, Bai J, Xue ZG, Liao YG, Zhou XP, Xie XL. Cellulose
2014, revised
CELL 339
Fabrication and characterization of cellulose functional
materials using ionic liquid 1-ethyl-3-methylimidazolium
acetate (EmimAc)
Jinhui Pang1, [email protected], Xueming Zhang1,
[email protected],
Qiaohui
Zhang1,
[email protected], Miao Wu1, [email protected],
Runcang Sun1,2, [email protected]. (1) Beijing Key
Laboratory of Lignocellulosic Chemistry, Beijing Forestry
University, Beijing, China (2) State Key Laboratory of Pulp and
Paper Engineering, South China University of Technology,
Guangzhou, China
With the fossil resources reduction and their negative impacts
on the environment, there is growing demand for development
of renewable and biodegradable materials as substitutes for
petroleum-derived synthetic polymers. Cellulose, the most
abundant natural biopolymer on the earth, is considered as
one of the most promising polymeric resource, such as
cellulose films, food casings, absorption materials and
hydrogels. In this study, cellulose films, modified cellulose
beads and nanoporous cellulose hydrogels were successfully
prepared using ionic liquid 1-ethyl-3-methylimidazolium acetate
as solvent. Cellulose films were prepared using different
cellulose (pine, cotton, bamboo, MCC) as raw materials. The
results showed that all the cellulose films displayed a
homogeneous and smooth structure and the transition of
crystal structure from cellulose I to II was occurred after the
production process. Furthermore, the cotton linters and pine
film samples possessed the most excellent thermal stability
and mechanical properties, which were suggested by the
highest onset temperature (250 ºC) and tensile stress (120
MPa) respectively. The modified cellulose beads were
characterized by a high porosity with open-pore structures and
improved nitrogen adsorption surface areas, which could
greatly improve the adsorption properties. In addition, the
results from nanoporous cellulose hydrogels indicated that the
hydrogels possessed an excellent swelling and deswelling
behaviors, these notable properties exhibited its potential
utilization in agriculture aquasorb and drug carrier.
CELL 340
Flexible route for solely biomass-derived p-xylene and
terephthalic acid
Fei Wang, [email protected], Zhaohui Tong. University of
Florida, Gainesville, Florida, United States
p-xylene (PX) is conventionally produced from petroleum and it
has been largely oxidized for the preparation of terephthalic
acid (TPA), the monomer precursor mainly for polyethylene
terephthalate (PET). Herein we report a flexible synthesis route
to p-xylene (PX) and terephthalic acid (TPA) from biomassderived isoprene and acrolein in mild conditions. At first, an
important intermediate, 4-methyl-cyclohex-3-enecarbaldehyde,
was prepared in a 75% yield through Diels-Alder reaction
between isoprene and acrolein in the presence of Lewis acid
(zinc chloride) as the catalyst. Then, p-Xylene was obtained
either through Wolff—Kishner reduction followed by a dehydroaromatization or an aromatization using cobalt-manganesebromide catalyst followed by a reduction reaction. We also
found that TPA could be directly converted from the
aromatized product 4-methylbenzaldehyde in a high yield
(91%) by an oxidation reaction using industrial-available cobalt
(II) acetate (0.5 mol %) and magnesium acetate (0.5 mol %) as
the catalysts.
CELL 341
Cellulose nanocrystals as reinforcing agent in meltspinning of polypropylene
Xiaomin Lu, [email protected]. Forest Biomaterials, NC State
University, Raleigh, North Carolina, United States
The purpose of this study is to develop a new nonwoven
platform to produce polypropylene composites featuring biobased materials. These new fibrous and film composites are
expected to display improved thermal-mechanical properties
when compared to the base materials. In addition to cellulose
nanocrystals (CNC), the reinforcing function of another kind of
nanocellulose, namely nanofibrillar cellulose (NFC), was
evaluated. Polypropylene fibers with given amounts of
nanocellulose were produced via melt spinning. The CNC/NFC
loading was varied from 0.5 to 3.5 wt% and its effect on fiber
properties was investigated. Even though the nanocelluloses
formed some aggregates within the PP fiber structure, the
melting temperature, crystallinity and PP molecular orientation
were maintained. The addition of nanocelluloses increased the
tensile properties of PP fibers when the nanocelluloses loading
is as low as 0.5 wt% and the thermal stability of PP fibers. The
crystallization process was found to be facilitated by the
addition of nanocellulose.
CELL 342
Continuous hydrothermal liquefaction of cellulosic and
lignocellulosic biomass
Justin Billing2, [email protected], Andy Schmidt2, Todd
Hart2, Gary Maupin2, Richard T. Hallen1, Douglas C. Elliott3. (1)
MSIN P8-60, Pacific NW Natl Lab, Richland, Washington,
United States (2) Pacific Northwest National Laboratory,
Richland, Washington, United States
Alpha-cellulose, Loblolly Pine forest product residual and corn
stover were pretreated to prepare aqueous slurries at about 10
to 15 wt% solids. Hydrothermal liquefaction of the slurries was
performed in a bench scale continuous flow reactor system at
feed rates ranging from 1 to 2 liter/hour. The reaction
temperature was 300-350°C (Tc,water=374°C) with resulting
pressures between 2500-3000 psi. Testing was conducted to
evaluate the effects of processing conditions on bio-oil yields
and bio-oil quality. HTL bio-oils have low water content and are
lower in oxygen (ca. <10%) than oils from fast pyrolysis but
have high viscosity (up to 1×104 cSt at 40°C). The HTL bio-oils
were upgraded in a continuous flow hydrotreatment reactor to
prepare a final product for evaluation as a petroleum refinery
intermediate.
CELL 343
Overview of the catalyst and process research and
development efforts related to the PNNL glycerol to
propylene glycol process
John Frye1, [email protected], Alan Zacher2, Todd Werpy3.
(1) Pacific Northwest National Laboratory, Richland,
Washington, United States (3) ADM, Decatur, Illinois, United
States
PNNL, in cooperation with the U.S. D.O.E. and CRADA partner
Archer Daniels Midland, Co. has co-developed and
commercialized a process for converting bio-based glycerol to
propylene glycol. The technology was initially developed as a
trickle bed process at PNNL using highly active and selective
carbon-based catalyst systems. This talk will give a brief
overview of the catalyst and process evolution from the project
inception to the over 4000 hour catalyst life study, and
subsequent pilot-scale testing at ADM.
CELL 344
Award
Address (Kathryn
C. Hach
Award for
Entrepreneurial Success sponsored by the Kathryn C.
Hach Award Fund). Scale up challenges of first of a kind
renewable chemicals
Todd Werpy1, [email protected], John Frye2, Alan
Zacher2. (1) ADM, Decatur, Illinois, United States (2) Pacific
Northwest National Laboratory, Richland, Washington, United
States
ADM has successfully scaled up and commercialized a
catalytic technology licensed from Pacific Northwest National
Laboratory for the production of propylene glycol from glycerin.
The technology is currently being practiced at 200,000 metric
tons per year at our corn wet milling facility in Decatur, Illinois.
The plant is capable of producing both industrial grade and the
world’s only USP grade propylene glycol. This presentation will
discuss the challenges and successes of scaling up a new to
the world renewable technology from primarily a technical
perspective but also from a customer and market perspective.
indicated that all the parameters have effects on the
cellulose/Cu(OH)2/CuO hybrids, power density had an effect on
the phase transformation of Cu(OH)2 to CuO, and the addition
of H2O2 played an important role in the shape of cellulose
hybrids, which provided an indirect evidence on the H2O2induced oxidation route for the transformation process from
Cu(OH)2 to CuO during the ultrasound irradiation process.
These results maybe direct the synthesis and potential
applications of cellulose hybrids in the near future.
CELL 346
Defined cellulose-polymer hybrid materials by synthesis
under homogeneous reaction conditions
Marcus W. Ott, [email protected], Markus
Biesalski. Macromolecular Chemistry, Technical University of
Darmstadt, Darmstadt, Hessen, Germany
Cellulose is the most abundant biopolymer in the world and
has various unique properties like thermal and mechanical
stability and certain chemical properties, i.e. every repeating
unit has three hydroxylic groups with different reactivities.
Because of these and other reasons cellulose based materials
are under investigation until today. The aim of my work is to
prepare novel cellulose based hybrid materials with a brush or
comb like architecture containing a cellulose backbone and
synthetic polymer grafts. The synthesis strategy involves the
covalent attachment of polymerisable groups (so called CTAs
(chain transfer agent)) onto cellulose. The CTA-groups are
immobilized predominantly on the 6-O-position with low DSValues which leads to limited solubility of these derivatives.
Because of this, the remaining hydroxyl groups become
modified by aliphatic esters or other chemical species in order
to enhance solubility of the cellulosic material in various
common organic solvents and makes further homogeneous
modifications possible. As a following step, the cellulose
derivatives act as a macro-CTA in a controlled radical
polymerisation, using monomer, initiator and free sacrificial
CTA. If the immobilized CTA groups on the cellulose derivative
react in a similar fashion like the CTA groups in solution, it
should be possible to generate highly defined cellulosepolymer hybrid materials with tailor made properties.
CELL 347
CELL 345
Understanding the mechanism of ultrasound on the
synthesis of cellulose/Cu(OH)2/CuO
Ke Yao, [email protected]. Beijing Forestry University,
Beijing, China
Understanding the mechanism of ultrasound from metal
hydroxide to oxides via an ultrasound irradiation method is of
great importance for broadening and improving their synthesis
and industrial applications. The purpose of this article was to
explore the mechanism of ultrasound on the synthesis of
cellulose/Cu(OH)2/CuO hybrids. The influences of various
reaction parameters including the volume of H2O2, heating
method, pulse mode of ultrasound irradiation, sonication time,
and power density on the cellulose/Cu(OH)2/CuO hybrids were
investigated in detail by means of X-ray diffraction (XRD),
scanning electron microscopy (SEM), energy-dispersive X-ray
spectra (EDS), thermogravimetric analysis (TGA), and
derivative thermogravimetry (DTG). The experimental results
Carbon dot (CD) modified cellulose nanocrystals (CNC) for
biosensing and -imaging
Jiaqi Guo1, [email protected], Ilari Filpponen1,
Orlando J. Rojas1,2. (1) Department of Forest Products
Technology, Aalto University, Espoo, Finland (2) Department
of Forest Biomaterials, North Carolina State University,
Raleigh, North Carolina, United States
TEMPO-oxidized cellulose nanocrystals (TO-CNC) were
modified by covalent EDC/NHS coupling of luminescent, waterdispersible carbon dots (CDs). The prominent properties of
CDs include stable photoluminescence, hypotoxicity and
excellent biocompatibility which are desirable features for
example in biological systems and bioimaging applications.
Quartz crystal microgravimetry with dissipation monitoring
(QCM-D) and surface plasmon resonance (SPR) were used to
investigate the attachment of CDs on TO-CNC. Moreover,
atomic force microscopy (AFM), scanning electron microscopy
(SEM) and transmission electron microscopy (TEM) were
applied to characterize the main morphological features of the
produced bio-hybrid materials. Main results and possible
applications for such systems will be discussed.
CELL 348
Carbon quantum dots from biomass: Synthesis and
functionalization
xiaohui wang1, [email protected], Zicheng Liang1,
Runcang Sun2. (1) South China University of Technology,
Guangzhou, China (2) South China Univ of Tech, Guangzhou
Guangdon, China
Biomass, mainly refers to lignocellulose, was considered as
the most promising material in substitution of the materials
from petroleum in the past decades due to their renewability,
affordability, biocompatibility and environmental compatibility.
However, thousands of biomass resources still have been
squandered every yea. Thus, pursuing effective way for
utilization of biomass had become an urgent subject. In this
work, biomass and derivatives (including cellulose,
hemicellulose, chitosan and alginate) were used, respectively,
as the carbon resources to synthesize CQDs via a greenly
one-step hydrothermal treatment. In the whole process, no
organic solvents or strong acid/alkaline was needed. The
obtained CQDs were highly aqueous solubility and exhibited
blue fluorescence under ultraviolet excitation. The quantum
yields (QY) of these CQDs were around 2%, except for
chitosan with inherent amino moieties (up to 13%). Surface
functionalization is regarded as apowerful method to tune the
surface properties of CQDs. When functionalized by
ammonium hydroxide or organic molecules with amino
moieties, tunable emission wavelength of CQDs could be
observed and the QYs were greatly increased depending on
the functionalization agents. The highest QY up to 16% were
obtained by simply adding ammonium hydroxide in the
hydrothermal solution, which was much higher than those
obtained by using organic molecules with amino moieties as
functionalization agent (about 7%). Further investigations
revealed low cytotoxicity, good biocompatibility and
outstanding electronic properties of the biomass CQDs,
endowing them with potential application in biomedicine,
imaging, catalysis and sensors. Our work provides a new idea
for value-added utilization of biomass resources, and this
green and low-cost synthetic method was expected to apply in
large-scale production.
CELL 349
Inkjet printed paper-based sensing device for colorimetric
determination of contaminants in drinking water
Petra Gasparic1, [email protected], Andreas Kornherr2,
Silvo Hribernik1, Karin Stana-Kleinschek1. (1) Institute of
engineering materials and design, University of Maribor,
Faculty of Mechanical Engineering, Maribor, Slovenia (2)
Mondi Uncoated Fine & Kraft Paper GmbH, Wien, Austria
Quality of drinking water differs in many parts of the world and
is usually assessed based on national standards and
international guidelines. The most important document in this
field are WHO (World health organization) Guidelines for
Drinking Water Quality. Depending on the source, drinking
water quality is not always easy to determine. Hence a need
for inexpensive disposable colorimetric sensors has emerged.
Paper as an inexpensive and abundant material from natural
resources is, owing to its unique properties, an ideal substrate
for
creating
such
sensing
devices.
In our work hydrophobic patterns and colorimetric indicators
were printed using inkjet technology, while the capillary action
of the paper allows water samples to move within the
hydrophobic pattern in order to reach the indication sites. The
advantage of such system is that it requires a small sample
volume only.Different types of commercially available and
widely used sizing agents were used to create a variety of
hydrophobic patterns, i.e. ASA (alkyl succinic anhydride) and
AKD (alkyl ketene dimer). The wettability of these patterns was
studied by means of static water contact angle measurements.
In addition, a study of the interaction between the hydrophobic
agents and model cellulosic surface was performed using
quartz crystal microbalance with dissipation (QCM-D). The
topography of the printed patterns was visualized with
scanning
electron
microscopy
(SEM).
The combination of these methods will allow us to fully
understand the mechanisms of interaction of sizing agents with
cellulose substrates and fabricated surfaces with aqueous
analytes, thus paving the way to create an efficient and precise
sensing device.
CELL 350
Improving the redispersability of cellulose nanofibrils
Erkko I. Filpponen, [email protected], Anu Anttila,
Orlando J. Rojas. Department of Forest Products Technology,
Aalto University, Espoo, Finland
The possibility to re-disperse dried cellulose nanofibrils (CNF)
is beneficial for the logistic purposes. In this work,
Carboxymethyl cellulose (CMC) was adsorbed onto birch pulp
before its fluidization to CNF. This procedure promoted the
disintegration of the fibrils and also helped the re-dispersion of
the dried CNF. Different amounts of CMC related to the original
pulp were employed. The morphology of produced CNF was
characterized by atomic force microscopy (AFM) and
transmission electron microscopy (TEM). The amount of
adsorbed CMC onto pulp was measured by titration and its
effects to the re-dispersability will be discussed.
CELL 351
Carboxymethylated lignin (CML) in liquid and solid foams
Shuai LI1, [email protected], Orlando J. Rojas2,1. (1) Forest
Biomaterials, North Carolina State University, Raleigh, North
Carolina, United States (2) Forest Products Technology, Aalto
University, Espoo, Finland
Due to its complex natural structure and amorphous
characteristics, lignin can be burnt as a low value solid fuel.
However, its multifunctional and surface active properties can
be tailored after upgrading as a high value added product.
Carboxymethylation was used to functionalize industrial Kraft
lignin to make it water soluble at neutral pH conditions. The
functionalized lignins were characterized for molecular weight
by GPC, elemental composition by CHN Elemental Analyzer,
and degree of substitution by 31P NMR. Also, the surface
activity of CML was assessed via surface tensiometry. Here we
demonstrated the capability as a foaming agent. With CML,
liquid foams were formed via agitation and compress air
bubbling, respectively. The foamability and stability were
measured with varying conditions including CML concentration,
temperature, pH, water hardness, mixing rate and air content.
Turbiscan was used to measure foam stability and bubble
collapse. Based on the lignin foams produce we discuss some
possible uses in the areas of fiber technology and solid foams.
CELL 352
Cellulose
nanocrystals
as
2D
chiral
inducers:
Enantioselective catalysis and transmission electron
microscopy 3D characterization
Madhu Kaushik1, [email protected], Charles
Benoit1, Ciprian M. Cirtiu1, Audrey H. Moores2. (1) Chemistry,
McGill University, Montreal, Quebec, Canada (2) Chem Dept,
McGill University, Montreal, Quebec, Canada
Biomaterials offer a great opportunity to replace existing nonsustainable approaches, as they possess unique and specific
properties that have been used in the context of optical,
electronic, and environmental science and catalysis, etc.1-3
These systems blend applicability with sustainability-linked
properties including non-toxicity, earth abundance, biodegradability. One such renewable and sustainable material is
derived from the biopolymer, cellulose, through acid hydrolysis
by concentrated sulphuric acid, known as the cellulose
nanocrystal (CNC). Enantioselective catalysis has been the
method of choice to synthesize pure chiral molecules in the
pharmaceutical and agrochemical industry. The “chiral pool”,
provided to us by nature, is classical means of generating
chiral molecules and enriching racemic mixtures.4 The transfer
of this idea in heterogeneous catalysis has however known
some limitations. Our research demonstrates the potential of
CNCs to be used for 2D chiral induction in heterogeneous
hydrogenation of carbonyl compounds, where the catalyst is a
CNC-hybrid composite that integrates palladium nanoparticles
onto the CNC surface (PdNPs@CNCs). Furthermore, we also
work on 3D-imaging of this sustainable material to better
understand its properties as a catalytic support.
(1) Habibi, Y.; Lucia, L. A.; Rojas, O. J. Chem Rev 2010, 110,
3479.
(2) Rak, M. J.; Friscic, T.; Moores, A. Faraday Discuss. 2014.
(3) Thakur, V. K.; Thakur, M. K.; Raghavan, P.; Kessler, M. R.
ACS Sustainable Chemistry & Engineering 2014, 2, 1072.
(4) Katsuki, T.; Sharpless, K. B. J. Am. Chem. Soc. 1980, 102,
5974.
United States (2) Dept. of Wood Science Engineering, Oregon
State University, Corvallis, Oregon, United States
The favorable properties of poly(vinylidene fluoride) (PVdF)
make it an interesting polymer for many different applications
including flexible sensors, actuators, batteries, filters and
magnetoelectric devices. It is a non-reactive and thermoplastic
semi-crystalline polymer with five different crystal structures (α,
β, γ, ε and δ) depending upon its chain conformation. The β
phase is more desirable because its all trans (TTT) planar
structure provides the highest remnant polarization and thus
has higher piezoelectric properties than the other crystal
phases. There are some limitations regarding the use of PVdF.
For instance, producing high piezoelectric properties requires
multistage processing (mechanical stretching under field from
the α-phase). This is incompatible with micro fabrication.
Solution cast PVdF films can have high β phase content, but
usually show a high degree of porosity, and are fragile. Several
literature reports have shown improved properties in solution
cast
PVdF
by
incorporating
nano
particles.
Cellulose nanocrystals (CNCs) have very high stiffness and
have been used to increase the mechanical properties of
various polymers, including PVdF. In the present study we
introduce a new solution casting technique to increase the
mechanical properties of PVdF using aligned CNCs and
compare the results to the Nairn Model
CELL 354
Two-stage separation
nanocrystals
and
alignment
of
cellulose
Yang Hu, [email protected], Noureddine Abidi. Texas Tech
University, Lubbock, Texas, United States
Cellulose nanocrystals (CNCs) are nanofibers consisting of
short-chains of β-glycan hydrolyzed from cellulose. A typical
characteristic of CNCs from different sources presents a wide
range of nanofiber size from 70 nm to more than 1000 nm in
length and from 3 nm to 50 nm in width. CNCs isolated from
cellulose by sulfuric acid hydrolysis have been extensively
studied and industrially employed. However, studies on the
separation and categorization of CNC nanofibers with different
sizes are very limited. In this study, a two-stage separation
method based on a double-layer dialysis tubing assembled by
3500 MWCO and 8000 MWCO pore size membranes was
used to categorize CNCs after sulfuric acid hydrolysis of
cellulose macromolecules from cotton fibers. The resultant
CNCs nanofibers with an approximate size were subsequently
aligned in a low-voltage electrical field. Scanning electron
microscopy,
X-rays
diffraction,
gel
permeation
chromatography, thermogravimetric analysis, Fourier transform
infrared, and particle-sizer were used to characterize the
CNCs. The CNCs with an approximate size and molecular
weight of 3500-8000 Da were obtained. The aligned and
uniform CNCs-based film exhibited superior mechanical
properties and liquid crystal behavior.
CELL 355
CELL 353
Reinforcing piezoelectric films with cellulose nanocrystals
Life cycle assessment of high performance nanocellulosereinforced advanced fibre composites
Meisam
Shir
Mohammadi1,
[email protected], John Simonsen2,
john Nairn2. (1) Oregon State University, Corvallis, Oregon,
Hervy Martin1, [email protected], Sara Evangelisti1,
Paola Lettieri2, Koon-Yang Lee2. (1) Chemical Engineering,
University College London, London, United Kingdom (2)
Department of Chemical Engineering, University College
London, London, United Kingdom
Customer demands for more environmental-friendly consumer
goods and an intensifying legislative pressure for greener as
well as carbon neutral technologies are forcing materials
suppliers and manufacturers to consider the environmental
impact of their products at all stages of their life cycle, including
processing, recycling and final disposal. As a result, industry,
end-users and local authorities will need to move away from
traditional waste management methods and will require new
strategies for reuse and recycling. In order to maintain the
environmental credentials of the matrix, synthetic fillers, such
as glass-, carbon fibres and even nanotubes/fibres should be
replaced by renewable biodegradable ones. In this context,
bacterial cellulose (BC) or plant derived nanofibrillated
cellulose (NFC) serve as ideal candidates as reinforcement
due to their low density, renewability and biodegradability.
However, it is unclear whether the claims of environmental
benefits of these materials can be justified. It is timely to reconsider these claims. Therefore in this study, the
environmental impact associated with the manufacturing of
high
performance
nanocellulose-reinforced
polymer
composites is presented. The fermentation process necessary
to produce BC nanofibrils was found to place a heavy burden
on the environment. The production of BC requires 236 MJ/kg
of non-renewable energy and induces 9.5 kg CO2-eq/kg in
global warming potential (GWP). This is due to the low yield of
the process (3.2g of BC recovered per liter of medium) and the
energy required for the purification step. NFC, on the other
hand, has a lower environmental burden, requiring only 44
MJ/kg of energy but inducing a bonus of 0.21 kg CO2-eq/kg in
GWP compared to the production of BC. Nevertheless, our life
cycle assessment showed that the environmental impact of the
resulting high performance NFC or BC-reinforced polymer
composite are comparable to that of commercially available
polylactide
(PLA)
and
even
glass-fibre
reinforced
polypropylene (GF/PP). This is due to the reinforcing ability of
nanocellulose in polymer matrices, producing materials with
higher specific tensile properties compared to PLA and GF/PP.
In addition to this, a hot spot analysis of the manufacturing of
NFC or BC-reinforced polymer composites is also discussed in
this presentation.
DMSO to produce the crucial precursor 6-azido-6deoxycurdlan. On one hand, O-acylated 6-amido-6deoxycurdlan was produced by a one-pot method of
Staudinger reduction, followed by reaction in situ with excess
carboxylic anhydride, without isolation of the 6-amino
intermediate. On the other hand, the O-2, 4 groups were
acylated with hydrophilic oligo(ethylene oxide) esters, so as to
enhance aqueous solubility. The azide groups of the resultant
6-azido-2,4-di-O-trioxadecanoylcurdlans were then reduced
with sodium borohydride to produce water-soluble 6trioxadecanoamido-6-deoxycurdlan.
Alternatively,
direct
borohydride reduction of the parent azido precursor afforded 6amino-6-deoxycurdlan which, unexpectedly, was also watersoluble. Additionally, 6-azido curdlan was treated with
triphenylphosphine in the presence of benzaldehyde and
sodium cyanoborohydride to produce 6-monoalkylamine via
one-/two-step procedures. Regioselectivity and degree of
substitution of those derivatives were characterized by means
of 1H-, 13C- NMR and FTIR- spectroscopy, elemental analysis,
and titration.
CELL 356
Regioselective preparation of curdlan derivatives
aminated at the C-6 position for biomedical applications
Ruoran Zhang1, [email protected], Kevin J. Edgar2. (1)
Macromolecular Science and Engineering, Virginia Tech,
Blacksburg, Virginia, United States (2) Mail Code 0323,
Virginia Tech, Blacksburg, Virginia, United States
CELL 357
There has been growing interest in aminopolysaccharide
synthesis due to their critical natural functions and potential for
biomedical applications. Regioselective introduction of amino
groups into polysaccharide backbones is a challenging
endeavor. Natural curdlan is a linear β-(1→3)-glucan that is of
interest both for its physical properties and its biomedical
applications. Aminocurdlans are intriguing target molecules for
study of, for example, their interactions with the proteins that
form tight junctions between enterocytes. A series of aminated
curdlan derivatives were synthesized starting from 6-bromo-6deoxycurdlan. Curdlan was first regioselectively brominated at
the C-6 position in DMAc/LiBr. The bromide was then
displaced by nucleophilic substitution with sodium azide in
Sam A. Pendergraph2, [email protected],
Christopher Carrick1, Lars Wagberg3, Anna Carlmark4, Mats K.
Johansson5, Gregor Klein1, Andrea Trager6. (1) Royal Institute
of Technology, Stockholm, Sweden (2) Fibre and Polymer
Technology, Royal Institute of Technology, KTH, Arlington
Heights, Illinois, United States (3) KTH Fibre Polymer Techn,
Stockholm, Sweden (4) Fibre and Polymer Technology, KTH
Royal Institute of Technology, Stockholm, Sweden (5) Royal
Inst of Tech, Stockholm, Sweden (6) Royal Institute of
Technology, KTH, Stockholm, Stockholm, Sweden
Macroscopic cellulose probes for contact adhesion
Accurate quantification of cellulosic materials remains a difficult
technical challenge in applications. In this work, we describe a
new procedure to form amorphous cellulose spheres with
diameters on the order of millimeters in size. The spheres can
be obtained with minimal roughness, typically 1-2 nm in root
mean square values. Implementing a custom-built contact
adhesion apparatus, we utilize these smooth probes to quantify
adhesion that previously has not been observed. In the final
part of the study, we create functionalized surfaces through
established organic and polymer chemistry. We demonstrate
the ability to implement novel polymerizations to create unique
cellulosic interfaces. The modifications are then quantified
through the contact adhesion testing to measure the
differences in interfacial strength. Furthermore, we evaluate
the polymer dynamics that are involved in the contact adhesion
testing.
CELL 358
Determination of useful parameters to decide the
suitability of a biomass to be used as raw material for
thermochemical processes
Allen Puente-Urbina, [email protected]. School of
Chemistry, Costa Rica Institute of Technology, Cartago, Costa
Rica
Biomasses can be considered as important feedstocks for
energy processes in regions where agricultural or agroindustrial activities produce significant amounts of this kind of
materials. One of the most important applications of such class
of materials is its use as solid fuel in combustion. However,
there are other types of thermochemical processing that have
gained considerable attention in recent years (e.g. gasification,
pyrolysis). Pyrolysis is a thermal decomposition occurring in
the absence of oxygen. It is an important process itself as well
as the first step of other processes as combustion and
gasification. Its progress can be divided into four stages: 1)
heating of the material and release of free moisture and loosely
bound water, 2) dehydration of the biomass leading to the
release of H2O and low-molecular-weight gases (e.g. CO,
CO2), 3) decomposition of large molecules into char,
condensable and non-condensable gases, 4) cracking of
volatiles into char and non-condensable gases. The overall
process is affected by both physical and chemical feedstock
characteristics, and also by other conditions related with its
operation. We are analyzing different biomasses from Costa
Rica in order to obtain useful parameters to decide their
suitability to be used as raw materials for thermochemical
processes. Chemical and physical characteristics of this kind of
materials are considered. Properties such as composition,
morphology, fluid diffusivity, and crystallinity are under study as
well as their relation with pyrolysis processes developed using
thermogravimetric analysis.
CELL 359
Performance of a low-cost portable carbonizer for the
valorization of lignocellulosic wastes
Eileyn Perez, [email protected]. Instituto Tecnólogico de
Costa Rica, Cartago, Cartago, Costa Rica
Lignocellulosic wastes in Costa Rica are often not optimally
managed. When disposed in a landfill, such wastes shorten its
useful lifetime, imply transportation and management costs,
and emit greenhouse gases without first having rendered their
energy or other products they can yield. One option of
valorization for lignocellulosic wastes is carbonization. A low
cost, simple-operating, portable carbonizer was designed and
built at the Instituto Tecnológico de Costa Rica. It can be
replicated at any metal-mechanics workshop, mostly
constructed with widely available re-used materials. It is able to
process up to 50 kg feedstock batches, and it minimizes
smoke emissions as compared to local traditional methods, by
burning the pyrolytic gases to maintain the temperature
required in the process. This model is very much within reach
for small farmers, but may as well serve for SMEs interested in
valorizing their wastes. To assess its performance, two locally
common wastes were carbonized in it, namely construction
waste-wood and waste-wood from a palette factory consisting
exclusively of Gmelina arborea wood. Variables as moisture
content, heat content, densities, color, odor, mechanic
resistance, sonority, volatiles content, ash content, germination
inhibition, and earthworm avoidance, were assessed in the
feedstock, in the charcoal, or in both materials. The tests were
selected in view of the two main uses foreseen for the
charcoal: to obtain clean heat, and as a soil amendment. The
palette factory waste showed excellent yields between 30 %
and 33 % w/w of a sonorous, lustrous and very slightly odorous
charcoal, all traits of good quality. Its moisture after stabilizing
for at least 3 weeks in air was 5 % to 8 %, apparent density
was 140 kg/m3 to 170 kg/m3 density was 210 kg/m3 to 310
kg/m3 heat content varied from 29.5 kJ/g to 30.7 kJ/g, and
volatiles from 10 % to 33 %. Results for other wastes will be
shown at the conference. The time per batch was 5:25 hours to
7:10 hours. Firewood needed to initiate the process was 33 %
to 38 % of the total per batch, and can be sensibly reduced by
combining 2 carbonizer reactors. The performance of the
carbonizer is, so far, outstanding, and improvements are
foreseen.
CELL 360
New organic composites for FDM applications
Rainer Christoph2,3, [email protected], Jose VegaBaudrit1. (1) LANOTEC, San Jose, Costa Rica (2) Institituto de
Ciencia Tecnología e Inovación, Universidad Francisco
Gavidia, San Salvador, I am not in the U.S. or CANADA, El
Salvador (3) Nanotecnia, San Salvador, El Salvador
The recent emergence and proliferation of low-cost digital
manufacturing techniques, for example fused deposition
modeling (FDM), bears the new and very promising potential of
innovating small local industries Latin America. FDM provides
the capability of locally defining, designing and producing
manifold objects for a wide range of applications, and at
affordable costs. It allows societies to produce locally, to selfsupply specific local demands. This is especially important for
developing societies, where a vast majority of technological
goods is currently being imported. For these countries, new
production techniques such as FDM foster local production and
reduce the present strong dependence on imports. An
important prerequisite for such development is the local
availability of adequate FDM equipment (including spares) and,
importantly, both affordable and sustainable FDM material
solutions. We focus on the development of new composites for
FDM applications, in view of producing highly functional
objects with lowest possible environmental impact. Our
approach consists in reinforcing biodegradable polymers, such
as PLA (polylactic acid) with nano cellulose and high-strength
organic fiber fragments. We present a two step, FDMprocedure for the production of composite test samples. In a
first step organic material is deposited in FDM-prefabricated
containment structures which are then sealed. The second
step consits in producing 3D objects with FDM, using the
sealed material material containment structures. We highlight
the production process for organic composite test samples and
present results obtained from the experimental determination
of their mechanical and morphological properties. Specific
examples of functional objects, fabricated with such new
composites, shall also be included.
sp, Bacillus subtilis, and Saccharomyces cerevisiae), with the
idea to apply this procedure on the field, and once the
lignocellulosic material is degradated the component can be
reincorporated to the soil working as a fertilizer. Therefore
trying to develop an environmentally sustainable solution for
the pineapple producers, reducing the amount of pesticides
applied to this residue. Monitoring of the degradation was
conducted by cuantification of the cellulose and lignin, degree
of polymerization of cellulose, enzymatic activity and
microscopy. Another strategy consisted in performing
nanocellulose extraction from the pineapple leaves, which is
based on chemical treatments such as alkaline extraction,
bleaching, and acid hydrolysis to obtain microcrystalline
cellulose and then nanocellulose extraction using sulfuric acid
hydrolysis and sonication. The product obtained was
characterized by thermogravimetric analysis (TGA), infrared
spectroscopy (FTIR), X-ray diffraction (XRD), zeta potential,
transmission electron microscopy (TEM) and particle size.
CELL 362
Carbonize it or not? A simple test method for biomassic
materials
Jaime F. F. Quesada-Kimzey, [email protected]. Escuela
de Química, Instituto Tecnológico de Costa Rica, Cartago,
Cartago, Costa Rica
Organic composite test sample fabricated in FDM.
CELL 361
Strategies for the utilization of cellulosic
generated from the pineapple cultivation
residues
Marianelly Esquivel Alfaro, [email protected], Galia
Moreno Cento, Dorell Rojas Fonseca, Karla Ramírez Amador,
Guillermo Jiménez Villalta. Polymers Research Laboratory
(POLIUNA), Universidad Nacional de Costa Rica, Heredia,
Costa Rica
Pineapple cultivation in Costa Rica produces about 300 tons of
stubble per hectare which must be treated quickly to prevent
the spread of the Stomoxys calcitrans fly, which might affects
livestock. The post-harvest residue of pineapple consists of
plant stems and leaves, with the following physicochemical
composition in dry basis: 45.32% alpha-cellulose, 25.63%
lignin, 17.43% hemicellulose, 8.9% moisture, 4.64% ashes,
38.50% solubility in hot water, 37.01% solubility in cold water
and 8.69% in cyclohexane / ethanol extract. Two strategies to
use these residues are proposed in this work; the first by
conducting material degradation using a consortium of
bacteria, yeast and fungi (Pleurotus ostreatus, Lactobacillus
Agroindustrial processes are often burdened by the costs and
difficulties of the management of waste biomass. When not
managed properly, the burden is on the environment and local
communities. Valorization of waste is preferable to
management, as it usually can at least cover its costs and
additionally be environmentally and socially more consequent.
One option for waste biomass is carbonization. The main
product, charcoal, can have a variety of uses, ranging from
energy vehicle to the revolutionary soil amendment named
"biochar". The market for charcoals is ever expanding.
Different charcoals are obtained from different feedstocks. In
the same carbonization process, different biomassic materials
may lead to significantly different yields and qualities.
Additionally, temperature and pressure variations lead to
variations in yields and qualities from the same feedstock.
Nevertheless, in most processes taking place in small scale
production, pressures are near atmospheric and temperatures
vary between 300 °C and 600 °C. Under such conditions,
different feedstocks typically yield between 20 % and 40 %
m/m, and heat content preserved in the charcoal ranges
between 67% and 13% of the original. In the latter case, >85%
of the energy in the original material would be lost to the
environment in the bonds of air- or waterborne pollutants, so it
should not be carbonized except if the gases are to be used. A
simple inexpensive method requiring only a balance and a
furnace, with the potential of a reference method, is hereby
proposed. Its purpose is to assess expectable charcoal yields
and qualities from any dried biomassic material. It was applied
to a variety of biomassic materials in order to determine its
reliability, with excellent results. On 4 different biomasses,
repeatability of the essay was determined with n > 15, yielding
variation coefficients below 5 %. The essay was additionally
carried out on 15 different biomasses with n =2 or n =3,
yielding variation coefficients below 3 %. The method can be
complemented by determination of heat content of the
charcoal, in order to make a decision regarding its eventual
carbonization as a means of valorizing the material as an
energy vehicle. A complementary case study, involving coffee
husk, is presented as an example.
CELL 363
Emulsified systems containing cellulose nanofibrils (CNF)
Carlos A. Carrillo1,2, [email protected], Tiina Nypelö3,1,
Orlando J. Rojas4,1. (1) Department of Forest Biomaterials,
North Carolina State University, Raleigh, North Carolina,
United States (2) Escuela de Ingenieria Quimica, Universidad
de Los Andes, Merida, Venezuela, Bolivarian Republic of (3)
Department of Chemistry, University of Natural Resources and
Life Sciences, Vienna, Vienna, Austria (4) Department of
Forest Products Technology, Aalto University, Espoo, Finland
The use of cellulose nanofibrils (CNF) in different applications
has grown exponentially since this nanomaterial was first
isolated more than 30 years ago. The incorporation of CNF in
emulsified systems is a subject that has received limited
attention but has a great potential given CNF ability to stabilize
interfaces. Here we investigated the effect of incorporating
CNF in emulsified systems. Soybean oil was used as the
organic phase and water-in-oil (W/O) microemulsions and
normal emulsions were prepared containing CNF in the
aqueous phase. Also, multiple emulsions of the water-in-oil-inwater (W/O/W) type were obtained when the composition of
the system was changed. The emulsions obtained were
analyzed and characterized using different techniques. The
presence of CNF in the aqueous phase enhanced the stability
of the W/O/W emulsion, especially at high concentrations of
the nanomaterial
CELL 364
Adsorption of inorganic photo-active nanoparticle/enzyme
hybrid systems on surfaces modified with cellulose
obtained from natural and industrial residues: A QCM
study
Iker Iñarritu3, [email protected], Antonio Topete4,
[email protected], Roxana López-Simeon5, Eduardo
Torres2, Jose Campos-Teran1. (1) Departamento de Procesos
y
Tecnología,
Universidad
Autónoma
MetropolitanaCuajimalpa, México, D.F., Mexico (2) Centro de Química,
Universidad Autónoma de Puebla, Puebla, Puebla, Mexico (3)
Posgrado en Ciencias Naturales e Ingeniería, Universidad
Autónoma Metropolitana-Cuajimalpa, México, D.F., Mexico (4)
Departamento de Fisiología, Universidad Autónoma de
Guadalajara, Guadalajara, Jalisco, Mexico (5) Posgrado en
Biotecnología,
Universidad
Autónoma
MetropolitanaIztapalapa, México, D.F., Mexico
Hybrid nanomaterials which incorporate inorganic photo-active
nanoparticles (NPs) and enzymes immobilized on different
supports have recently captured the attention of many
scientists and technologists. These systems have been
extensively used on a large number of applications including
biomedical and environmental analytic and diagnosis tools,
photocatalysis, and photodynamic cancer therapy, etc. For
instance, it has been reported that semiconductor NPs, as well
as gold NPs, are able to generate reactive oxygen species
upon illumination with light with the appropriate wavelength
that can be used as co-substrate in numerous peroxidase
catalyzed reactions, having in this way a photo-active catalytic
system. On the other hand, cellulose nano- and microfibers
have been used as supports to immobilize the aforementioned
hybrid composite systems. Cellulose have several interesting
properties such as high strength and stiffness, ease of
functionalization, low weight and cost, biodegradability and
renewability, which make it a first order candidate material to
be used as support for the immobilization of NPs. Selfassembling processes based on electrostatic, hydrophobic,
hydrogen bonds, or through conjugation with specific ligands
might be an efficient strategy to produce novel composite
materials combining the optical useful properties of inorganic
NPs with the structural virtues of cellulose fibers. Therefore,
the study of photo-active NP-cellulose interfacial interactions
as well as the stability of the conjugated systems is of great
interest for the development of immobilized hybrid
nanomaterials. With this aim, in this work we will present
Quartz Crystal Microbalance adsorption study of the
immobilization of NP-enzyme complexes, composed by
peroxidases and mercaptoacetic acid-capped CdS NPs or
citrate-capped gold NPs, at surfaces modified with cellulose
obtained from algae residues and “nejayote” (a liquid mixture
produced as a residue of corn tortilla production). In the latter
case, cellulose obtained was functionalized with ferulic acid
trough a laccase enzymatic treatment. FTIR, and UV vis
spectra confirmed the covalent bond between cellulose and
oxidized ferulic acid. Adsorption isotherms at different
temperature, pH and electrolyte conditions were considered to
evaluate the NP-enzyme-cellulose interfacial interactions.
CELL 365
Drying kinetics as a convenient method to determine
relative diffusivity of water in woody biomasses
Allen Puente-Urbina1,2, [email protected], Jean P.
Morales-Aymerich2, Yong Sik Kim3, Julio F. Mata1. (1) Biomass
Laboratory, School of Chemistry, University of Costa Rica, San
Pedro de Montes de Oca, San José, Costa Rica (2) Latin
American Chair of Landscape Forestry Management, Tropical
Agricultural Research and Higher Education Center, Turrialba,
Cartago, Costa Rica (3) Division of Wood Chemistry &
Microbiology, Department of Forest Products, Korea Forest
Research Institute, Seoul, Korea (the Republic of)
Drying is a fundamental procedure in many technological
processes. This unit operation reflects primarily the diffusivity
of liquids (e.g. water) within the porous matrix of materials. The
drying of residual biomasses is an important issue in regions
where agricultural or agro-industrial activities may provide
significant amounts of this kind of materials as residual
products to be used as renewable solid fuels.
For drying, combustion and gasification of biomasses, internal
fluid diffusivity is a most important aspect. We have used an
uncomplicated method based on drying kinetics for the
determination of relative diffusivity of water in woody
biomasses (Ulate-Segura and Mata-Segreda, 2014*). Every
material shows a specific drying curve that depends on its
chemical and physical characteristics. Observed results can be
registered as mass - time data (m vs. t). There is an initial
linear relationship (constant -dm/dt) due to the evaporation of
water covering the solid that behaves as free liquid. This period
will last for as long as the rate of liquid arrival from inside the
material to the surface equals the rate of evaporation. Once
the system achieves the critical condition tc - xc (where x is the
extent of drying at the time t), the drying rate decreases as the
process takes place. In this stage the rate of drying is
dependent on factors other than the intrinsic liquid volatility.
It is reasonable to state that fluids diffuse faster in porous
materials with high xc values, allowing the use of this
parameter as relative measure of liquid diffusivity.
14 Samples of wood sawdust were analyzed. xc Values
observed were between (0,21 ± 0,01) and (0,41 ± 0,02). Also,
the data allow the calculation of other parameters that can be
useful to decide the suitability of use of a specific woody
biomass as solid fuel. One is the apparent specific surface
area through which the evaporation of water takes place.
Another useful piece of information derived from the
measurements is the energy cost involved during drying that
can be easily obtained from duration of the drying and
performance
of
the
moisture
analyzers.
*Ulate-Segura, D. G.; Mata-Segreda, J. F., Int. J. Renew.
Energy Biofuels 2014, DOI: 10.5171/2014.970016.
CELL 366
Enzymatic pretreatment to improve cellulose solubility in a
green solvent of NaOH/urea
Liming Zhang1, [email protected], Tingting You2, Lu
Zhang1, Feng Xu3. (1) Beijing Forestry University, Beijing,
China (2) Beijing Forestry University, Beijing , China
Cellulose, as an environmentally friendly and renewable
biomaterial, could be converted into a variety of products.
However, the application of cellulosic materials is hampered
due to its insolubility. In this study, enzymatic pretreatment was
reported to promote the dissolution of polar cellulose in
NaOH/urea solution. The solubility of cellulose was strongly
depended on the pretreatment time and degree of
polymerization (DP). The untreated cellulose with a DP of 590
was hardly (less than 0.5%) dissolved in NaOH/urea. After
pretreated by cellulase (2 FPU/g of untreated cellulose) for 6 h,
cellulose DP decreased to 392 and its solubility increased to
6%. With the reduction of amorphous cellulose, the crystallinity
of poplar cellulose increased from 44.6% to 52.4%. Though the
crystallinity increased, the solubility of cellulose in cold
NaOH/urea solution was improved due to decrease of DP. The
results suggested that the effect of DP on the cellulose
dissolution in NaOH/urea solution is much more important than
that of crystallinity. The enzymatic pretreatment was proved to
be an effective and green method to promote dissolution of
cellulose.
untreated cellulose sample
The insoluble part of the treated sample
CELL 367
Development and characterization of compatible cellulose
and cellulose blended with soy protein membranes using
a novel solvent system
Eugene F. Douglass2, [email protected], Richard
Kotek1. (1) Textiles Engineering Chemistry and Science, North
Carolina State Univ, Raleigh, North Carolina, United States (2)
Chemistry,
Nazarbayev
University,
Astana,
Aqmola,
Kazakhstan
A new environmentally friendly solvent system has been
developed to make cellulose (image 1) and cellulose blend
membranes.Current industrial methods for making cellulose
membranes are relatively expensive, use toxic or dangerous
solvents,and
have
environmental
concernsregarding
hazardous waste production. It was determined there was a
need to see if this novel system could be used for membrane
production, we were successful. These membranes were
produced, and they were characterized, and found to have
physical properties comparable with current cellulose
membranes.We then used these results to attempt the
development of blend materials, with unique properties. We
developed these membranes with pure cellulose and blended
with soy protein to make a composite membrane with unique
properties. These compatible blends of protein with cellulose
had never been accomplished before. The methods of
characterizing these materials are also useful in determining
compatibility of polymers with one another in a solid system.
We discovered these new blend materials have interesting
chemical and physical characteristics, and adding these
biomaterials remains compatible at the macro and micro level
with cellulose. These materials were then characterized and
found to have similar physical properties compared to
conventional cellulose membranes (Table 1).
Cellulose dissolved in novel solvent system.
The dissolution of cellulosic macromolecules is the first
predominant step to broaden the application of cellulosic
materials, the most abundant naturally-derived polymer in the
world. In this study, three solvent systems containing
NaOH/urea, DMAC/LiCl and ionic liquid (3-butyl 1immidazolum chloride) were selected to dissolve cellulose from
different sources including microcrystalline cellulose (Avicel
PH-101), cotton linter powder and filter paper (CF11) in order
to target an effective dissolution method. Electron scanning
microscopy, Fourier transform infrared spectroscopy, BET,
wide angle X-ray diffraction, and dynamic mechanical analysis
were used to characterize the morphology, functional groups,
surface porous morphology, crystallinity and mechanical
behavior, respectively, of films prepared by casting dissolving
cellulose and CO2 supercritical dehydration. The electricallyresponsive films were subsequently prepared by the oxidative
polymerization of aniline on the film surface. The electrical
properties of the resulting films were measured by 4-probe
resistivity method and exhibited good conductivity.
CELL 370
Cellulose/PVA composite films prepared by NaOH/urea
solvent: Structure and properties
Comparison of Physical Properties of Membranes made with
cellulose or cellulose blended with various forms of Soy protein.
CELL 368
Role of urea in dissolution of cellulose
[email protected],
Yoshiharu
Noriyuki
Isobe4,2,
1
Nishiyama , Satoshi Kimura2, Masahisa Wada3, Shigenori
Kuga2. (1) CERMAV, Grenoble, France (2) The University of
Tokyo, Tokyo, Japan (3) Biomaterials Science, The University
of Tokyo, Tokyo, Japan (4) Laboratoire Rhéologie et Procédés,
Université Joseph Fourier, Grenoble, France
To clarify the role of urea in dissolution of cellulose, solubility
test, DSC, and X-ray diffractometry were performed. From the
eutectic peak in the DSC profiles, it was found that urea does
not have direct interaction. In addition, we performed
preliminary experiments of small angle X-ray scattering (SAXS)
on cellulose oligomer (DP = 7) dissolved in alkali (lithium
hydroxide, LiOH) solution. Although the values of radius of
gyration (Rg) were almost the same, the intensity got smaller
with the addition of urea. This means that urea does not
change the molecular conformation of cellulose oligomer but
decrease the electron density. Namely, urea is likely to
stabilize the alkali-hydrated cellulose molecules by taking out
abundant alkali molecules that are not necessary for hydration
of cellulose and rather can be an origin of the formation of
alkali-cellulose crystal, which leads to precipitation of cellulose.
CELL 369
Effective dissolution of cellulose for making electricallyresponsive films
Sanjit Acharya, [email protected], Yang Hu, Noureddine
Abidi. Texas Tech University, Lubbock, Texas, United States
Min XU1,2, [email protected], Hao Ge1,2, Xianghui
Wang1. (1) department of physics, East China Normal
University, Shanghai, China (2) Shanghai Key Laboratory of
Magnetic Resonance, Shanghai, China
With more and more attention paying to environmental
protection, biocompatible and degradable materials will have a
better prospect. Cellulose, as one of the most important natural
polymer materials, is applied more and more wild after the
invention of water/NaOH/urea solvent system[1-3]. In this work,
PVA was combined with cellulose in NaOH/urea solvent with
different freezing/thawing cycle times. A series of films were
prepared from the mixed solutions and characterized by Solidstate NMR, mechanical measurements and blood compatibility
measurement.The results of 1H solid state NMR and XRD
experiments indicated that the crystallinity of the composite
films was lower than the crystallinity of either cellulose or PVA
films. The spin diffusion NMR experiments showed that after
freezing/thawing cycles, the compatibility between cellulose
and PVA of the composite films was much better than the films
without freezing/thawing process. The strong interaction makes
the PVA cannot be washed off during the long time soaking
and washing.The mechanical measurements and blood
compatibility measurements were also performed. The results
showed cellulose/PVA composite films had better mechanical.
The stress of the composite films increased 20~50% compared
with pure cellulose film. Both pure cellulose and cellulose/PVA
films showed good blood compatibility. The hemolysis of all the
samples was on the range of 0~2%, which is far below the
accepted threshold value of 5%, implying good blood
compatibility. Besides, the blood clotting time of all the samples
are longer than 90min, indicating that the cellulose/PVA
composite films have very good antithrombogenic property.
From the experiments all above, we believe that the
cellulose/PVA composites have great potential in biological
application.
The further biocompatibility research is still
undergoing.
1. E.V.R. Almeida, E. Frollini, A. Castellan, V. Coma.
Carbohydrate Polymers. 2010, 80, 655
2. Ran Li, Lina Zhang, Min Xu. Carbohydrate Polymers. 2012,
87, 95
3. Chunyu Chang, Ang Lue, Lina Zhang. Macromolecular
Chemistry and Physics. 2008, 209, 1266
CELL 371
Facile ionic liquid-mediated technology for cellulose
nanocrystals production directly from wood
Hatem Abushammala1,3, [email protected], Ingo
Krossing2,3, Marie-Pierre G. Laborie1,3. (1) Chair of Forest
Biomaterials, University of Freiburg, Freiburg, Germany (2)
Institute of Inorganic and Analytical Chemistry, University of
Freiburg, Freiburg, Germany (3) Freiburg Materials Research
Center, University of Freiburg, Freiburg, Germany
Cellulose Nanocrystals (CNCs) are traditionally produced using
strong acid-catalyzed hydrolysis of cellulosic sources. Such
severe route generally requires pure forms of cellulose as a
starting material, such as pulp and microcrystalline cellulose,
while no reports exist about the extraction of CNCs directly
from lignocelluloses such as wood. Therefore, mild and direct
CNC production routes from wood are needed. Ionic liquids
(ILs) have shown a great potential for wood dissolution,
processing, and fractionation. They are often qualified as
“green solvents” because of their recyclability and reusability.
More importantly, their dissolution affinities to wood polymers
can be tailored by varying their constitutive ions and the
applied dissolution conditions (temperature and time). In
optimized conditions, ILs might be particularly suited for
simultaneous wood pulping and nanocellulose extraction. This
presentation discusses the first report about the extraction of
CNCs directly from wood. The performance aspects of wood
pulping and CNC extraction and the properties of the produced
CNCs are covered in addition to the overall process
optimization.
Acknowledgments: This research is funded by German
Academic Exchange Service (DAAD), German Society of
International Collaboration (GIZ) and Brazilian Department of
higher Education (CAPES program) through the Novas
Parcerias program for Brazilian-German academic exchanges.
temperatures analogous to cellulose dissolution processes
(100 - 120 °C), and were periodically investigated employing a
broad range of spectroscopic and chromatographic
techniques.3 Dialkylimidazolium carboxylate ionic liquids are
not inert towards cellulose, and their tendency to form NHeterocyclic Carbenes,4 their so- called ‘non-innocent’ nature,
plays a vital role. By contrast, chloride anologues retain the
beneficial property of good cellulose solubility, whilst lacking
the undesirable tendency of form adduct side-products.
1. J. P. Hallett and T. Welton, Chem. Rev., 2011, 111, 3508.
2. A. Brandt, J. Gräsvik, J. P. Hallett and T. Welton, Green
Chem., 2013, 15, 550.
3. M. T. Clough et al., submitted to Green Chem.
4. M. T. Clough, K. Geyer, P. A. Hunt, J. Mertes and T. Welton,
Phys. Chem. Chem. Phys., 2013, 15, 20480.
CELL 372
Ionic liquids: Not always innocent solvents for cellulose
Matthew T. Clough1, [email protected], Karolin
Geyer2, Patricia Hunt1, Sunghee Son2, Uwe Vagt2, Tom
Welton1. (1) Imperial College London, London, United Kingdom
(2) BASF SE, Ludwigshafen, Germany
Room-Temperature Ionic Liquids (RTILs) are typically
constituted of bulky, asymmetric and charge-diffuse ions,1 and
are characterised by their high densities and vanishingly low
vapour pressures. Over the course of the past two decades,
the applications of ionic liquids have become very varied and
far-reaching, foremost as solvents for sustainable processes,
electrolytes, and recently in deconstruction of lignocellulosic
Cellulose is the world’s largest biorenewable
biomass.2
resource. Strong intermolecular and intramolecular H-bonds
hold together the individual polymer strands, rendering
cellulose insoluble in the majority of conventional solvents; this
‘recalcitrant’ behaviour presents a major challenge to
harvesting such an abundant resource. Carboxylate, chloride
and dialkyl phosphate ionic liquids are capable of solvating
cellulose,2 and represent promising alternatives to the existing
and far-from-ideal ‘Lyocell’ and ‘Viscose’ technologies.
However, the possibility of decomposition reactions occurring
between
solvent
and
solute
must
be
carefully
considered.Mixtures of ionic liquids with cellulose, and
subsequently with smaller model compounds, were heated to
Proposed mechanism for reaction of ‘non-innocent’ ionic liquid
[C2C1im][OAc] with D-(+)-glucose, yielding C2-substituted ‘adducts’
with shortening hydroxyalkyl chains.
CELL 373
How ionic liquids effect glucose and cellobiose solvation:
Insights from enhanced sampling molecular dynamics
techniques
Vivek S. Bharadwaj1, [email protected], Timothy
Ashurst1, Timothy Schutt1, Christopher M. Maupin2. (1)
Department of Chemical and Biological Engg, Colorado School
of Mines, Golden, Colorado, United States (2) Alderson Hall
Rm 437, Colorado School of Mines, Golden, Colorado, United
States
One of the major challenges to utilizing cellulosic feedstock
and converting them to biofuels has been the recalcitrance of
crystalline cellulose to hydrolysis techniques, both enzymatic
and chemical. Ionic Liquids (ILs) are a unique class of solvents
that are characterized by low vapor pressure, low flammability
and can be designed with specific solvation properties by
choosing appropriate cationic and anionic groups. Imidazolium
based ILs have been found to be proficient at cellulose
dissolution and have led to the development of successful
pretreatment technologies for priming cellulosic feedstock to
make them more amenable for hydrolysis. However, the IL
pretreatment technologies are limited by their cost of
production and compatibility with enzymatic technologies for
hydrolysis. A molecular level understanding of the solvation
mechanisms of Imidazolium based ILs is currently lacking and
is necessary for improving the performance and overcoming
current limitations of IL pretreatment technology. In this study
we use molecular dynamics (MD) simulations to systematically
analyze the impact of the alkyl chain length on the solvation
characteristics of imidazolium-acetate based ILs on glucose
and cellobiose. The results of the study indicate that the ILs
solvate glucose and cellobiose differently as compared to
water thereby significantly impacting the configurational space
explored by them. The simulations are consistent with
experimental values of diffusion and densities. We reveal how
hydrogen bonding networks change in the presence of ILs and
demonstrate that the dynamics in ILs is reduced due to the
inherent viscous nature of ILs. Enhanced sampling techniquesUmbrella sampling and Well Tempered Metadynamics have
been utilized to elucidate the free energy surfaces that govern
the ω dihedral (O6-C6-C5-O5) in glucose and the φ (O5-C1O4-C4)- ψ (C1-O4-C4-C5) configurational space around the
glycosidic bond in cellobiose for the water and 3 Imidazoiumacetate ILs (Ethyl Methyl, Butyl Methyl and Octyl Methyl
Imidazolium Acetate). The results indicate that the ILs restrict
the ω dihedral in glucose to the gauche-trans configuration and
stabilize very specific φ-ψ conformations for the glycosidic
bond.
polymerisation of paper-based cellulose will be presented,
ranging from typical climates in libraries and archives to worst
case situations such as old buildings in polluted urban
environments. The proposed application of the model is
intended to assist stakeholders in decision making towards
optimizing the preservation of paper-based heritage. It will
provide a tool that enables to evaluate the impact of the
environment and thus the choice of the best cost benefit
mitigation strategies adapted in each particular context and
situation.
[1] Ekamstam, A.The behaviour of cellulose in mineral acid
solutions: Kinetic study of the decomposition of cellulose in
acid solution. Berichte der Deutschen Chemischen
Gesellschaft
(1936)
69A,
553–559
[2] Zou X, Uesaka T, Gurnagul N. Prediction of Paper
Permanence by Accelerated Aging I. Kinetic Analysis of the
Aging
Process.
Cellulose
(1996)
3,
243-267
[3] Tétreault J, Dupont A-L, Bégin P, Paris S. The Impact of
Volatile Compounds Released by Paper on Cellulose
Degradation in Ambient Hygrothermal Conditions. Polymer
Degradation and Stability (2013) 98, 1827–1837
CELL 375
Ancient paper as a multicomponent system: A novel
approach to the kinetics of its degradation
Sara Zaccaron1, [email protected], Paolo F. Calvini2,
Renzo Ganzerla1. (1) Molecular Sciences and Nanosystem,
Ca' Foscari University Venice, Venice, Italy (2) School of
Cultural Production and Conservation of the Cultural Heritage,
Ca' Foscari University Venice, Venice, Italy
CELL 374
Degradation of paper under adverse
conditions: Modeling considerations
environmental
Jean Tétreault 2, Paul Bégin2, Anne-Laurence Dupont1,
[email protected]. (1) Centre de recherche sur la
conservation, Muséum national d'histoire naturelle, Paris,
France (2) Canadian Conservation Institute, Ottawa, Ontario,
Canada
Research data on the impact of the environment on the
degradation of paper using accelerating ageing tests has been
available for several decades. Attempts to correlate the
information with predicted levels of deterioration of paper in
natural ageing conditions are scarcer. The purpose of the
present research is to explore these correlations in various
environmental conditions including the presence of outdoor
and indoor airborne pollutants. Using the model for
degradation of linear polymers which is usually applied to
cellulose, and based on first order reaction kinetics proposed
by Ekenstam [1], Zou developed a model for determining the
degradation reaction rate constant k [2]. This model was tuned
in the present work to include the impact of different pollutants,
relative humidity levels and temperature on paper stability.
Different equilibrium and empirical equations were used for the
determination of the two main variables hydrogen ion
concentration and moisture content. The impacts of
temperature and degradation state of cellulose were
investigated and the protective effect of carbonyl volatile
compounds on cellulose degradation evidenced in our previous
experiments [3] was examined further. The proposed model is
described based on data from our previous research, and
scenarios predicting the decay over time of the degree of
This kinetic study aims to shed some light on degrading
processes occurring to papers in closed environments. An indepth investigation has been carried out with a novel insight
into cellulosic materials. Unlike the majority of previous
researches, this project has based on two main key points: (1)
the paper is a complex system constituted by synergistically
interacting components; (2) a long-lasting approach is of
paramount importance to have a reliable insight into the
degradation pathway throughout the whole process. To this
end, a gelatin sizing and different iron-gall inks have been
considered as main components of the system and their
interaction with cellulose in ancient paper documents has been
investigated. Moreover, in order to fully exploit recent kinetic
approaches proposed by Calvini and co-workers (2008), the
complex nature of the mechanism of degradation has been
unraveled through more than 400 days of accelerated ageing
in sealed vessels.The obtained results clearly underpinned an
autocatalytic mechanism of cellulose breakdown, greatly
enhanced by iron-gall inks through the release of degrading
volatile organic compounds (VOCs: both acids and oxidizing
species) in a very short time, as compared to the whole ageing
process. Furthermore, experimental evidences have been
provided for the protective role of the gelatin sizing with its
beneficial reduction of the rate of cellulose degradation by
buffering negative effects of produced degrading compounds.
Calvini, P.; Gorassini, A.; Merlani, A. L. Cellulose 2008, 15,
193-203
CELL 376
CELL 377
Cellulose as a detector for assessing storage materials for
cultural heritage objects
Durability and permanency of formulated traditional Malay
black ink on European handmade paper upon accelerated
aging tests
Eric Breitung, [email protected], Marcie Wiggins,
Linhchi Nguyen. Preservation Research and Testing Division,
Library of Congress, Washington, District of Columbia, United
States
The Library of Congress has a quality assurance program for
testing materials that come into contact with collections in
storage or on display to ensure those materials will not harm
collections. The program utilizes standard tests to ensure
materials meet specifications, and uses the Oddy test for
specific materials assessment. The traditional Oddy test
assesses the impact of material off-gassing on collection items
through the corrosion of metal coupons, a result that does not
necessarily correlate well to the Library's primarily paper-based
collections. This presentation focuses on research in the
Preservation Research and Testing Division that uses paper
instead of metal as a sensor and multiple analytical methods to
assess the degradation level of the paper sensor. Common
book and paper preservation materials such as book cloths,
binding boards, foams, and adhesives were subjected to
accelerated aging in the presence of Whatman No.1 filter
paper (cellulose) and the traditional Oddy metal sensors, then
evaluated with ion chromatography (IC) and ultraviolet-visible
(UV-Vis)
spectroscopy.
Gas
chromatography-mass
spectrometry (GC-MS) was the primary technique
implemented to identify the origin of IC signals that both related
to cellulose degradation products and volatile organic
compounds that absorbed into the cellulose sensor. Additional
analysis of corrosion products formed on the metal coupons
with x-ray diffraction (XRD) was related to compounds found
using solid phase micro-extraction (SPME) GC-MS of the
aqueous extraction of the aged cellulose sensors. The
assessment of the impact of these specific products on
collection materials to better understand the often contradictory
results obtained from the Oddy test, and how a new test might
better inform the library, archive, and museum paper
conservation community, will be discussed.
Paper and metal sensor accelerated aging configurations.
Rajabi Abdul Razak1, [email protected], Raihan
Othman2, Mandana Barkeshli1. (1) Applied Arts and Design,
International Islamic University Malaysia, Kuala Lumpur,
selangor Darul Ihsan, Malaysia (2) Department of Science in
Engineering, International Islamic University Malaysia,
Gombak, Selangor Darul Ehsan, Malaysia
We investigate a traditional Malay formulation of black ink
comprising soot particles suspended in water, mixed with
cashew gum binding agent and natural additives. The
formulated ink, drawn on a European handmade paper
(Cartiere Magnani), is then subjected to two types of standard
accelerated aging test; standard method for moist-heat aging
(ISO 5630-3:1996) 85°C and 65% relative humidity with
interval period 1,2,3,6, and 12 days, and the light fastness test
according to the standard procedures ASTM D 3424 & ASTM
G 155 (Xenon Arc) with total exposure of 120 hours. In both
techniques, the color changes are evaluated through visual
inspection against a grey scale and also instrumentally
measured color coordinates. For comparison, the tests are
also repeated on Chinese and Indian commercial inks. The
traditional Malay black ink underwent both accelerated ageing
procedures without any significant changes in the visible
reflectance spectra and the total color difference. The
commercial Indian, however, shows considerable fading upon
the light fastness test. These results substantiate the durability
and permanency of the traditionally formulated Malay black ink.
CELL 378
Cellulose acetate lamination: A comparison of naturallyaged laminates with artificial aging predictions
Molly McGath, [email protected], Sonja JordanMowery, John Baty, Mark Pollei. Conservation and
Preservation, Johns Hopkins University, Baltimore, Maryland,
United States
Cellulose acetate (CA) lamination was a conservation/
preservation treatment used to strengthen paper and protect
important documents from mechanical, biological and
environmental damage from the 1930s-1990s throughout the
United States. Lamination was perhaps the first conservation/
preservation treatment for paper documents to have been
rigorously studied and tested. However, while artificial aging
studies conducted by the National Bureau of Standards in the
1930s and again 1950s predicted the stability of the laminates
to be on the scale of hundreds of years, the long-term stability
of the treatment has been questioned in recent decades. The
goal of this study was to evaluate generally the current
condition of laminates and compare this to what was predicted
by the NBS artificial aging studies. This study includes review
of published and unpublished documentation, site visits of
institutions with relevant collections, a survey of institutions,
and an analytical case study of well-documented laminates at
Maryland State Archives. The literature review highlighted the
necessity of deacidification of acidic paper prior to lamination,
the fact that not all CA films marketed for lamination were of
archival stability, and that artificial aging indicated long-term
stability of CA-laminate when the paper was neutral and the
film was archival. Site visits have generally shown laminates
that appear stable based on visual examination. Survey results
survey reveal that there is a large quantity of laminated
documents that include a range of formats: commonly
manuscripts, letters, maps and newspapers; and media: iron
gall ink and carbon-based writing ink being the most prevalent
across collections. Most respondents (76%) indicated that the
condition of their laminated documents was either somewhat or
mostly good. In spite of this generally positive review of
laminated documents, many respondents (42%) indicated that
their institution had had some lamination reversed. Chemical
and pH analysis of a well-documented collection adds
additional objective information to this discussion as questions
remain about non-observed induction periods for deterioration
of the plastic. This analysis, still in process, provides data on
the naturally aged documents that can be compared to what
was learned in artificial aging studies conducted in the 1930s
and the 1950s and also with studies done on naturally aged
specimens in the 1950s.
CELL 379
Paper
strengthening
and
desacidification
by
polyaminoalkylalkoxysilane copolymer networks: A model
study
Camille Piovesan1,2, [email protected], AnneLaurence Dupont1, Odile Fichet2, Isabelle Fabre-Francke2,
Bertrand Lavédrine1, Hervé Chéradame3. (1) Centre de
recherche sur la conservation, Muséum national d'histoire
naturelle, Paris, France (2) Laboratoire de Physicochimie des
Polymères et des Interfaces, Cergy-Pontoise, France (3)
Laboratoire Analyse et Modélisation pour la Biologie et
l'Environnement, Evry, France
The main cause of decay of paper is its acid content, which in
combination with time of exposure ultimately leads to
mechanical failure. Deacidification helps paper fight acidity
produced during the natural aging process but has no
strengthening effect1. We have developed a stabilization
methodology for simultaneous deacidification and fiber
strengthening based on the copolymerization of polysiloxanes
using compounds with different alkoxy and amine
functionalities2. Two di-alkoxysilanes, with one amine function
(AMDES, aminopropylmethyldiethoxysilane) and with two
amine
functions
(AEAPMDMS,
N-(2-aminoethyl)-3aminopropylmethyldimethoxysilane), and a tri-alkoxysilane
(APTES, aminopropyltriethoxysilane) were copolymerised and
used as fiber dry strengthening agents in a model paper made
of pure cellulose. Deacidification is ensured by the amine
function while the random insertion of flexible linear segments
into a rigid polymer network through copolymerization of triand dialkoxysilanes should allow the formation of a flexible
polymer network. This should mitigate the rigidity imposed
when a dense network is inserted in the paper fibers, and
possibly help restructure degraded amorphous regions of
cellulose by more efficiently interconnecting the fibers. Two
treatment methods were used for the treatment. The
polymerization and copolymerization of the polysiloxanes in the
paper were investigated by using infrared spectroscopy and by
measuring the soluble fraction amount extracted (characterized
by NMR) from the treated papers. The study of the
physicochemical properties of the treated paper (mechanical
strength measurements and alkalinity) demonstrated that, the
required deacidification feature was verified and that the
different treatments allowed an efficient strengthening of the
cellulose fibers to various extents. This novel preservation
strategy for acidic and fragile paper especially targets
documents that are currently unfit for purpose because of their
very
poor
conservation
condition.
1. Souguir Z, Dupont A-L, d’Espinose de Lacaillerie J-B,
Lavedrine B, Cheradame H (2011) Chemical and
Physicochemical Investigation of an Aminoalkylalkoxysilane As
Strengthening
Agent
for
Cellulosic
Materials.
Biomacromolecules
12:2082-2091
2. Piovesan C, Dupont A-L, Fabre-Francke I, Fichet O,
Lavedrine B, Cheradame H (2014) Paper strengthening by
polyaminoalkylalkoxysilane copolymer networks applied by
spray or immersion – A model study. Cellulose 21:705-715
CELL 380
Parylene
coatings
strengthening
for
cultural
heritage
paper
Lei Pei, [email protected], Mark Pollei, Sonja JordanMowery, John W. Baty. Johns Hopkins University, Baltimore,
Maryland, United States
Parylene (a class of polymers of the base monomer paraxylylene), deposited via chemical vapor deposition (CVD),
underwent preliminary investigation in the 1990s to strengthen
brittle cultural heritage papers. The deposited monomers
polymerize in situ via radical-radical coupling, forming a thin,
conformal coating that strengthens paper. Other unique
properties of this technology are its mold resistance and its
ability to treat all the pages of a book simultaneously. In the
last 20 years, however, Parylene treatment has received
limited recognition within the conservation community and no
further study. Stated concerns include the uncertainty about
the permanence and durability of the treatment and the lack of
reversibility.
However, this potential treatment is worth revisiting because:
1) certain important assessments of the efficacy of Parylene
treatment were not performed in the previous work. These
include the optimization of the Parylene layer thickness for
conservation needs, the aging of treated papers rather than the
films by themselves, and the ability to conduct subsequent
conservation treatments following deposition. 2) CVD
deposition chambers have become cheaper and are more
compact. There are new analytical techniques to characterize
the coating. There are also new Parylene materials, including
soluble Parylene, which addresses the concern over
reversibility.
We will present the results obtained from visible
spectrophotometry and mechanical testing before and after the
accelerated aging of newsprint in a sealed vessel with
saturated sodium bromide at 80°C. Parylene coated paper
shows ten times higher folding numbers in MIT folding
endurance testing, over 60% higher in tensile strength, and
30% higher in Elmendorf tear resistance than the papers
without Parylene coating both before and after the aging. We
also investigated the behavior of Parylene coated paper in
standard paper conservation treatments. These results show
that Parylene-treated groundwood pulp book papers from year
1951 reveal many of the characteristics of a new wood pulp
paper, in term of rattle, turn radius, and general tactile
experience. Additionally, Parylene treated paper is receptive
to, and can even improve upon, conventional paper and book
conservation treatments such as tear mending, guarding,
washing and resizing, and book and case binding.
CELL 381
Paper deacidification using polysaccharide and alkaline
nanoparticles
The strategy and policy of European Union on the bioeconomy
sector will be presented, with a focus on research and
innovation programs.
CELL 383
[email protected],
Tamilselvan
Mohan1,
Lunjakorn Amornkitbamrung1, Rupert Kargl2, Silvo Hribernik2,
Karin Stana-Kleinschek2, Volker Ribitsch1. (1) Institute of
Chemistry, University of Graz, Heinrichstraße 28, AT-8010
Graz, Austria (2) Institute for Engineering Materials and
Design, Faculty of Mechanical Engineering, Smetanova 17,
2000 Maribor, Slovenia
The deterioration of paper based items such as books and
other written documents over time has been a major threat for
libraries and archives for many decades. Among several other
reasons, the acidity generated upon natural aging of paper is
the main cause of deterioration. The dominant chemical
reaction that occurs during aging is the acid-catalyzed
hydrolysis of cellulose, the main component of paper.1-2 Acid
hydrolysis leads to an irreversible depolymerisation of cellulose
chains and consequently accounts for a substantial loss of
mechanical strength.2-3 To overcome the above issues, in this
work, we developed an organic solvent based process using a
polysaccharide derivative and alkaline nanoparticles. This
reagent was employed for deacidification and strengthening of
old and brittle paper. This method removed the acidity
completely, introduced an alkaline reserve of 60 meq (OH)/100 g and simultaneously increased the tensile strength of the
paper up to 70%. Further it was possible to tune the pH, the
alkalinity, the tensile strength and the hydrophobicity of the
paper by coating with an appropriate concentration or type of
the alkaline nanoparticles and polysaccharide derivative with
different molecular weight.
1. P. Baglioni, D. Chelazzi, R. Giorgi and G. Poggi, Langmuir,
2013, 29, 5110-5122.
2. R. Giorgi, L. Dei, M. Ceccato, C. Schettino and P. Baglioni,
Langmuir, 2002, 18, 8198-8203.
3. G. Poggi, N. Toccafondi, L. N. Melita, J. C. Knowles, L.
Bozec, R. Giorgi and P. Baglioni, Appl. Phys. A, 2014, 114,
685-693.
CELL 382
European Union policy and initiatives for developing the
bioeconomy sector
Patrick R. Navard, [email protected]. Mines
ParisTech, Sophia Antipolis, France
In order to cope with an increasing global population, rapid
depletion of many resources, increasing environmental
pressures and climate change, Europe needs to radically
change its approach to production, consumption, processing,
storage, recycling and disposal of biological resources. The
target of the Bioeconomy program is to help Europe to live
within its limits. The sustainable production and exploitation of
biological resources will allow the production of more from less,
including from waste. It will also contribute to limiting the
negative impacts on the environment, reduce the heavy
dependency on fossil resources, mitigate climate change and
move Europe towards a post-petroleum society. Bioeconomy
in Europe has an estimated annual turnover of around two
trillion euros, employing around 22 million people, in
agriculture, forestry, fisheries, food and chemicals.
Renewable materials research in the U.S. Forest Service:
A perspective
World L. Nieh, [email protected]. USDA Forest Service,
Washington, District of Columbia, United States
The U.S. Forest Service is one of the seventeen agencies in
the U.S. Department of Agriculture (USDA). The U.S. Forest
Service mission is to sustain the health, diversity, and
productivity of the nation’s forests and grasslands to meet the
needs of present and future generations. Under this mission,
Forest Products research in the U.S. Forest Service provides
the science and technology to support agency priorities, such
as forest restoration, and bring value to U.S. landowners. Our
research program consists of solid wood utilization, wood fiber
utilization, the utilization of renewable polymers, chemicals
from wood, and manufacturing of products from wood. U.S.
Forest Service renewable materials research also supports
several U.S. National initiatives and priorities. The U.S.
National Nanotechnology Initiative (NNI) is the world’s leading
national nanotechnology initiative. U.S. Forest Service is the
leader in U.S. cellulose nanomaterials research. Cellulosebased and carbon-based nanomaterials are two current focus
points of the U.S. NNI. The USDA is a member of the U.S.
Biomass R&D Board. As such, the Forest Servicer biorefinery
R&D directly contributes to our Nation’s energy security goals.
Recently, the U.S. House of Representatives passed the
Revitalize American Manufacturing and Innovation Act of 2013.
This legislation would create a network of regional institutes
across the country, each focused on a unique technology,
material, or process relevant to advanced manufacturing.
Forest Service R&D is examining this opportunity in support
Congressional, Presidential, Departmental and Agency goals.
Green building is an area supported by USDA and the Forest
Service. U.S. Forest Service R&D will continue to pursue
opportunities in green building research. Our future will be a
biobased society. Renewable materials from the forest will play
a major role in citizens’ life – from the clothes they wear, to the
food they eat, to the transportation equipment they use, to the
fuels, the electronics, the furniture and housing they rely on.
When a citizen needs to relax and recharge, the entire family
will recreate in a forest. The human society will always rely on
the forest to provide us with resources that are essential to our
living. U.S. Forest Service R&D will continue to conduct
renewable materials research to provide the science and
technology in support of our Nation and agency mission of
sustaining the health and productivity of U.S. forests.
CELL 384
Biobased industries initiative: Realizing the European
bioeconomy potential
Patrick
van
Leeuwen1,
Patrick
R.
Navard2,
[email protected]. (1) Bio-based Industries
Consortium, Brussels, Belgium (2) Mines ParisTech, Sophia
Antipolis, France
On 9 July 2014, the European Union (EU) and industry
grouping, the Bio-based Industries Consortium (BIC), launched
a new European Public-Private Partnership on Bio-based
Industries (BBI). The aim is to trigger investments and create a
competitive market for bio-based products and materials
sourced locally and "Made in Europe", tackling some of
Europe’s biggest societal challenges. €3.7 billion will be
injected into the European economy between 2014 and 2024 €975 million from the European Commission and €2.7 billion
from the Bio-based Industries Consortium - to develop an
emerging bioeconomy sector. Through financing of research
and innovation projects, the BBI will create new and novel
partnerships across sectors, such as agriculture, agro-food,
technology providers, forestry/pulp and paper, chemicals and
energy. The aim of the BBI is to use Europe's untapped
biomass and wastes as feedstock to make fossil-free and
greener everyday products. At the heart of it are advanced
biorefineries and innovative technologies that will convert
renewable resources into sustainable bio-based chemicals,
materials and fuels. Organized in five value chains – that range
from primary production to consumer markets – the BBI will
help fill the innovation gap between technology development
and commercialization, sustainably realizing the potential of
bio-based industries in Europe. The BBI is a shift from a fossiland imports-based society to increase Europe’s share of
sustainable economic growth, and is expected to create tens of
thousands of jobs (80% in rural areas), revitalize industries,
diversify farmers’ incomes, and reduce GHG emissions by at
least 50% in comparison to fossil-based applications. The BBI
will manage the investments in the form of research and
innovation projects that are defined in annual Calls for
Proposals and implemented across European regions. In line
with Horizon 2020 rules, all stakeholders are invited to submit
innovative proposals and demonstrate progress beyond stateof-the-art.
Acknowledgement: Bio-based Industries Consortium (BIC)
CELL 385
Biomass raw materials-related issues on bioeconomy
strategies, research and development, and industrial
implementation
Denilson Da Silva Perez, [email protected]. New
Materials DIvision, FCBA, Grenoble, France
Circular biomass bioeconomy includes significant industrial
sectors converting biomass to pulp, paper, packaging, tissue
paper, boards, furniture, carpentry and construction materials,
textile fibres, biofuels, bio-energy, and special chemicals,
among others. The forest-based wood products in Europe
consist of 200 000 companies, employing 1.9 million people
and providing around 75 billion Euros in added value to the EU
economy. It contributes to some 8% of the EU’s total
manufacturing added value and sustainably manages forests
covering 35% of the EU’s landmass. In addition, there are
about 16 million forest owners and 3-4 million industrial jobs in
industry, to a large extent in rural areas and in SMEs.
However, the EU forest industry is facing major structural
changes. On one hand, important downsizing in pulping
production capacities due to the expansion of eucalyptus pulps
in South America concomitant with very fast reduction of
printing paper consumption has been observed in the last
years. On the other hand, the demand for new products
especially in bioenergy/biofuels, special fibre products and
chemicals sectors have also considerably increased, even if
very few real examples of true biorefinery units exist today. In
this presentation, the biomass materials-related issues related
to these new sectors, which will compose the essential core of
the circular biomass bioeconomy in a near future, will be
approached. Firstly, the difficulties in inventorying forestry and
agricultural biomasses availability and the factors explaining
the large differences between existing and exploitable
biomasses resources will be described on the basis of our own
experiences in on-going R&D and demonstration projects.
Then, the quality assessment and the variability of biomasses
and its suitability for different applications (pulp and paper,
boards, biofuels, bioenergy, chemicals) will be addressed. In
particular, a focus will be given on the current analytical
techniques and the needs of adapting them for large broad of
biomasses: forestry, including wood, bark, residues, stumps,
twigs/leaves, etc, and agriculture, including harvesting
residues, food residues industry or energetic crops) and the
pre-treated biomasses. Finally, the impact of different raw
materials on the performance of new biorefinery concepts
coupled with availability and costs analysis will be addressed
as part of the strategy for future industrial implementations in
different countries in Europe.
CELL 386
Network with COST Action FP1205: Innovative
applications of regenerated wood cellulose fibers
Åsa Östlund, [email protected], Dennis Jones. SP Wood
Technology, SP Technical Research Institute of Sweden,
Stockholm, Sweden
The key benefit from this European Cooperation in Science
and Technology (COST) Action network is to raise awareness
across the wider scientific and industrial community of the
potential of using native and regenerated cellulose-based
fibres for a variety of emerging high technology and uses.
Society is placing an increasing demand on materials and
there is a need for industries to become more resource aware
to make use of the potential in renewable, sustainable
resources, such as wood. Within this network we lift up the
potential of cellulose uses within the specific working groups
focusing on: A. Fabric and Textile manufacture – the need to
utilise alternative fibre sources from wood; B. Science and
uses of nanocellulose – as with all other nanoparticulate
science, the manufacture and use of nanocellulose provides a
range of opportunities based on the surface properties of the
material; and C. Cellulose foams and films – the use of
biomaterial foams and films is becoming increasingly important
and this working group will consider biocompatibility,
biodegradability, thermal and chemical stability. The COST
Action is arranging Meetings, Short Term Scientific Missions
and Training Schools to increase collaboration between Junior
and Senior researchers within Europe.
[www.cost.eu/domains_actions/fps/Actions/FP1205;
www.costfp1205.com]
CELL 387
Horizon 2020: EU research and innovation program
Karin Stana-Kleinschek, [email protected]. Faculty of
Mechanical Engineering, Institute of Engineering Materials and
Design, Laboratory for Characterization and Processing of
Polymers, University of Maribor, Maribor, Slovenia
Horizon 2020 is the biggest EU Research and Innovation
program ever with nearly €80 billion of funding available over
seven years (2014 to 2020), in addition to the private
investment that this money will attract. Horizon 2020 is the
financial instrument implementing the Innovation Union, a
Europe 2020 flagship initiative aimed at securing Europe's
global competitiveness. By coupling research and innovation,
Horizon 2020 is focusing on excellent science, industrial
leadership and tackling societal challenges. The goal is to
ensure Europe produces world-class science, removes barriers
to innovation and makes it easier for the public and private
sectors to work together in delivering innovation. The main
features and the implementation of this program will be
presented, with a special focus on renewable materials.
CELL 388
Preparation and characterization of antimicrobial cellulose
beads
Denise Petri2, [email protected], Leandro S. Blachechen2,1, Pedro
E. Fardim1. (1) Abo Akademi University, Turku, Finland (2)
University of Sao Paulo, Sao Paulo, Brazil
Cellulose beads with ~ 3 mm of diameter and high circularity
were obtained by dripping cellulose solutions (5 wt%, 6 wt%
and 7 wt%) dissolved in NaOH7%/urea12%, into HCl 2M
coagulation bath. Carboxylic groups were generated on beads
surface through NaClO/NaClO2/TEMPO oxidation method,
achieving total charge density of ~ 0.77 mmol/g. Pristine (CB)
and oxidized (OCB) beads were characterized by means of
optical images analyses, scanning electron microscopy (SEM)
and compression tests. Both types of beads, CB and OCB,
were used as adsorbent for poly(4-vinyl-N-pentyl pyridinium)
bromide, QPVP-C5, a bactericidal agent. The adsorption of
QPVP-C5 on CB and OCB was evaluated by means of FTIRATR, UV-Vis, CHN elemental analyses and X-ray
photoelectron spectroscopy (XPS). The adsorbed amount of
QPVP-C5 was remarkably higher on OCB than on CB, due to
ionic interactions. Desorption was less than 5%. The
interaction between neat OCB or OCB coated and two different
amounts of QPVP-C5 and Gram-positive bacteria Micrococcus
luteus was assessed by changes in turbidimetry, SEM and
elemental analyses. Bacteria adsorbed on the surface of neat
OCB and weakly QPVP-C5 coated OCB due to hydrogen
bonding or ion-dipole interaction. Notorious bactericidal action
was observed for OCB samples coated with large amount of
QPVP-C5.
CELL 389
Secondary liposomes stabilized by the electrostatic
deposition of chitosan-tannin composites as potential
delivery systems for proteins
Sergio Madrigal-Carballo1, [email protected], Jorge
Araya-Matey1, Emilia Alfaro-Viquez1,2, Daniel EsquivelAlvarado1, Christian G. Krueger2, Jess D. Reed2. (1) CENIBiot,
National Center for Biotechnological Innovations, San Jose,
San Jose, Costa Rica (2) Reed Research Group, University of
Wisconsin-Madison, Madison, Wisconsin, United States
Liposomes, spherical bilayer vesicles formed by dispersion of
certain polar lipids in aqueous solvents, have attracted
considerable attention in the food and agricultural industries in
recent years because of their ability to act as targeted releaseon-demand carrier systems for both water- and oil-soluble
functional compounds such as antimicrobials, flavors,
antioxidants, and bioactive ingredients. Encapsulation of
functional components in liposomes has been shown to
increase their stability and maintain their activity in
environments that typically lead to rapid degradation. On the
other hand, one of the major limitations of liposomes is that
they have a tendency to leak and lose encapsulated
components over time. Previous studies had demonstrated
that adsorption of a second layer of polymer around the
liposomes by electrostatic deposition, has been shown to be
very effective at improving the stability of emulsions, could
improve the stability of liposomes and provide an inexpensive
means to tailor the surface properties of liposomes.
In a previous work we have been shown the effect of coating
soybean lecithin liposomes with chitosan biopolymer, via
ionotropic gelation mechanism based on electrostatic
interactions. In the present work, we will show for the first time,
the effects of an electrostatic stabilization of liposomes using a
natural polymeric coating agent, based on chitosan-tannin
composites, that will work either as a coating agent, but also as
a potential delivery system for active compounds, such as
proteins and drugs.
S. Madrigal-Carballo, S. Lim, G. Rodríguez, A.O. Vila, C.G.
Krueger, S. Gunasekaran, J.D. Reed. J. Functional Foods,
2010, 2, 99.
J.D. Reed, C.G. Krueger, S. Madrigal-Carballo. TanninChitosan composites. USPTO, 2014, US 8,642,088 B2.
Acknowledgments: Authors are deeply thankful to the
Wisconsin Alumni Research Foundation (WARF) for the
financial support for this research.
Figure 1. Effect of chitosan-tannin composite concentration on
surface charge (z-potential, left) and size (apparent hydrodynamic
diameter, right) of secondary liposomes stabilized by electrostatic
deposition technique.
CELL 390
Chitosan-Collagen hybrid 3D-scaffolds
biomaterials for tissue engineering
as
potential
Priscilla Cubero-Mora1, Emilia Alfaro-Viquez2, Daniel EsquivelAlvarado2, Marianelly Esquivel-Alfaro1, Sergio MadrigalCarballo1,2, [email protected]. (1) National University,
Polymers Research Laboratory, Heredia, Heredia, Costa Rica
(2) CeNAT-CONARE, National Center for Biotechnological
Innovations (CENIBiot), San Jose, San Jose, Costa Rica
Chitosan has been applied to promote extracellular matrix
(ECM) formation in tissue regenerative therapy. The superior
tissue compatibility of chitosan may primarily be attributed to its
structural similarity to glycosaminoglycan in ECM. Chitosan
has been reported to be biocompatible, bio-absorbable and
particularly, is considered a good wound-healing accelerator.
Dermis and scaffolds made from chitosan exhibit weak
antigenicity, biodegradability, and superior biocompatibility
(hemostatic and cell-binding properties) by comparison to the
synthetic polymers, such as poly(lactic acid) (PLA),
poly(glycolic acid) (PGA), and polyethylene terephthalate
(PET). As a scaffold, chitosan-based materials in the form of a
sponge have been considered the most popular 3D-scaffolds
for dermal regeneration. Of the many scaffold materials being
investigated, collagen has been shown to have many
advantageous features. Highly porous collagen lattice sponges
have been used to support in vitro growth of many types of
tissues. We isolated chitosan from native shrimp waste
streams and collagen from tilapia aquaculture waste byproducts. Hybrid 3D-scaffold biomaterials were successfully
obtained by mixing chitosan with collagen at different molar
ratios. Chitosan-collagen hybrid composites were formulated
as 3D sponge-like scaffolds, applying previously developed
methodologies involving solvent casting and freeze-drying.
Chitosan-collagen hybrid 3D-scaffolds were characterized
according to its water uptake capacity, thermal behavior (DSC)
and morphology (SEM). Chitosan-collagen hybrid 3D-scaffolds
for tissue engineering have been successfully optimized and
characterized according to its thermal behavior, water
absorption capacity, porosity and morphology. We are
currently starting cell growth studies on the scaffolds using
model epithelial cells.
degradable by periodate oxidation (OBC), porous with aid of
specific porogens, and addition of the natural bone
osteoconductive calcium deficient hydroxyapatite (CdHA)
yielded a composite BC-CdHA). The present study compares
the cellular response of BC scaffolds with the nonwoven and
oriented fiber structure. The first group included samples of
BC, BC-CdHA, OBC, and OBC-CdHA. The second group
included BC-TS, BC-CdHA-TS, OBC- TS, OBC-CDHA-TS. The
viability of equine mesenchymal stem cells (EqMSC) on all BC
scaffolds was determined using MTS assay. The proliferation
of the EqMSC on all oriented BC tubular samples after two
days was much greater than observed for the corresponding
non-woven BC samples. Thus, indicating a definite effect of
chain orientation in the BC scaffold on the adhesion and
proliferation of EqMSC. Similar effect was observed for
EqMSC differentiation.
CELL 392
Tannin-chitosan composite nanoparticles as alternatives
to antibiotics
Christian G. Krueger2, [email protected], Emilia Alfaroviquez2,1, Sergio Madrigal-Carballo1, Jess D. Reed2. (1)
CENIBiot, National Center for Biotechnological Innovations,
San Jose, San Jose, Costa Rica (2) University of WisconsinMadison, Madison, Wisconsin, United States
Figure 1. Illustrative picture of chitosan-collagen hybrid 3Dscaffolds. A- Preparation of hybrid scaffolds. B- Physical appearance
of hybrid scaffolds. C- Swelling behavior of hybrid scaffolds. D, ESEM micrographs of chitosan alone (D) and chitosan-collagen (E)
hybrid scaffolds.
CELL 391
Effect of fiber orientation in bacterial cellulose scaffold on
cellular response: Adhesion, proliferation, differentiation
of equine mesenchymal stem cells
Roberto S. Benson, [email protected]. Materials Science
and Engineering, University of Tennessee, Knoxville,
Tennessee, United States
A very promising approach to restoring normal function to
damage bone tissue is the use of scaffolds seeded with cells to
promote the regeneration process. The scaffold material(s)
should be biocompatible with properties similar to components
of natural bone, degradable and endowed with the capacity to
regenerate the lost tissue function. In our laboratory we have
developed porous degradable bacterial cellulose scaffolds.
Bacterial cellulose (BC) is a natural polysaccharide extruded
as ultra thin fibers approximately 1.5 nm in width. The fibers
aggregate to form ribbons that combine due to extensive intra
and intermolecular bond hydrogen bonding to form a stable
gel-like membrane. Earlier in-vitro results indicated that BC
scaffolds seeded with equine mesenchymal stem cells
possessed capability to promote cell adhesion, proliferation,
and differentiation. The BC used in our investigation was made
Naturally occurring renewable resources that inhibit microbial
adhesion are important alternatives to antibiotics and may help
stem the alarming increase in drug resistant bacteria. We have
invented novel composite biomaterials comprising formulations
of tannin, extracted from cranberries (fruit, juice or press cake),
and chitosan, manufactured from shrimp shells. The
composites are versatile and can be formulated into useful
biomaterials such as nanoparticles, 3-dimensional foams, and
films. Bacterial invasion of gut epithelial cells (enterocytes)
provides a mechanism by which pathogens are protected from
complements, antibodies, and other immune defense
molecules, which in turn, allows the pathogens to colonize and
persist in the gut. Results of a dose-response experiment
indicate the cranberry tannin-chitosan composite nanoparticles
significantly reduced invasion of Caco-2 cells by extraintestinal pathogenic E. coli (ExPEC). The nanoparticles
significantly inhibited the ability of the pathogen to invade the
Caco-2 cells by 40%, 80% and 96% at a total polyphenolic
concentration of 0.2 µg, 0.5µg and 0.75µg GAE/ml
(respectively). Figure 1 shows scanning electron micrographs
exploring the effect of tannin-chitosan composite nanoparticles
on ExPEC surface structures that are involved in cell adhesion
and subsequent inhibition of invasion of intestinal epithelial
cells in vitro. When the pathogen was exposed to the tanninchitosan composite nanoparticle material, extensive coating
and cross-linking on multiple bacteria was seen. Results
suggest the cranberry tannin-chitosan composite materials
physically coat the surface virulence factors of ExPEC, which
in turn prevents invasion of the intestinal epithelial cell.
CELL 394
Improved thermal stability of polylactic acid (PLA) film
using β-cyclodextrin inclusion complex with PLA
Katia Rodriguez1, [email protected], YoungTeck Kim2,
Youngjae Byun3. (1) Sustainable Biomaterials , Virginia Tech ,
Blacksburg, Virginia, United States (3) Packaging Science ,
Clemson University, Clemson , South Carolina, United States
Figure 1. Scanning electron micrograph of tannin-chitosan
nanopaticles coating extra-intestinal pathogenic E. coli surface
structures
CELL 393
Bacterial
cellulose
research
Colombia, Finland, and the US
experience
between
Cristina Isabel Castro Herazo4, Robin Zuluaga Gallego3, Julio
Arboleda5, Hannes Orelma2, Luis O. Morales6, Piedad Gañán4,
Orlando J. Rojas5,1, [email protected]. (1) Forest
Biomaterials, North Carolina State University, Raleigh, North
Carolina, United States (2) Department of Forest Products
Technology, Aalto University, Espoo, Finland (3) New
Materials Research Group, Pontificia Bolivariana University,
Medellín, ANT, Colombia (4) Universidad Pontificia
Bolivariana, Medellin, Colombia (5) Aalto University, Espoo,
Finland (6) University of Helsinki, Helsinki, Finland
In this presentation we summarize a fruitful collaboration
between Universidad Pontificia Bolivariana in Colombia, Aalto
University in Finland and NC State University in the US.
Relevant aspects in this collaboration will be highlighted as an
example of effective cross-fertilization of ideas. More
importantly, we will discuss the utilization of a celluloseproducing acetic acid bacterium discovered by collaborators in
Medellin and isolated from commercially available Colombian
homemade fruit vinegar, Gluconacetobacter medellinensis sp.
nov. The bacterial cellulose was utilized in the in-situ
production of composites with polyvinyl alcohol that displayed
enhanced thermo-mechanical properties compared to the
individual components and that was assisted by physical and
chemical crosslinking. The development of organic-inorganic
hybrids as well as superhydrophobic materials will be
highlighted as well as the deployment of BC for nutrient
enrichment and affinity bioseparation. The spectrum of
products based on BC will be finally illustrated in the
development of materials with purposes in art and design,
taking advantage of films and aerogel forms. A common thread
to be discussed was the deployment of surface chemistry
concepts to maximize the intrinsic properties and possible
functions of BC.
The formation of β-cyclodextrin-inclusion complex (IC) with
PLA and the effect of IC on PLA based films were investigated.
Surface morphology, thermal, barrier, and mechanical
properties of the composite films were measured at varying IC
(1, 3, 5, and 7%) concentration and compared with two control
systems: pure PLA film and PLA films incorporating β-CD (1
and 5%). The PLA IC incorporated composite films (IC-PLACFs) had uniform distribution of ICs in the film structure without
signs of ICs agglomeration. In contrast, control films exhibited
β-CDs agglomeration due to poor interfacial interaction
between β-CD and PLA moieties. According to the thermal
property analysis, 5% IC incorporation into PLA matrix
decreased 7-fold the dimensional changes of the IC-PLA-CFs
at the temperature range of 20 to 80oC in contrast to pure PLA
film and it showed significant improvement of on-set
temperature for dimensional change. On the other hand, the βCD-PLA-CFs did not show any improvement in thermal
expansion comparing to the pure PLA film. The glass transition
and crystallization temperature of all composite films were
shifted to the higher temperature region as a function of IC
concentration and the crystallinity of the PLA based composite
films were increased comparing to the pure PLA film due to the
nucleating function of β-CD. All composite films had higher
oxygen and water vapor permeability as IC or β-CD content
increased in comparison to the pure PLA film. PLA-CFs had
lower tensile strength and elongation at break than the pure
PLA film due to the filler character of β-CD and IC. In
conclusion, this study demonstrated that the IC incorporation is
a valuable technique for enhancing the thermal stability of PLA
based films.
CELL 395
Biotechnological valorization of waste sludge in a food
industry: Design and evaluation process at lab scale
Javier M. Naranjo1, [email protected], wilmar osorio
viana2, Angela Merchan1, Laura Gomez1. (1) Environmental
Engineering, Universidad Católica de Manizales, Manizales,
Caldas, Colombia (2) envirnonmental engineering, universidad
catolica de manizales, Manizales, Caldas, Colombia
Water is one of the most important resources used in the food
industry. However, the wastewater generated must be treated
before its final disposal. The main byproduct obtained from an
Industrial Wastewater Treatment Plant (IWWTP) in a food
industry is sludge. The generated sludge is usually a
suspension with high solids content (organic matter). The
correct disposal of these byproduct is an obligation and a
constant need for industries because it implies a cost in
handling, transportation and disposal. Nevertheless, the
traditional management of sludge is their disposition as a
residue (commonly in a landfill or security cells) disregarding
their potential as a raw material. For this reason, the
researches in sludge valorization have grown in the recent
decades looking for clean and sustainable technologies for
utilization, optimization and efficient use of sludge generated
by IWWTP, and a reduction in the operation costs. The sludge
valorization techniques most frequently used are: production of
fertilizers, soil improvement, composting and eco-brick
production. The application of sludge recovery processes can
generate new business lines for the industrial sector improving
its economic viability, reducing their negative environmental
impacts and contributing to the strengthening of its
competitiveness, especially in developing countries. In this
work, a theoretical and experimental study for the valorization
of the industrial sludge (biosolids) obtained from an IWWTP in
a food industry in Manizales city (Colombia) was performed for
obtaining compost for soil improvement. Physicochemical and
microbiological characterizations of sludge were obtained in
order to establish the quality and composition of the sludge
generated, to select properly the treatment and stabilization
and to evaluate experimentally at laboratory scale a
biotechnological alternative for its valorization. Different tests
were applied for the characterization of the sludge samples,
such as: pH, alkalinity, acidity, moisture, ashes, chemical
oxygen demand, biochemical oxygen demand, mesophilic
aerobic microorganisms, molds and yeasts, total and fecal
coliforms, Salmonella sp. As a result, a technological process
was proposed considering the composition and quality of
sludge, the best conditions of composting, and the lower
process cost. This work is an interesting result that can be
applied in different food industries which generate high
quantities of sludge in their IWWTP.
CELL 396
Functionalization of bacterial nanocellulose membranes
with Triticum vulgare for wound dressing applications
Marlon Andres Osorio Delgado1, Isabel Oriz1, Jorge
Velásquez-Cock1, Robin Zuluaga Gallego1,2, Orlando J.
Rojas3, Maria S. Peresin4, Piedad Gañán1,2, Cristina Isabel
Castro Herazo1, [email protected]. (1) Universidad
Pontificia Bolivariana, Medellin, Antioquia, Colombia (2) New
Materials Research Group, Pontificia Bolivariana University,
Medellín, ANT, Colombia (3) Forest Biomaterials, North
Carolina State University, Raleigh, North Carolina, United
States (4) Technical Research Centre of Finland, VTT, Espoo,
Finland
Bacterial nanocellulose (BNC) is a promising biomaterial for
medical applications. Besides its morphology that mimics the
structure of collagen, it is produced at relatively low cost; it is
biocompatible and can be used as a carrier in drug delivery
systems [1–3]. Wound dressing application can be benefited if
BNC is combined with Triticum vulgare aqueous extracts
(TVE), a natural product with well-known stimulating and
healing properties [4,5]. Therefore, we incorporated TVE in
BNC membranes by simple impregnation and evaluated the
behavior of the resultant biomaterial for wound dressing as a
function of TVE loading. The components were characterized
for cyto- and geno-toxicity as well as for their thermomechanical properties, gas permeability, biocompatibility and
morphology (SEM). The results indicate a tensile Young
modulus similar to that of excised human skin (60 to 100 MPa)
[6] and an enhanced thermal behavior of system compared to
the single components. These characteristics make it suitable
as a wound dressing material. Additionally, the microstructure
of BNC based on nanoribbons (50-70 nm) is similar to that of
collagen, which combined with TVE induces human fibroblasts
proliferation
on
the
surface
of
the
biomaterial.
[1] W. Czaja, A. Krystynowicz, S. Bielecki, and R. M. Brown,
“Microbial cellulose-the natural power to heal wounds.,”
Biomaterials, vol. 27, no. 2, pp. 145–51, Jan. 2006.
[2] L. Fu, J. Zhang, and G. Yang, “Present status and
applications of bacterial cellulose-based materials for skin
tissue repair.,” Carbohydr. Polym., vol. 92, no. 2, pp. 1432–42,
Feb. 2013.
[3] M. Kucharzewski, A. Franek, and S. M. Academy, “Topical
treatment of non-healing venous leg ulcers by cellulose
membrane,” Phlebologie, vol. 6, no. 1, pp. 147–151, 2003.
[4] D. A. Vanden Berghe, Q. R. Yang, J. Tott, and A. J.
Vlietinck, “Specific Stimulation of Human Endothelial Cells by
Triticum vulgare Extract and its Biologically Active Fraction,”
Phyther. Res., vol. 7, no. May 1992, pp. 172–178, 1993.
[5] J. J. Coutiño-Mata, J. Cuenca-Pardo, and C. D. J. ÁlvarezDíaz, “Manejo de las áreas donadoras de injertos de piel
tratadas con gasa con Triticum vulgare vs gasa con petrolato,”
Cir. Plast., vol. 12, no. 2, pp. 61–64, 2002.
[6] A. Ní Annaidh, K. Bruyère, M. Destrade, M. D. Gilchrist, and
M. Otténio, “Characterization of the anisotropic mechanical
properties of excised human skin.,” J. Mech. Behav. Biomed.
Mater., vol. 5, no. 1, pp. 139–48, Jan. 2012.
CELL 397
NMR
spectroscopy,
relaxometry,
diffusion,
and
rheological studies of cellulose in the ionic liquid 1-butyl3-methylimidazolium chloride
Michael E. Ries2, [email protected], Tatiana Budtova1,
Asanah Radhi2. (1) CEMEF/Mines ParisTech, Sophia Antipolis,
France (2) Physics and Astronomy, University of Leeds, Leeds,
United Kingdom
Imidazolium-based ionic liquids are low vapour pressure,
powerful cellulose solvents, allowing the dissolving of cellulose
up to 25 wt.%; they are thus very promising solvents for
making fibres, films and aerogels. We have studied cellulose
solutions in the ionic liquid 1-butyl-3-methylimidazolium
chloride (BMIMCl). This system has been investigated using
NMR spectroscopy, diffusion, relaxometry and rheology. Our
set of cellulose concentrations (0, 1, 2, 5, 8 and 10 % w/w)
were examined over a range of temperatures (30 °C to 100
°C).The change in 1H chemical shift, measured at 400 MHz,
revealed that the resonances belonging to the imidazolium ring
had the strongest dependences on cellulose concentration,
with them moving upfield on the addition of cellulose. This is
consistent with the usual explanation for the dissolution of
cellulose by this IL, in which the Cl anion preferentially leaves
the cation to break the inter- and intra- hydrogen bonds of the
cellulose chains. NMR relaxometry was carried out both at high
field (400 MHz) and low field (20 MHz). At high field the
relaxation times measured showed a weak dependence on
cellulose concentration, indicating that fast local reorientations
of the protons (timescale ~ 1 / 400 MHz) were not affected by
the dissolution of cellulose. Conversely, the low field relaxation
times were significantly altered on the addition of the
carbohydrate. The dependences of the spin-lattice and spinspin relaxations from these low field experiments were found to
be well-described by the classic Bloembergen-Purcell-Pound
theory. From this analysis a rotational correlation time for the
cation as a function of temperature and cellulose concentration
was determined. Rotational correlation times from the low field
NMR relaxometry tauc were combined with the NMR diffusion
D and viscosity data showing that the Stokes-Einstein-Debye
formulae correctly relate these parameters, see the Figure
below. From this analysis a microviscosity for the ions was
determined.
CELL 398
Dissolution, regeneration, and characterization
cellulose and cellulose/chitin in ionic liquid
of
Poorna
T.
Wansapura,
[email protected],
Noureddine Abidi, Tanya Jackson, Yang Hu, Edward L.
Quitevis. Texas Tech University, Lubbock, Texas, United
States
Cellulose is considered the most abundant natural polymer on
earth. Its insolubility in water and in most organic solvents
limits its application for the preparation of new biomaterials. In
this research, we report on the dissolution and regeneration of
cellulose in ionic liquid 1-butyl-3-methylimidazolium chloride
(BMimCl). Microcrystalline cellulose and cellulose from cotton
fibers were used in this research. Pre-treatment with
microwave plasma was used to investigate its effect in
enhancing the solubility. The objective of plasma treatment is
to cleave bonds and facilitate the diffusion of the ionic liquid
between the cellulose macromolecule chains for effective
dissolution. The preparation of “bio-component” regenerated
fiber (cellulose-chitin) was also investigated. The regenerated
biomaterials (cellulose and cellulose-chitin) were characterized
using Scanning electron microscopy, Fourier Transform
infrared
spectroscopy,
wide-angle
X-ray
diffraction,
thermogravimetric analysis.
electrostatic charge is delocalized and with melting points
below 100 ºC. Because of the vast number of possible
chemical structures and molecular interactions, the
macroscopic properties of ILs can be tailored for specific
applications, in particular, for the dissolution of cellulose. In this
talk we will describe recent work in our laboratories in the
development of ILs that can both dissolve cellulose and
exfoliate graphene. The ultimate goal of these studies is the
development of processes for the fabrication of cellulosegraphene composite materials. It is well known that ILs with
basic anions are able to break up the strong hydrogen bonds in
cellulose. We have recently shown that aralkylimidazolium
based ILs can exfoliate graphene without covalent
functionalization or an additive stabilizer (Bari et al., Coll. Surf.
A, 2014, 463, 63-69). DFT calculations indicate that π-π
interactions between graphene and the aromatic groups on the
cation help stabilize graphene-IL dispersions. We find that ILs,
formed by combining aralkylimidazolium cations with basic
anions, can exfoliate graphene to form stable graphene-ILs
dispersions and also dissolve microcrystalline cellulose Iβ. Xray diffraction indicates that the cellulose regenerated by the
addition of water to the cellulose-IL solutions is cellulose II.
CELL 400
Application of two-stage ionic liquid-mediated system for
cellulose nanocrystals (CNCs) production
Jia Mao, [email protected]. Chair of Forest Biomaterials,
University of Freiburg, Werthmannstr. 6, 79085, Freiburg,
Germany
Concentrated acid-catalyzed hydrolysis is the most common
method for producing CNCs from cellulosic sources. This
production route is however limited by the large consumption
of corrosive acids and the low reaction yield. In this
presentation, we demonstrate that CNCs can be obtained in a
maximum theoretical yield using a mild two-stage hydrolysis
system based on the ionic liquid (IL) 1-butyl-3methylimidazolium hydrogen sulfate. The presentation includes
a thorough chemical investigation of reaction efficiency and
CNC properties in addition to the optimization of this novel ILbased route for three cellulosic materials viz. microcrystalline
cellulose (MCC), bleached softwood (Scots Pine, Pinus
Sylvestris) and bleached hardwood (Birch, Betula) kraft pulp
fibers. Finally, this method is explored for the extraction of
CNCs from deinking reject pulp.
CELL 399
CELL 401
Dissolution of cellulose and exfoliation of graphene by
aralkylimidazolium-based ionic liquids
Eshan Gurung2, Kayla Mendoza2, George Tamas2, Rozana
Bari4, Tanya Jackson5,3, Poorna T. Wansapurna5,3, Micah
Green1, Noureddine Abidi3,5, Edward L. Quitevis2,
[email protected]. (1) Chemical Engineering, Texas
A&M University, College Station, Texas, United States (2)
Chemistry & Biochemistry, Texas Tech University, Lubbock,
Texas, United States (3) Fiber & Biopolymer Research
Institute, Texas Tech University, Lubbock, Texas, United
States (4) Chemical Engineering, Texas Tech University,
Lubbock, Texas, United States (5) Plant & Soil Sciences,
Texas Tech University, Lubbock, Texas, United States
Ionic liquids (ILs) are organic salts comprised of large ions with
flexible and asymmetric molecular structures in which the
Synthesis of ionic
lignocellulosic waste
liquids
for
pretreatment
of
Alejandro Camacho-Dávila1, Victor Martínez-Burciaga1,
[email protected],
Gabriel
I.
Israel-Orozco1,
[email protected], Salvador Rubio-Perea2, Guillermo
González-Sánchez2, Lourdes Ballinas-Casarrubias1, Luis
Villanueva1, [email protected]. (1) Universidad Autonoma
De Chihuahua, Chihuahua, Mexico (2) CIMAV, Chihuahua,
Chihuahua, Mexico
Agro industrial wastes are produced annually worldwide
causing an important environmental impact. In our country
sawmills produce around 3.9 millions of cubic meters per year,
generating 100 tons of waste. Sawdust is the main sub-product
of this activity, and it is commonly disposed in the environment
without control. It is composed mainly of cellulose,
hemicellulose and lignin, thus it can be treated to recuperate
these biopolymers. The principal objective is to remove
hemicellulose and lignin, while simultaneously keeping
cellulose unaltered. In the traditional methods, huge quantities
of toxic chemicals may be produced, such as in kraft, sulfite
and soda treatments. The recent restrictions derived from
environmental laws, and the full assessment of chemical
effects, have emphasized the development of alternative
procedures for biomass conversion. Ionic liquids (ILS) have
been widely studied in the last years, as a very attractive
alternative for green chemistry. They are molten salts which
have very attractive characteristics such as wide temperature
of operation, high solubility of many organic materials, and low
vapor pressure at low temperatures, among other properties.
In this work the principal objective was the synthesis of three
different ionic liquids and their assessment as dissolving media
for lignocellulosic waste. The Bmim Cl and Amim Cl ionic
liquids were synthesized by different reported routes, as well
the Bmim Aco, using sodium and silver acetates. The reactions
were
as
follows
in
the
adjunct
image.
The different calculated yields for ILS synthesis were from 6097%. RMN and FTIR spectra evidence ILS structures. The ILS
without further purification were assessed for cellulose
recovery from sawdust dissolving at 30° C during one hour.
HPLC analysis of sugar fractions, obtained after sulfuric acid
hydrolysis, were from 60-80% for cellulose in the solid fraction.
In the solid fraction, no hemicellulose was evidenced and less
of 10% of lignin was obtained.
World is continuously increasing and has to be provided by
textiles for clothing and plastic consumables. Dissolving pulp is
a high purity cellulose pulp which is the raw material for many
value added products such as textiles and cellulose esters and
ethers, which are used to produce fibers, films, filters etc. For
establishing future paper pulp based biorefineries, the
decreasing need for paper pulp can be combined with the
increasing demand for dissolving pulp. IONCELL-P is a
modern fractionation method using ionic liquids (IL) and water
to upgrade the hemicellulose rich paper pulp to high purity
dissolving pulp and coproduce polymeric hemicellulose without
yield losses. Understanding the effect of chosen fractionation
parameters and the mechanism of the fractionation is crucial to
design more complex business cases where the ILs can be
utilized in multiple process steps (for example: IONCELL-P
fractionation then spinning with IONCELL-F, an IL based fiber
spinning technology). Eventually in a well-designed process
the IL can be recycled from many different applications in a
combined recycling system. The effect of different raw
material, used IL and applied water content is already known.
To understand the mechanism of the fractionation, pure
polysaccharides were fractionated with the IONCELL-P. The
molecular weight distribution of the polysaccharide fractions
could be tuned by the amount of water used in the
fractionation. This also gives a new perspective on how to
further improve IL-water based fractionations.
CELL 403
Optimization of a low temperature
pretreatment process using ionic liquids
lignocellulosic
Constance Schall, [email protected], Samira
Vasheghani Farahani. Univ of Toledo, Toledo, Ohio, United
States
CELL 402
From paper pulp tp dissolving pulp to textile fibres with
ionic liquids using IONCELL-P&F
Agnes M. Stepan, [email protected]. Department of
Forest Products Technology, Aalto University, Espoo, Finland
In recent years with the 21st century´s digital revolution the
global demand for paper has started to decrease in the
developed countries. On the other hand the population of the
Terrestrial biomass (lignocellulosic material) is composed of
three major components: cellulose, a highly crystalline polymer
of glucose; hemicellulose, a complex polymer of xylose and
other sugar derivatives; and lignin, a polyphenyl propanoid
macromolecular assembly that is covalently cross-linked to
hemicellulose. The components of biomass can serve as a
source of carbon based feedstock for fuel and chemical
production in much the same way that crude oil serves as the
carbon feedstock in petrochemical refineries. In particular, the
sugars derived from the cellulosic and hemicellulosic portions
of biomass can be converted to value added chemicals
through a sugar platform. Due to the structural complexity of
lignocellulosic biomass and the inaccessibility of biomass
polysaccharides to water and catalysts, extremely slow
hydrolysis rates result. In particular, the high crystallinity of
cellulose in native biomass, while imparting structural integrity
and mechanical strength to the material, renders it
recalcitrance towards hydrolysis. These slow hydrolysis rates
have been increased by pretreatment of biomass with ionic at
temperatures typically ranging between 120 and 160°C. In the
studies presented, room temperature pre-processing is
coupled with ionic liquid incubation (IL) at low temperatures
ranging between 30 and 50°C, producing an easily
hydrolysable cellulosic substrate at dramatically lower
incubation temperatures. Moreover, by altering the IL
displacement solvents, this method can be tuned to retain or
reject biomass components from the IL phase, providing a
potential method for separation of hexose and pentose sugars.
CELL 404
Removal of the aqueous washing treatment aid ionic
fixative from paper
CELL 405
Analysis of paper surviving from a tragic scene
Julia Roller, [email protected]. Staatliche Akademie der
Bildenden Künste Stuttgart, Stuttgart, Germany
The ionic fixatives Rewin®EL and Mesitol®NBS are in
established use to prevent bleeding of water-sensitive media
during aqueous treatment. Their single or combined application
varies among practitioners, also with regard to the inclusion
and intensity of any subsequent rinsing. Lack of rinsing and
local fixative application is known to risk paper discoloration.
This contribution studies the function of aqueous rinsing
subsequent to fixative application to avoid these side effects
and optimize the treated paper's future stability. For the first
time it examines whether and how effectively subsequent
rinsing steps benefit the fixative-treated paper, in particular:
diminish fixative residues; diminish discoloration formation;
benefit cellulose aging with respect to oxidative and hydrolytic
degradation; change the paper's electrostatic load caused by
fixative residues. Experimental results on 119 treated and
artificially aged test papers show that rinsing is of importance
for diminishing the residue and thereby any negative effect of
remaining fixatives on the stability of the paper. Rewin® EL
residues showed negative side effects; Mesitol®NBS had no
negative, and may have a positive effect on the paper
condition. In conclusion, one 15-min aqueous rinse is the
minimum required, while three 10-min rinses are
recommended when using the fixatives on paper objects.
Kyujin Ahn, [email protected], Thomas Zweckmair,
Andreas Schedl, Antje Potthast. Chemistry, BOKU Vienna,
Vienna, Austria
Paper substrates are highly vulnerable to catastrophic events
such as flooding and fire as well as vandalism. Physical
damage and partial losses of the paper objects are generally
unavoidable due to such events, and thus conservation
treatments are usually mandatory. As physical deterioration of
the paper is severe in that case, its chemical properties are
recognized less important in general. However, it is valuable to
understand chemical changes of the paper substrates induced
by a disaster for better preservation and for a judgment to
which extent the conservation treatment has to be performed.
In the present study, we have obtained a rag paper object
which partially survived from a fire and analyzed its chemical
properties by means of various analytical methods. The
molecular status of the cellulose as well as low molar mass
degradation products were measured. As many of the applied
analytical methods (SEC, GCMS, DESI-MS), required only
micro-sampling, we could perform mapping of the object by
various chemical parameters. Comparison to an identical
duplicate provided a more profound understanding of chemical
changes in the event of fire. Hence, benefits and limits of
conservation treatment can be discussed.
CELL 406
Dyes used by Iranian masters in paper dyeing process
based on Persian medieval recipes
Mandana Barkeshli1,2, [email protected]. (1)
Department of Applied Arts and Design, International Islamic
University Malaysia, Kuala Lumpur, selangor Darul Ihsan,
Malaysia (2) Chairman of The Islamic Manuscript Association ,
United Kingdom, Cambridge, Malaysia
During Taimurid and Safawid to Qajar periods the Iranian
masters introduced number of dyes under categories of
primary, secondary and mixed colors in dying process of paper
to prepare suitable support for purpose of calligraphy and
paintings. In this paper complete historical analysis is carried
out to identify different types of dyes, shade of colors used,
and the application of techniques recommended in paper
dyeing process based on Persian medieval recipes.
To accomplish this, 19 manuscripts have been selected from
13th to 19th century and studied in full detail; the recipe from
each manuscript has been extracted according to each color
while the materials and techniques are also categorized and
compared thoroughly. For easy reference, different types of
materials and techniques used in each color including dyes,
minerals, mordents and acids used for preparation of each dye
have been described separately with reference to the related
treatises and their respective authors.
CELL 407
Damage caused by iron ions or pigments (Prussian blue)
during aging of Japanese paper
Keiko Kida3, [email protected], Masamitsu Inaba2, Antje
Potthast1, Noriko Hayakawa3. (1) Chemistry / renewable
resources, BOKU Vienna, Vienna, Austria (2) Conservation
Science, Tokyo University of the arts, Taito-ku, Tokyo, Japan
(3) Center for Conservation Science and Restoration
Techniques, National Research Institute for Cultural
Properties, Tokyo, Taito-ku, Tokyo, Japan
Paper is often damaged by ink or pigments containing
transition metal ions. The damage of artificially aged kozo
paper (Japanese paper) by iron ions or Prussian blue pigments
(iron ferrocyanide) was studied. The degradation induced by
iron ions is suggested to be a synergistic process comprising
both hydrolytic and oxidative reactions. The degradation state
of the cellulose polymer in kozo paper was investigated using
fluorescence labeling of carbonyl and carboxyl groups in
combination with GPC-MALLS. In addition to cellulose, kozo
paper contains a relatively high amount of hemicellulose which
was investigated by determination of uronic acids and neutral
carbohydrates.
Iron ions caused a decrease of the weight average of
molecular weight (Mw) of kozo paper and an increase in the
amount of carbonyl groups owing to the oxidative reactions
that occur in kozo paper over the aging time; however the
amount of carboxyl groups was observed to decrease as
shown in Fig. 1. Pigments were observed to cause similar, but
less severe, damage in kozo paper. A decrease in the amount
of uronic acid from the hemicellulose in kozo paper is
considered to be the dominant factor in the observed decrease
of carboxyl groups, as the oxidative reaction would increase
the amount of carboxyl groups. The amount of both uronic acid
and xylose from hemicellulose was influenced by iron ions over
the aging time, indicating the decomposition of hemicellulose.
This result suggested that the hemicellulose in kozo paper was
affected first and prevented the hydrolytic and oxidative
degradation of cellulose, which might enable kozo paper to last
a long time.
Fig. 1 The amount of carboxyl groups in kozo paper over the aging
time(80 , 65%rh), Ku: untreated, Ki: iron ferrocyanide treated, Khs:
H2SO4 treated, Ks: FeSO4 treated, Kc: FeCl3 treated
CELL 408
Stabilization of green copper based pigments
Jasna Malešič1, [email protected], Jana Kolar2,
Manfred Anders3. (1) Conservation and Preservation, National
and university library, Ljubljana, Slovenia (2) Morana RTD,
Ivančna Gorica, Slovenia (3) Zentrum für Bucherhaltung
GmbH, Leipzig, Germany
Copper ions and acids in pigments, such as verdigris and
malachite lead to enhanced degradation of the paper carrier.
Stabilization treatment should therefore include addition of
alkalis to combat acid hydrolysis of cellulose and antioxidants
to retard oxidative degradation catalyzed by copper ions. In the
proposed paper, treatments used by conservators for
stabilization of papers containing green copper based
pigments will be reviewed. Furthermore, two recently proposed
treatments containing antioxidant tetrabutylammonium bromide
and calcium carbonate will be evaluated. The first treatment is
based on interleaving of paper samples containing malachite
or verdigris pigments, with papers, impregnated with alkaline
buffer and antioxidant at elevated relative humidity and applied
pressure. The second one is based on the use of non-aqueous
suspensions of nano-calcium carbonate particles and
tetrabutylammonium bromide. The results of the ageing
behavior of the paper samples containing verdigris and
malachite pigments exposed to artificial thermal ageing,
followed by the determination of the molecular weight
distribution by size exclusion chromatography (SEC) and the
changes of color by colorimetry will be presented and
discussed.
CELL 409
Electron paramagnetic resonance as a probe for metal
ions and radicals in paper
Alfonso Zoleo, [email protected], Maddalena Bronzato.
Department of Chemical Sciences, University of Padova,
Padova, Italy
Electron Paramagnetic Resonance (EPR) is a technique
devoted to the identification and characterization of
paramagnetic species, i.e. chemical species with unpaired
electrons. Very common paramagnetic species which can be
detected through EPR in ancient and modern paper are the
ions Fe(III), Mn(II), Cu(II) and radicals, where Fe(III), Cu(II) and
radicals play a relevant role in paper degradation. Specifically,
Fe(III) is almost ubiquitous in ancient paper. Here we propose
an overview of the EPR signals in ancient, modern and
artificially aged paper, and how they are related to interesting
features of the paper, such as degradation, paper origin, and
oxidation level. We show how the technique can be combined
with other techniques to provide detailed indications to
characterize ancient and artificially aged paper.
CELL 411
Biomass supply chain innovation: A case study
Sam Jackson, [email protected]. Genera Energy
Inc., Vonore, Tennessee, United States
Paramagnetic species EPR-detected in ancient paper
CELL 410
German Leading-Edge cluster "Bio-Economy" as an
example of a modern innovation strategy
Rainer M. Busch, [email protected]. Self employed, BadenBaden, Baden-Wuerttemberg, Germany
One of the most common gaps in the innovation process is
known as 'The Valley of Death'. Risks associated with earlystage (unproven and proven technologies) and middle-stage
(pre-commercial) technologies are by private investors seen as
too risky, and are therefore often not funded. The problem for
the developers is that the technologies at these stages are too
advanced in their development to qualify for public research
and development subsidies or other types of financial support a further problem may be that the capital required is larger than
what the government finance programmes can provide. On the
other hand, the company is too new and unproven to receive
private financing. The Leading Edge cluster “Bio-Economy”,
which is one of the five winners of the German Leading Edge
cluster competition in 2012, connects all economical branches
which are relevant for a bio-economy such as agriculture and
forestry, construction, pulp and paper and chemical and
plastics processing industry. Accompanied by service
providers, enterprises and research organisation from these
branches, the cluster Bio-Economy for the first time reflects
innovation and value chains in a bio-economy across branch
borders. The cluster strives primarily for the material usage of
beech wood with high value creation (wood as a material of
construction and as a raw material for the chemical industry),
supplemented by the energetic usage of the residues. The
following high-level strategic goals are being followed:
• To sustainably maximize value creation of non-food biomass
through coupled production and cascaded utilisation in order to
generate chemicals, new materials and energy. To speed up
innovation through the integrated, temporally and spatially
coordinated up-scaling of processes and plants from laboratory
to demonstration and industrial scale. The cluster’s two
technical centres are located in Rottleberode in the Harz area
und around the Fraunhofer Chemical & Biotechnological
Process Centre in Leuna. The presentation will show how the
cluster realizes its strategies in practice.
An efficient and optimized feedstock solution requires tight
integration of all elements of the biomass supply chain. Genera
Energy has focused on developing front to back, integrated
supply chain solutions to benefit the entire biobased industry.
The company works to optimize crop portfolio selection and
production as well as downstream operations including
harvesting, logistics, storage, and preprocessing. Through
continuous innovation, Genera has developed industry leading
best practices for feedstock logistics. Selecting, producing, and
harvesting a type of biomass crop or residue is a complex
operation and should be given due diligence in any supply
chain. Genera has developed innovative and practical
agronomic systems to produce a wide array of energy crops.
However, post-harvest activities are often an undervalued part
of the feedstock supply chain. Once biomass is harvested, the
biomass supply chain becomes a unique inventory
management system. This system includes the management
of equipment, capital and labor requirements associated with
storage and transportation; timing and quality management in
storage; managing and scheduling pickup, as well as transport
and delivery logistics. All feedstocks are subject to physical
material and quality losses which inevitably leads to economic
losses. Paying close attention to the key contributors of
material loss as well as other inefficiencies in the supply chain
will make sure that your inventory management does not
negatively contribute to the bottom line. Inventory management
is followed by feedstock preprocessing. Variable crops from
the field must be converted into uniform format feedstocks.
Preprocessing is driven by three primary feedstock
characteristics: moisture, bulk density, and flowability.
Feedstock quality management is critical to achieve maximum
throughput of grinding equipment and to reduce energy
consumption. Genera Energy and its partners at its Biomass
Innovation Park, have developed systems that allow for
flexibility in feedstock characteristics during processing while
delivering a uniform product to the customer. Addressing these
issues is a very critical component to successfully processing
biomass.
CELL 412
European Polysaccharide Network of Excellence (EPNOE)
Pedro E. Fardim1, [email protected], Jan van Dam2. (1) Abo
Akademi University, Turku, Finland (2) Agrotechnology &
Food, Wageningen University and Research Centre,
Wageningen, Germany
EPNOE (European Polysaccharide Network of Excellence) is a
research, education and knowledge transfer network that
connects companies (from large multinational to SME’s)
focusing on all areas where polysaccharide and
polysaccharide-related products are used and academic and
research institutions working or interested in polysaccharides.
EPNOE’s main missions are: to offer a networking platform
enabling close interactions between members in order to
favour innovation, boost knowledge transfer and organise R&D
activities in a totally confidential manner; to organise basic and
applied research for the study of fundamental concepts, the
testing of new ideas and the development of new products
based on or containing polysaccharides; to organise education
in polysaccharide science at the level of continuing education
for companies and of post-graduate students and post-docs.
More information about EPNOE is available at www.epnoe.eu.
Finnish bioeconomy cluster
Pedro E. Fardim1, [email protected], Markku Leskela2. (1) Abo
Akademi University, Turku, Finland (2) University of Helsinki,
Helsinki, Finland
CELL 413
Sun Grant Initiative: Bringing a regional focus to a
national opportunity
Timothy G. Rials, [email protected]. The University
Tennessee, Knoxville, Tennessee, United States
CELL 415
of
The Sun Grant Initiative (SGI) addresses national bioenergy
production goals through multidisciplinary research programs
that reflect regional differences in biomass production
capabilities. Working closely with federal agencies (USDA,
DOE, and DOT), the five Sun Grant Centers and the Pacific
Subcenter coordinate their respective activities at the national
level. Each SGI region awards funds through a competitive
grants process, with scientific merit review of the proposals to
ensure that the highest quality science is being conducted. In
partnership with the Department of Energy’s Bioenergy
Technology Office, Sun Grant has also coordinated a major
research program that has advanced the science and
technology of feedstock production from major biomass
sources. The Regional Feedstock Partnership has reviewed
existing biomass productivity data, provided new information
on growth and yield from coordinated field trials, and generated
valuable insights into sustainable practices for agricultural
residue removal. This presentation will highlight the value of
the land-grant university system and discuss the Sun Grant
Initiative’s impact on the nation’s goal to reduce its
dependence on petroleum.
CELL 414
Interregional Scientific/Industrial Centre (BIO)-PolymersMaterials-Technologies for Economy, POLINTEGRA, as a
model of cooperation between business and science
Danuta Ciechanska, [email protected]. Managment,
Insitute of Biopolymers and Chemical Fibres, Lodz, Poland
Three Polish research institutes, Institute of Biopolymers and
Chemical Fibres (Łódź), Institute of Heavy Organic Synthesis
"Blachownia" (Kędzierzyn-Koźle) and Industrial Chemistry
Research Institute (Warsaw) the Scientific/Industrial Centre
took the initiative to create a network called “(BIO)-PolymersMaterials- Technologies for Economy, in short POLINTEGRA.
It will be a network gathering business organizations
(companies, consulting, etc.), research institutes, institutes of
the Polish Academy of Sciences and university research
centers. POLINTEGRA will provide the right forum for an
effective cooperation between scientific entities and
entrepreneurs. POLINTEGRA is a permanent consortium
aimed at developing R & D projects focused on several
designated research areas. 33 research units and 29 business
organizations are members of the Centre. The essential tasks
of the Centre are to develop partner’s competences as well as
supporting and coordinating their activities, building common
research projects as within Horizon 2020 and coordinating
activity towards technology transfer and innovation.
Finnish Bioeconomy Cluster FIBIC is one of six Strategic
Centers for science, technology and innovation in Finland
(SHOK). The aim of FIBIC is to turn science and technology
into sustainable bio-based solutions. We offer businesses and
research organizations a new way of engaging in close, longterm cooperation and leveraging the best competences and
resources. FIBIC combines research and companies for
innovative solutions. We believe in a more innovative,
resource-efficient and competitive society. We are accelerating
Finland to become a pioneer in the sustainable bioeconomy.
Research programs are the core FIBIC’s activities. Our ongoing research programs are related to the development of
intelligent and resource-efficient processes, future biorefineries
and bioenergy solutions. More information about FIBIC is
available at www.fibic.fi.
CELL 416
4D product: Integration over time is the only way to
understand sustainability
Mark E. Jones, [email protected]. R&D, The Dow Chemical
Company, Midland, Michigan, United States
You can’t know whether a product is sustainable just by
looking. Feedstock choice is an important part of determining
sustainability, but is only one part of determination.
Sustainability is a question of time, integrating knowledge of
production, use and end-of-life. Far too often, hype has
surpassed reality, boundary conditions have been neglected
and actions are taken that don’t truly lead to a sustainable
future. Singular focus on attributes like renewable content or
biodegradability can give the wrong answer. Quality
engineering, with attention to energy and material flows,
energy return, and thermodynamic constraints must be
considered. Products of the chemical industry create
sustainable solutions through direct energy savings or by being
significantly better than the next alternatives during use.