ACHIEVEMENTS IN GREEN SAMPLE
PREPARATION FOR THE GAS
CHROMATOGAPHIC DETERMINANTION
OF ORGANIC ENVIRONMENTAL
POLLUTANTS
Agata Spietelun1, Adam Kloskowski1, Michał Pilarczyk1,
Jacek Namieśnik2
1Department
of Physical Chemistry
of Analytical Chemistry
Faculty of Chemistry
Gdańsk University of Technology
G. Narutowicza Str. 11/12
80-233 Gdańsk, Poland
Tel: (058) 347 1010
E-mail: [email protected]
2Department
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Green Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia
FURTHER CHALLENGES OF ANALYTICAL CHEMISTRY
accurately monitoring the state of the environment and
the processes taking place in it
determining an wide range of analytes, often present in
trace and ultratrace amounts in sample matrices with
complex or variable compositions
need to introduce to analytical practice new
methodologies and equipment in order to comply with
the principles of sustainable development and green
chemistry
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Green Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia
(SHORT HISTORY)
GREEN CHEMISTRY
2003
the GREEN CHEMISTRY INSTITUTE (EPA)
came into being in the USA. It fosters contacts
between governmental agencies and industrial
corporations on the one hand, and university
research centres on the other
1997
IUPAC Working Party on Green Chemistry
founded
1996
1995
Paul Anastas coined the term GREEN
CHEMISTRY in the ‘Green Chemistry
Program’, inaugurated by the US EPA in
1991
the first national conference devoted to
GREEN CHEMISTRY took place in Poland
– EkoChemTech’03
the first international GREEN CHEMISTRY
symposium took place
an annual award was established for
achievements in the application of GREEN
CHEMISTRY principles
1991
Green Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia
GREEN CHEMISTRY
PRINCIPLES of GREEN CHEMISTRY (P.T. Anastas,
J. Warner, Green Chemistry. Theory and Practice, Oxford
University Press, New York, 1998, p. 30)
PRINCIPLES of GREEN CHEMICAL TECHNOLOGY
(N. Winterton, Green Chem., 3, G 73 (2001))
PRINCIPLES of GREEN CHEMICAL ENGINEERING
(P.T. Anastas, J.B. Zimmerman, Design through the Twelve
Principles of Green Engineering, Environ. Sci.Technol., 37,
5, 94A-101A, (2003).)
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Green Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia
GREEN CHEMISTRY
‘Green chemistry, is the invention, design and application of chemical
products and processes to reduce or to eliminate the use and
generation of hazardous substances’
P. T. Anastas, J. C. Warner, Green Chemistry: Theory and Praktice. Oxford Science Publications, Oxford (1998)
GREEN ANALYTICAL CHEMISTRY-GAC
‘The use of analytical chemistry techniques and methodologies that
reduce or eliminate solvents, reagents, preservatives, and other
chemicals that are hazardous to human health or the environment and
that also may enable faster and more energy efficient analyses
without compromising required performance criteria’
H. K. Lawrence, Green Analytical Methodology Curriculum
http://www.chemistshelpingchemists.org/GreenAnalyticalMethodologyCurriculum.ppt#257,2,Curriculum
Green Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia
5
PUBLICATIONS ON GREEN ANALYTICAL CHEMISTRY
200
Ourestimation
estimation
Our
Cumulative number of publications
250
150
100
50
0
1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2011
Year of publication
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Green Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia
GREEN ANALYTICAL CHEMISTRY- GAC
solvent-free sample
preparation techniques
green solvents
and reagents
reduced scale of analytical
operations
application of agents
enhancing the efficiency
of specific operations
reduced time delay in
obtaining reliable
analytical information
reduced professional
exposure of analytical
chemists
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Green Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia
EVALUATING THE ENVIRONMENTAL IMPACT OF ANALYTICAL PROCEDURES
TOOLS:
Life Cycle Assessment (LCA)1
Eco- Scale2
Eco-Compass3
Consoli, F., D. Allen, R. Weston, I. Boustead, J. Fava, W. Franklin, A. Jensen, N. de Oude, R. Parrish, R. Perriman, D.
Postlethwaite, B. Quay, J. Séguin and B. Vigon., ‘Guidelines for life cycle assessment: A ‘Code of practice’, SETAC, Brussels
and Pensacola, 1993.
1
Aken K., L. Strekowski, L. Patiny, EcoScale, a semi-quantitative tool to select an organic preparation based on economical
and ecological parameters, Beilstein J. Org. Chem. 2, 3, 2006.
2
3 “Home
Sustainability Assessment”, http://www.ecocompass.com.au/
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Green Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia
DIFFERENT LEVELS OF EVALUATING THE GREEN CHARACTER OF ANALYTICAL ACTIVITIES
Comparative evaluation of the environmental
impact of:
solvents and reagents;
agents enhancing efficiency of analytical work;
analytical instruments and whole protocols used for
the same purposes;
whole analytical laboratories of course working in
the same area.
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Green Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia
NO SAMPLE PRETREATMENT
BEFORE ANALYSIS NECESSARY
AN IDEAL SOLUTION
BUT:
• only a limited number of such techniques!
• new ones are not to be expected in the near
future
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Green Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia
KNOWN TYPES OF DIRECT MEASUREMENT TECHNIQUES
 Potentiometric techniques (ion-selective electrodes- ISE)
 Flameless atomic absorption spectrometry
(in a graphite cuvette)
 Inductively coupled plasma emission spectrometry (ICP)
 Neutron activation analysis (NAA)
 X-ray fluorescence spectrometry (XRF)
 Surface analysis techniques (AES, ESCA, SIMS, ISS)
 Immunoassay (IMA)
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Green Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia
SOLVENTLESS (SOLVENT‐FREE) SAMPLE PREPARATION TECHNIQUES
preconcentration of an analyte to a level above
the limit of detection of the measuringmonitoring instrument
removal of interferents, which may affect
analyte identification and determination
simplification of the sample matrix
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Green Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia
CLASSIFICATION OF SOLVENT‐FREE SAMPLE PREPARATION TECHNIQUES
SOLVENT-FREE SAMPLE PREPARATION TECHNIQUES
Application of stream
of inert gas as extractant
Solid phase extraction techniques
with thermal desorption:
Membrane extraction techniques
Static Headspace analysis (S-HS)
Purge and Trap (PT)
Membrane Inlet Mass Spectrometry (MMS)
Dynamic Headspace (D-HS)
Closed Loop Stripping Analysis (CLSA)
Membrane Extraction with Sorbent Interface (MESI)
Cryotrapping (CT)
Gum-Phase Extraction (GPE)
Hollow Fibre Sampling Analysis (HFSA)
Inside Needle Dynamic Extraction (INDEX)
On-line Membrane Extraction Microtrap (OLMEM)
Inside Needle Capillary Absorption Trap (INCAT)
Membrane Purge and Trap (MPT)
Stir Bar Sorptive Extraction (SBSE)
Pulse Introduction Membrane Extraction (PIME)
Headspace Sorptive Extraction (HHSE)
Semi Permeable Membrane Devices (SPMD)
Open-Tubular Trapping (OTT)
Thermal Membrane Desorption Application (TMDA)
Coated Capillary Microextraction (CCME)
Passive permeation dosimeters+thermal desorption
Thick Film Open Tabular Trap (TFOT)
Thick Film Capillary Trap (TFCT)
Solid-Phase Microextraction (SPME)
Supercritical Fluid Extraction SFE
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Green Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia
POSSIBLE APPLICATION OF SUBCRITICAL WATER AS AN EXTRACTANT
DIFFICULT NON-POLAR
EASY
POLAR
PCB
PAH
Organohalogen pesticides
Monoterpenes
Triazines and organonitrogen
pesticides
Explosives (HMX, RDX, TNT)
Phenols, amines
280oC
100oC
S.B. Hawthorne, A. Kubatowa, Hot (subcritical) water extraction, in: Sampling and sample preparation for field
and laboratory collective work, edited by J. Pawliszyn), Elsevier, 2002, pp. 587-608
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Green Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia
IONIC LIQUIDS – SOLVENTS OF THE 21ST CENTURY
IONIC LIQUIDS are salts containing:
• an organic cation;
• an anion (usually inorganic).
Terminology
•room-temperature ionic liquid (RTIL);
•non-aqueous ionic liquid;
•molten salt;
•liquid organic salt;
•fused salt
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Green Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia
INTERESTING AND PROMISING
PROPERTIES OF IONIC LIQUIDS
 at room temperature these salts are liquids;
 dissolve both inorganic and organic compounds;
 are thermally stable: their boiling points are high, often >
350°C;
 usually immiscible with water;
 are non-volatile (very low vapour pressure at 25°C);
 dissolve catalysts, especially complexes of transition metals;
 without simultaneously damaging the walls of glass or steel
reactors
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Green Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia
ANALYTICAL APPLICATION OF IONIC
LIQUIDS
Extraction techniques
A promising extraction medium
Gas chromatography
stationary phases (independently or as an
addition to silica beds)
Electrophoresis
Non-aqueous solutions
Micellar Electrokinetic
Chromatography
Buffer solution modifier
Mass spectrometry
(MALDI-MS, ESI-MS)
Spectroscopic techniques (UV,IR)
solvents with good solvation properties for both
polar and nonpolar compounds
Electrochemical techniques
(sensors)
important properties:
- high electrical conductance,
- wide electrochemical window,
- chemical and thermal stability,
- low vapour pressure
Atomic spectroscopy (ICP-AES)
Enhances sample nebulization
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Green Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia
SOLID‐PHASE DYNAMIC EXTRACTION (SPDE)
PRINCIPLE:
analytes are accumulated in the polymer coating of the inner
needle wall by pulling in and pushing out a fixed volume of air
to be sampled, through the gas-tight syringe for an
appropriate number of times within a fixed time. The vapour
pressure flowing over the accumulating phase layer is
continuously renewed.
The trapped analytes are recovered by thermal desorption
and analysed by GC or GC-MS
ADVANTAGES:
 Rapid and efficient sample enrichment
 Interfaces with any CombiPAL System, controlled by all
major GC/GC-MS
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Green Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia
INSIDE NEEDLE DYNAMIC EXTRACTION (INDEX)
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SOLID PHASE NANOEXTRACTION (SPNE)
PRINCIPLE:
Makes use of the strong affinity of PAHs for gold nanoparticles
IMPLEMENTATION:
Liquid samples (water) of volume ca 500 μl (!!!) are mixed with a colloidal
solution of gold. This is followed by the quantitative binding of PAH analytes to
the surface of gold nanoparticles, which are then removed in an ultracentrifuge
FINAL DETERMINATION TECHNIQUE:
HPLC-FD (fluorescence detector)
DETERMINATION OF PAH ANALYTES IN WATER POSSIBLE
AT THE PPB-PPT LEVEL
H.Wang, A.D. Campiglia, Anal. Chem., 80, 8202-8209 (2008)
Green Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia
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SOLID PHASE MICROEXTRACTION (SPME)
Construction:
1.
2.
3.
4.
5.
Plunger
Barrel
Injection needle
Inner needle
Coated fused silica fibre
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Green Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia
Principles of SPME
1. direct‐immersion SPME
2. headspace‐SPME Operation steps:
1.
2.
3.
4.
5.
6.
Imerison of the needel in the sample
Exposition of the fiber
Extraction of an analytes
Retraction of the fiber
Introduction of the fiber to injection port
Desorption of analytes
Green Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia

MILESTONES IN THE DEVELOPMENT OF SPME
SOLID PHASE MICROEXTRACTION (SPME) first paper on concept of SPME
1990
HEADSPACE SPME (HS-SPME) - Analytes are sampled from headspace above the sample,
particularly useful for analysing the composition of solid samples or samples containing matrix
constituents and in the extraction of very volatile analytes
1993
COOLED COATED FIBRE SPME (CCF-SPME) - approach improving extraction efficiency by
heating the sample and simultaneously cooling the SPME fibre. The temperature is easily
controlled by cooling the fibre coating from the inside with a coolant and by altering the core
diameter of the arrangement
1995
IN-TUBE SPME - the extraction phase is immobilized as the inner coating of the needle or part
of the chromatographic column. Analytes are retained in the extraction medium during a few
draw/eject cycles of the sample, or extraction takes place following a one-off filling of the needle
1997
FIBRE-IN-TUBE SPME - polymer core is inserted into the capillary of the in-tube SPME
arrangement. The core reduces the capillary volume, but the surface area of the sorbent is not
reduced
2000
SOLID-PHASE AROMA CONCENTRATE EXTRACTION (SPACE) - the SPACE rod is
fabricated from stainless steel coated with an adsorbent mixture (mainly of graphite carbon) fixed
on the head of a closed flask, where it adsorbs the aroma for a given time
2004
MEMBRANE-SPME (M-SPME) - physical separation of the two phases with a membrane
impermeable to both of them or by immobilization of the extracting agent in the
membrane pores
2009
Green Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia
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MAIN DIFFICULTIES WITH THE ISOLATION OF POLAR COMPOUNDS
low affinity
compounds
of
extraction
coatings
for
polar
the polar coating may partially dissolve in the
polar sample matrix
limited number of commercially available fibre
coatings for the isolation of polar compounds
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Green Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia
THE CONCEPT OF M‐SPME
SPME:
• simplicity
• short extraction time
• solventless
• automation
• GC compatible
• in-situ sampling
Membrane techniques:
• physical separation
• selectivity
• broad range of solvents
M-SPME
A. Kloskowski, M. Pilarczyk, J. Namieśnik, Anal. Chem., 81, 7363 (2009)
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Green Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia
SCHEME OF M‐SPME FIBRE
1) silica fibre
2) polar retaining medium (50μm coating of PEG)
3) non-polar membrane (90-100μm coating of PDMS)
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Green Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia
0
75
KPEG/Water
>> KPDMS/Water
s a m p l e
P D M S m e m b r a n e
p o l y e t y l e n e g l i k o l e
g l a s s
r o d
analyte concentration
Principles of extraction in M‐SPME
~175 ~200
distance from rod axis [m]
Green Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia

SORBENTS IN M‐SPME
PDMS
PEG
‐ non‐polar
‐ polar
‐ gum‐like or liquid‐like state
‐ gum‐like or liquid‐like state
‐ thermostable to around 300°C ‐ thermally resistant
‐ chemically neutral
‐ low melting point
‐ flexible
‐ high value of dielectric constant
‐ known values of partition coefficients
‐ known values of partition coefficients
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Green Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia
ABSORPTION VS ADSORPTION
ADSORPTION
artefact formation
incomplete desorption
strong catalytic interactions of adsorbents
ABSORTION
analytes are retained by dissolution
analytes can be desorbed at moderate temperatures
analyte decomposition can be ruled out
non-specific interactions between analyte and sorbent
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Green Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia
PRELIMINARY RESULTS ‐ phenoles
Compound
4-Chloro-3-methylphenol
2-Chlorophenol
2,4-Dichlorophenol
2,4-Dimethylphenol
2,4-Dinitrophenol
2-Methyl-4,6-dinitrophenol
2-Nitrophenol
4-Nitrophenol
Pentachlorophenol
2,4,6-Trichlorophenol
Linearity
range
(µg/L)
15-1500
3-300
3-300
3-300
10-1000
15-1500
3-300
15-1500
15-1500
10-1000
2
R
0.9953
0.9936
0.9987
0.9921
0.9963
0.9898
0.9945
0.9937
0.9914
0.9932
LOD (µg/L)
M-SPME
PA
7
43
15
9
110
81
9
150
83
61
50
530
120
110
950
680
60
1800
740
440
A. Kloskowski, M. Pilarczyk, J. Namieśnik, Anal. Chem., 81, 7363 (2009)
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Green Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia
PRELIMINARY RESULTS – VOC’s
COMPOUNDS obenzene (CB) p‐xylene (p‐X) o‐xylene (o‐X) isopropylbenzene (isoPB) n‐propylbenzene (n‐PB) 2‐chlorotoluene (2‐CT) 4‐chlorotoluene (4‐CT) t‐butylbenzene (t‐BB) sec‐butylbenzene (sec‐BB) 1.3‐dichlorobenzene (1.3‐DCB) 1.4‐dichlorobenzene (1.4‐DCB) LOD (ng/l) PEG/PDMS DVB/CAR/PDMS 0.23 0.16 0.13 0.11 0.10 0.12 0.13 0.08 0.08 0.12 0.13 0.41 0.33 0.24 0.27 0.27 0.31 0.35 0.23 0.12 0.37 0.37 Green Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia

ADVANTAGES OF M‐SPME
 Low cost;
 Good mechanical properties, extremely stable thermally;
 Improved extraction efficiency;
 Possibility of adjusting selectivity of sorption based on high dielectric
constant of PEG;
 Analytes retained by dissolution;
 Analytes can be desorbed at moderate temperatures;
 Extraction time is considerably shorter than that required with a solid
polymer
Outlook:
Possibility of utilizing highly polar materials as sorbents
Opportunity to overcome the difficulties with extracting polar
analytes from polar media
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Green Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia
RECENT PUBLICATIONS ON GREEN ANALYTICAL CHEMISTRY
 M. Tobiszewski, A. Mechlińska, B. Zygmunt, J. Namieśnik, Green analytical chemistry
in sample preparation for determination of trace organic pollutants, Trends Anal.
Chem., 28 (2009) 943.
 A. Kloskowski, M. Pilarczyk, J. Namieśnik, Membrane solid-phase microextraction –
a new concept of sorbent preparation, Analytical Chemistry, 81 (2009) 7363.
 M. Tobiszewski, A. Mechlińska, J. Namieśnik, Green analytical chemistry : theory and
practice, Chem. Soc. Rev., 39 (2010) 2869.
 A. Spietelun, M. Pilarczyk, A. Kloskowski, J. Namieśnik, Current trends in solid- phase
microextraction (SPME) fibre coatings, Chem. Soc. Rev., 39 (2010), 4524.
 M. Urbanowicz, B. Zabiegała, J. Namieśnik, Solventless sample preparation
techniques based on solid- and vapour-phase extraction, Anal. Bioanal. Chem., 399
(2011) 277.
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Green Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia
DEPARTMENT OF ANALYTICAL CHEMISTRY
CHEMICAL FACULTY
GDANSK UNIVERSITY OF TECHNOLOGY
Department of
Analytical Chemistry
This lecture can also be found on the homepage of the Department of
Analytical Chemistry
http://www.pg.gda.pl/chem/Katedry/Analityczna/analit.html
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Green Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia
EUROPEAN MASTER IN QUALITY IN ANALYTICAL LABORATORIES‐ EMQAL
http://eacea.ec.europa.eu/erasmus_mundus/
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Green Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia
The exploitation of white cabbage for phytoremediation and biofumigation of soils
(AGROBIOKAP)
Priority axis:
Action:
Sub‐action:
1. Research and development of novel technologies 1.3. Support for R+D projects carried out by scientific institutions on behalf of industrial companies
1.3.1. Development projects
Recommended subsidy: 3 391 950,00 PLN
Project deadline:
01.07.2007‐01.07.2013
CONTACT
Gdansk University of Technology, Chemical Faculty
G. Narutowicza 11/12 Str., 80-233 Gdańsk
phone/fax: 0048 58 347 26 25
e-mail: [email protected]
http://www.chem.pg.gda.pl/agrobiokap/
Project co-financed by European Union from European Regional Development Fund
in a framework of the Innovative Economy Operational Programme 2007-2013
Green Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia
Green Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia


MEMBERS OF MY RESEARCH GROUP
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Green Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia
THANK YOU FOR YOUR ATTENTION!
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Green Chemistry 2011 Innovations, 04-07.12.2011, Melbourne, Australia