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THE UNIVERSITY OF SYDNEY
School of Chemistry
2006
Research Report
Message from the Head of School
Page 3
Advice to Postgraduate Candidates
Page 4
New Faces for 2006
Page 5
Research Reports
Page 11
Research Centres
Page 99
Research Facilities
Page 107
Research Publications
Page 111
Research Fellowships and Grants
Page 131
Awards, Scholarships & Prizes
Page 147
2006 Staff and Student
Page 151
2006 Chemistry Graduates
Page 161
School of Chemistry
Annual Research Report
Professor Gregory G Warr
Names in parentheses following research project titles refer to joint researchers. Those names
with an asterisk or other symbols refer to non-University of Sydney Chemistry researchers.
Head of School
Telephone: +61 2 9351 2106
Facsimile: +61 2 9351 3329
Email: [email protected]
School of Chemistry
Building F11
Eastern Avenue
The University of Sydney
NSW 2006
AUSTRALIA
Telephone: +61 2 9351 4504
Facsimile: +61 2 9351 3329
Email: [email protected]*
Website: http://www.chem.usyd.edu.au/
*All staff can be emailed using:- [email protected]
© Copyright School of Chemistry 2007
Cover Design and Editing
by
Ms Anne Woods
School of Chemistry
The University of Sydney
Front Cover
Top left: The illustration shows a conductive atomic force microscopy (AFM) tip on the top of a selfassembled monolayer of 1,8-octanedithiols (formed by PhD student Peter Cafe). This technique and the
related scanning tunnelling microscopy (STM) technique is currently being used at the School of Chemistry
to measure the single molecule conductance of various molecules for potential applications in molecular
electronics.
From the Head of School
I
n 2006 the School of Chemistry at the University of Sydney cemented its position as one of the top research Chemistry
Departments in Australia. Members of the School enjoyed a 57% success rate in the ARC Discovery grants round announced
in 2006 and were also awarded a number of very substantial Linkage grants. Staff and students of the School received a number
of research awards during 2006 including the inaugural Alan Sargeson Award to Professor Cameron Kepert, the RACI’s Biota
Award to Dr Kate Jolliffe, and Dr Deanna D’Alessandro who received the RACI Cornforth Medal for the most outstanding PhD
thesis submitted in any branch of chemistry, chemical science or chemical technology.
The School has about 33 research groups spanning a wide range of Chemistry disciplines with identified areas of
research strength including: Biological and Medicinal Chemistry; Synthesis, Catalysis and Materials; Polymer and Colloid
Chemistry; Computational and Theoretical Chemistry; Supramolecular Chemistry; Reaction Dynamics and Kinetics; and Chemical
Spectroscopy.
The School is well-equipped with modern research instrumentation including major research facilities for NMR
Spectroscopy, Mass Spectrometry, X-ray Crystallography, Optical Spectroscopy, Electrochemistry, High Pressure Liquid
Chromatography, Analytical and Preparative Gas Chromatography, and High Performance Computing. Research infrastructure
(that underpins and supports all research programs) includes in-house mechanical and electronic workshops. The Madsen Library
(as a branch of the main University Library) holds all of the main Chemistry titles and also provides on-line access to national and
international databases.
In 2006, staff at the University of Sydney held 43 ARC Discovery grants, 14 ARC Fellowships, 22 ARC Linkage grants
and 1 Special Research Initiative Scheme grant. The School was award $16.8M in total research funding, including $13.7M from
the Australian Research Council (ARC). In addition, $2.3M was obtained from other government sources and industry; $786,892
from University of Sydney grants, $589,359 from bequests, and $4,525 from other donations.
Collaborative links with industry continued strongly through the Centre for Heavy Metals Research with Professor
Peter Lay as Deputy Director, the Key Centre for Polymer Colloids with Professor Bob Gilbert as its Director and the Organic
Synthesis Centre with Dr Malcolm McLeod as Director. All centres expanded already strong links with industry and other research
organisations both locally and internationally.
In 2006 there were approximately 104 graduate students enrolled in higher degrees in the School of Chemistry as well as
38 honours students undertaking a year of research to complete their undergraduate degree programs. This large cohort of research
students fosters a strong and vibrant environment for research and this continues to be a real strength of the School.
I would like to thank our Research Committee, chaired by Associate Professor Brendan Kennedy (Associate Head of
School, Research), for managing research matters within the School.
Top right: Illustration of a light-activated biosensor consisting of a ruthenium(II)terpyridine-cytochrome
c bioconjugate (synthesised by PhD student Joshua R. Peterson) on a conductive surface with an conductive
AFM tip on top. See Chem. Commun., 1899-1901, 2007.
Bottom: STM image of a self-assembled monolayer of a platinum-metallomacrocycle (synthesised by MSc
student Jonathon E. Beves). A model based on the X-ray structure of the this molecule is shown up top of
the image. See Dalton Trans.,744-750, 2006.
Professor Gregory G Warr
Head of School
School of Chemistry
Advice to Postgraduate Candidates
The University of Sydney’s School of Chemistry is one of the largest chemistry departments in Australia with a strong
record of achievement and an international research reputation. There are typically around 100 postgraduate students
undertaking research towards doctorate and masters degrees.
The School offers postgraduate programs in all areas of contemporary chemistry leading to the following degrees:
i Master of Science (MSc)
ii Doctor of Philosophy (PhD)
iii Graduate Diploma in Science (equivalent to 4th year of a BSc degree)
The School welcomes expressions of interest from both Australian and international students to undertake a postgraduate
degree in Chemistry.
All information on how to apply for candidature, scholarships, research projects in the School of Chemistry and other
information for both Australian and international students may be found at:
http://www.chem.usyd.edu.au/future/pg_degrees.htm
If you do not have Web access, please contact:
Australian Residents
The Postgraduate Coordinator
School of Chemistry, Building F11
Eastern Avenue
The University of Sydney
NSW 2006
AUSTRALIA
Phone: +61 2 9351 4504
Facsimile: +61 2 9351 3329
Email: [email protected]
Website: http://www.chem.usyd.edu.au/
International Students
International Office
Ground Floor, Building G12 (Services Building)
353 Abercrombie Street (Codrington Street entrance)
The University of Sydney
NSW 2006
AUSTRALIA
Phone: +61 2 9351 4079
Facsimile: +61 2 9351 4013
Email: [email protected]
Website: http://www.usyd.edu.au/international/
New
Faces
for 2006
School of Chemistry
Associate Professor Michael Kassiou
Brain and Mind Research Institute, Room 415 &
School of Chemistry, Room 412c
Telephone: +61 2 9351 0849
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_kassiou.html
Medicinal Chemistry / Molecular Imaging
Ligands for Imaging the Microglial Translator Protein (18 kDa) (James*, Luus*, Robertson)
The recognition that microglia activation is closely linked to the pathophysiology of brain disease has made the Translator
Protein (18 kDa) TSPO, formally known as the peripheral benzodiazepine receptor, an important therapeutic and diagnostic
target. We investigated the structure activity profile of molecular probes based on pyrazolopyrimidines and determined
parameters required for incorporation of radioisotopes while maintaining high binding affinity. The development of the
first fluorinated pyrazolopyrimidine (DPA-714) has allowed us to establish the pharmacokinetics and pharmacodynamics
of this new TSPO ligand when radiolabelled using in vivo imaging in living non-human primates.
[18F]DPA-714: Baboon PET Imaging (Baboon Body – Papio hamadryas)
60 minutes p.i.
Annual Research Report
a non-selective membrane pore which is permeable to hydrophilic molecules with molecular weight up to 900 Da. The
physiological function of P2X7 is as yet unknown, however its high expression in immune cells, particularly microglia,
and current research have suggested that it has an important role in neuroinflammatory and neurodegenerative processes.
We have developed a series of polycyclic ligands which display potent antagonistic properties at the P2X7 receptor.
Modification of the polycyclic moiety of these molecules represents new exciting approach for the development of suitable
radiolabelled molecular probes for use in brain imaging of P2X7 receptors using positron emission tomography (PET).
Sigma Receptors (Banister, Moussa, Coster*)
Since the discovery of sigma receptors, research has been ongoing
in an attempt to understand the functional roles of these sites.
Initial interest in sigma receptors was largely motivated by
the observation that the sigma site was a high affinity binding
site for psychoactive drugs including many of the atypical
antipsychotic drugs. Ligands which bind with high affinity at
sigma receptors have been shown to modulate and interfere with
several neurotransmitters and have potent activities in animal models suggestive of antipsychotic, cognitive enhancing,
neuroprotective, and antidepressant activities. We have recently reported the synthesis and binding a novel series of
trishomocubanes of the type 4-azahexacyclo[5.4.1.02,6.03,10.0 5,9.08,11]dodecane namely compounds 1 and 2 which display
high affinity for sigma-2 and sigma-1 receptor subtypes respectively. These molecules have also been shown to modulate
cocaine induced behaviours. These lead compounds provide the basis for
further refinement of the binding and functional activity of this class.
Arylalkyl 4-benzyl piperazines have only recently been reported as ligands
for sigma receptors. This receptor is of interest since many psychoactive
drugs including atypical antipsychotics bind to this site. We have developed
the prototypic radioligand, 1-benzofuran-2-ylmethyl-4-(4-[11C]methoxybenzyl)piperazine, and evaluated its potential as a tracer in the living baboon
brain (see images). We have demonstrated that this radioligand is capable
of imaging in vivo sigma receptor density. This will allow correlations to
be derived between changes in sigma receptor denisty and disease on-set
and progression.
Selected Publications
[18F]DPA-714 (baseline)
[18F]DPA-714 + DPA-714 (1 mg/kg)
Evaluating Novel Neuroprotective Agents (Leaver*, Truong* Henderson*)
Neuroprotective agents represent a novel therapeutic strategy towards the treatment of brain diseases. With the advent
of high-resolution microPET technologies it has become possible to image animal models of neurodegenerative diseases
such as Alzheimer’s disease, Parkinson’s disease and Multiple Sclerosis. We are currently utilising models of such
diseases for the evaluation of newly developed ligands targeting the Traslocator Protein (18 kDa), NR2B-NMDA and
sigma receptor subtypes as potential neuroprotective agents. These models coupled with molecular imaging techniques
allow for the in vivo evaluation of these pharmacological agents while ex vivo studies, using immunohistochemistry and
neuropathological examination allow validation of imaging studies. The Purinergic P2X7 Receptor (Gunosewoyo, Coster*, Bennett*)
The P2X7 receptor is an unusual non-desensitising cation selective ion channel directly gated by extracellular ATP. This
is the most interesting of the ionotropic P2X receptors. Upon stimulation by high concentrations of ATP it generates
1. Gunosewoyo, H, Coster, MJ and Kassiou, M. Molecular probes for P2X7 receptor studies. Curr. Med. Chem., 14, 1505-1523,
2007.
2. Boutin, H, Chauveau, F, Thominiaux, C, Kuhnast, B, Gregoire, MC, James, M, Jan, S, Brulon, V, Fontyn, Y, Selleri, S, Trebossen,
R, Hantraye, P, Dolle, F, Tavitian, B and Kassiou, M. [11C]DPA-713:a novel peripheral benzodiazepine receptor PET ligand for in
vivo imaging of neuroinflammation. J. Nucl. Med., 48, 573-581, 2007.
3. Quinlivan, M, Chalon, S, Vergote, J, Henderson, J, Katsifis, A, Kassiou, M and Guilloteau, D. Decreased vesicular acetylcholine
transporter and α4β2 nicotinic receptor density in the rat brain following 192 IgG-saporin immunolesioning. Neurosci Lett., 415,
97-10, 2007.
4. Waterhouse, RN, Collier, TL and Kassiou, M. Imaging sigma receptors: Applications in drug development. Curr. Pharm. Design,
13, 51-72, 2007.
5. Kozikowski, AP, Chellappan, SK, Henderson, D, Fulton, R, Giboureau, N, Xiao, Y, Wei, ZL, Guilloteau, D, Emond, P, Dolle, F,
Kellar, KJ and Kassiou, M. Novel acetylenic pyridines for use in PET imaging of nicotinic receptors. ChemMedChem., 2, 54-57,
2007.
6. Liu, X, Banister, SD, Christie, MJ, Banati, R, Meikle, S, Coster, MJ and Kassiou, M. Trishomocubanes: Novel sigma ligands
modulate cocaine-induced behavioural effects. Eur J Pharmacol., 555, 37-42, 2007.
7. James, ML, Selleri, S and Kassiou M. Development of ligands for the peripheral benzodiazepine receptor. Curr. Med. Chem., 3,
1991-2001, 2006.
8. Truong, L, Allbutt, H, Kassiou, M and Henderson, JM. Developing a preclinical model of Parkinson’s disease: A study of behaviour
in rats with graded 6-OHDA lesions. Behav. Brain Res., 169, 1-9, 2006.
9. Liu, X, Mattner, F, Katsifis, A, Christie, MJ and Kassiou, M. Influence of trishomocubanes on sigma receptor binding of N-(1benzyl-piperidin-4-yl)-4-[123I]iodobenzamide in vivo in the rat brain. Med. Chem., 1, 31-38, 2005.
10.Kassiou, M, Dannals, RF, Liu, X, Wong, DF, Ravert, RT and Scheffel, UA. Synthesis and in vivo evaluation of a new PET radioligand
for studying sigma-2 receptors. Bioorg. Med. Chem., 13, 3623-3626, 2005.
11.James, ML, Fulton, RR, Henderson, DJ, Eberl, S, Meikle, SR, Thomson, S, Allan, RD, Dolle, F, Fulham, MJ and Kassiou M.
Synthesis and in vivo evaluation of a novel peripheral benzodiazepine receptor PET radioligand. Bioorg. Med. Chem., 13, 6188-6194,
2005.
School of Chemistry
Dr Peter Rutledge
Annual Research Report
We are working to develop new iron-based oxidising systems which mirror these enzymatic reactions and convert simple
hydrocarbons to oxidised products.
Room 547
School of Chemistry, F11
Telephone: +61 2 9351 5020
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_rutledge.html
Peptide-based Heavy Metal Sensors (Scully)
Bio-Inspired synthesis and chemical biology
Our research uses the tools of organic synthesis, bio-organic and bioinorganic chemistry to develop new biologically-inspired catalysts
for important synthetic transformations and the breakdown of
environmental contaminants.
Heavy metals such as cadmium and mercury form some of the most toxic materials known, attacking their target organs
at very low concentrations. Various industrial activities have caused levels of these heavy metals in the environment to
rise over recent years. Some organisms have developed strategies to live in locales prone to high levels of cadmium and
mercury pollution, using sulfur-rich proteins such as metallothioneins and phytochelatins to bind and sequester the
toxic metal ions. These proteins incorporate a very high percentage of cysteine residues (≥ 30% of primary structure),
making them effective agents for heavy metal sequestration.
We are building on Nature’s approach to use thiol- and sulfide-rich peptides as agents for sensing and binding
mercury and cadmium in the environment. By tethering these peptides to electrochemical reporters, we have developed
a novel system for sensing these metals that is selective for mercury over cadmium and other thiophilic metals tested.
Work is now underway to improve the sensitivity of these systems and to create novel agents for metal sequestration.
Peptide Mimics of Nitrile Hydratase (Byrne, Houlihan)
Cyanide and organic nitriles are well known chemical toxins, but such
compounds also have considerable commercial utility and are used in a
range of industrial processes. The strategies currently available to deal
with the significant quantities of nitrile-containing waste generated
through these processes are severely limited. Nitrile hydratase enzymes
play central roles in the breakdown of nitriles in vivo, making them
attractive targets for a bioremediation approach to the treatment of
nitrile waste streams. Nitrile hydratases are also used increasingly as
biocatalysts in the industrial synthesis of polymers and the asymmetric
synthesis of fine chemicals incorporating amide functional groups.
Crystal structures of nitrile hydratases from several organisms reveal a remarkable ligand environment 1
around the active site metal. Two nitrogen atoms from main-chain amides bind to the metal (cobalt(III) or iron(III)),
along with three sulfur atoms, each in a different oxidation state. The five ligands are located in a short section of the
protein’s primary sequence, spread across six amino acids in one peptide chain.
We are developing new peptide and peptido-mimetic systems as bio-inspired catalysts for nitrile hydration,
and as mechanistic probes to study the unusual sulfur oxidation that occurs at the active site and elucidate a detailed
mechanism for nitrile hydratase catalysis.
New Catalysts for Hydrocarbon Oxidation (Barry,
Dungan, Wong)
The conversion of simple hydrocarbons (alkanes, alkenes and
aromatic compounds) to oxidised products (alcohols, epoxides and
diols) is an important goal in synthetic organic chemistry. Nature
uses a variety of iron-centred enzymes to oxidise such substrates
cleanly and selectively. Non-heme iron(II) oxidase enzymes (NHIOs)
such as naphthalene dioxygenase, isopenicillin N synthase and prolyl
hydroxylase catalyse a diverse array of oxidation reactions, using the
generalised active site environment 2 to activate molecular oxygen.
Selected Publications
1. Howard-Jones, AR, Elkins, JM, Clifton, IJ, Adlington, RM, Baldwin, JE and Rutledge PJ. Interactions of isopenicillin N synthase
with cyclopropyl-containing substrate analogues reveal new mechanistic insight. Biochemistry, 46, 4755-4762, 2007.
2. Daruzzaman, A, Clifton, IJ, Adlington, RM, Baldwin, JE and Rutledge, PJ. Unexpected oxidation of a depsipeptide substrate
analogue in crystalline isopenicillin N synthase. ChemBioChem, 7, 351-358, 2006.
3. Murphy, PV and Rutledge, PJ. Symbiosis in chemistry and biology. Nature Chem. Biol., 2, 59-62, 2006.
4. Rutledge, PJ. Nitriles with a heteroatom attached to the cyanocarbon. Comprehensive Organic Functional Group Transformations II,
Volume 5 Jones RCF, Katritzky, AR and Taylor, RJK (Ed.); Elsevier/Pergamon Press, 1023-1080, 2005.
5. Howard-Jones, AR, Rutledge, PJ, Clifton, IJ, Adlington, RM and Baldwin, JE. Unique binding of a non-natural l,l,l-substrate
by isopenicillin N synthase. Biochem. Biophys. Res. Comm., 336, 702-708, 2005.
6. Long, AJ, Clifton, IJ, Roach, PL, Baldwin, JE, Rutledge, PJ and Schofield, CJ. Structural studies on the reaction of isopenicillin
N synthase with substrate analogues δ-(l-α-aminoadipoyl)-l-cysteinyl-glycine and δ-(l-α-aminoadipoyl)-l-cysteinyl-d-alanine.
Biochemistry, 44 6619-6628, 2005.
7. Krall, JA, Rutledge, PJ and Baldwin, JE. Design and synthesis of an isopenicillin N synthase mimic. Tetrahedron, 61, 137-143,
2005.
8. Grummitt, AR, Rutledge, PJ, Clifton, IJ and Baldwin, JE. Active site mediated elimination of hydrogen fluoride from a fluorinated
substrate analogue by isopenicillin N synthase. Biochem. J., 382, 659-666, 2004.
9. Elkins, JM, Rutledge, PJ, Clifton, IJ, Burzlaff, NI, Roach, PL, Adlington, RM and Baldwin, JE. Crystallographic investigation of
the isopenicillin N synthase reaction with the unsaturated substrate analogue δ-(l-a-aminoadipoyl)-l-cysteinyl-d-vinylglycine.
Org. Biomol. Chem. 1, 1455-1460, 2003.
10
School of Chemistry
Research
Report
12
School of Chemistry
Associate Professor Robert S Armstrong
Honorary Staff
Room 146
School of Chemistry, F11
Telephone: +61 2 9351 3104
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_armstrong.html
inorganic and bioinorganic spectroscopy
Cancer Diagnosis in Tissues and Identification of Microbes by Vibrational Spectroscopy (Ali, Carter,
Lay, Johnson, Mountford*, Rich, Russell*, Sorrell*, Tam)
Microprobe infrared (IR) and Raman vibrational spectroscopy was used in conjunction with multivariate analysis to develop
new diagnostics for breast cancer, and in particular pre-cancerous lesions. IR and Raman images were plotted based on
the distributions of diagnostic peaks, including amide I (ν(C=O) at 1650 cm–1), lipid (δ(CH2/CH3) at 1445 cm–1) and
DNA (νs(PO2–) at 1240 cm–1). Strong correlations have been obtained for vibrational imaging diagnosis with diagnoses
obtained from standard pathology studies and NMR techniques. Vibrational spectroscopic techniques are also being
developed to identify pathogenic micro-organisms and to examine their susceptibility to new drugs.
XAS and Resonance Raman Studies of Hemes and Heme Proteins (Harris, Lay, Levina, Rich,
Witting*)
Resonance Raman and EPR spectroscopic and XAFS studies are being used to probe the active sites of heme proteins,
and their small molecule adducts. There is particular interest in how these proteins use the binding of NO or other
small molecules in signal processes, the immune system, for vasicodilation, and the role they might have in cardiovascular
disease.
Fullerenes: Their Complexes, Conjugates and Derivatives (Boyd*, Carter, Gallagher, Lay, Reed*,
Sen Gupta)
Research has continued into studies of the spectroscopy and bioinorganic chemistry of fullerene/porphyrin conjugates,
including water-soluble species. These conjugates have been shown to be very potent potential anti-cancer drugs, with
higher activity than cisplatin against a series of cell lines, including Pt-resistant lines. The spectroscopy, electrochemistry
and coordination chemistry of C60 and C70 are being investigated in detail.
Selected Publications
1. Gallagher, SH, Armstrong, RS, Lay, PA and Reed, CA. D-term scattering in the resonance Raman spectrum of C60 J. Am. Chem.
Soc., 116, 12091-12092, 1994.
2. Gallagher, SH, Armstrong, RS, Lay, PA and Reed, CA. Resonance Raman spectra of C70 in benzene. Chem. Phys. Lett., 234, 245248, 1995.
3. Gallagher, SH, Armstrong, RS, Clucas, WA, Lay, PA and Reed, CA. Resonance Raman scattering from solutions of C60 J. Phys.
Chem., 101, 2960-2968, 1997.
Annual Research Report
13
4. Gallagher, SH, Armstrong, RS, Bolskar, RD, Lay, PA and Reed, CA. Raman excitation profiles of C70 in benzene solutions.
Assignment of electronic spectrum in the region of 380-510 nm. J. Am. Chem. Soc., 119, 4263-4271, 1997.
5. Rich, AM, Armstrong, RS, Ellis, PJ, Freeman, HC and Lay, PA. Determination of iron–ligand bond lengths in horse heart met- and
deoxy-myoglobin using multiple-scattering XAFS analyses. Inorg. Chem., 37, (22), 5743-5753, 1998.
6. Rich, AM, Ellis, PJ, Tennant, L, Wright, PE, Armstrong, RS and Lay, PA. Determination of Fe–ligand bond lengths and the
Fe–N–O bond angles in soybean ferrous and ferric nitrosylleghemoglobin a using multiple-scattering XAFS analyses. Biochemistry,
38, 16491-16499, 1999.
7. Bae, IT, Tolmachev, Y, Mo, Y, Scherson, D, Scheidt, WR, Ellison, MK, Cheng, M-C, Armstrong, RS and Lay, PA. In situ Fe Kedge X-ray absorption spectroscopy of a nitrosyl iron(II) porphyrin adduct adsorbed on a high-area carbon electrode in aqueous
electrolytes. Inorg. Chem., 40, 3256-3258, 2001.
8. Terentis, AC, Thomas, SR, Takikawa, O, Littlejohn, TK, Truscott, RJW, Armstrong, RS, Yeh, S-R and Stocker, RJ. The heme
environment of recombinant human indoleamine 2,3-dioxygenase. Biol. Chem., 277, 15788-15794, 2002.
9. Kim, K-C, Hauke, F, Hirsch, A, Boyd, PDW, Carter, EA, Armstrong, RS, Lay, PA and Reed, CA. Synthesis of the C59N+ carbocation.
A monomeric azafullerene isoelectronic to C60. J. Amer. Chem. Soc. Commun., 125, (14), 4024-4025, 2003.
10.Gallagher, SH, Thompson, KC, Armstrong, RS and Lay, PA. The unusual intensity behaviour of the 281-cm−1 resonance Raman
band of C60 - a complex tale of vibronic coupling, symmetry reduction, solvatochromism and Jahn-Teller activity. J. Phys. Chem.
A., 108, (26), 5564-5572, 2004.
11.Aitken, JB, Thomas, SE, Stocker, R, Thomas, SR, Takikawa, O, Armstrong, RS and Lay, PA. Determination of the nature of the
heme environment in nitrosyl indolamine 2,3-dioxygenase using multiple-scattering analyses of x-ray absorption fine structure.
Biochemistry, 43, (17), 4892-4898, 2004.
12.Feng, L, Gell, DA, Zhou, S, Gu, L, Kong, L, Min Hu,YJ, Yan, N, Rich, AM, Armstrong, RS, Lay, PA. Gow, AJ, Weiss, MJ, Mackay,
JP and Shi Y. Molecular mechanism of AHSP-mediated stabilization of a-hemoglobin. Cell, 119, 629-640, 2004.
13.Immoos, CE, Suic, PJ, Czarnecki, K, Bocian, DF, Levina, A, Aitken, JB, Armstrong, RS and Lay, P. A. Bonding in HNO-myoglobin
as characterised by X-ray absorbance and resonance Raman spectroscopies. J. Amer. Chem. Soc., (Communication), 127, 814-815,
2005.
14.Levina, A, Armstrong, RS and Lay, PA. Three-dimensional structure determination using multiple-scattering analysis of XAFS:
Applications to metalloproteins and coordination chemistry. Coord. Chem. Rev., 249, 141-160, 2005.
15.Armstrong, RS, Foran, GJ, Hough, WA, D’Alessandro, DM, Lay, PA, Crossley, MJ. Spectroelectrochemical evidence for
communication within a laterally-bridged dimanganese(III) bis-porphyrin. J. Chem. Soc., Dalton Trans., 4805-4813, 2006.
14
School of Chemistry
Associate Professor Phil Attard*
Room 240
School of Chemistry, F11
Telephone: +61 2 9351 5878
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_attard.html
*ARC Professorial Fellow
Annual Research Report
15
reproduced the Green-Kubo time-correlation formulae for the hydrodynamic transport coefficients, which are one of the
few formally exact non-equilibrium results already known. Importantly, molecular-level computer simulation algorithms
were developed and implemented, and these verified the theory numerically and confirmed its computational feasibility.
The theory successfully reproduced literature results for the thermal conductivity of a Lennard-Jones fluid, and it was
found to be more efficient than equilibrium molecular dynamics Green-Kubo simulations. This is the first time that a
Monte Carlo simulation algorithm has been developed and applied to a non-equilibrium problem.
We anticipate that future research in non-equilibrium area will proceed both in the application of the theory
and in the analysis of its foundations. In the former case problems such as electrical conduction, driven diffusion, and
convection beckon. More fundamentally, extension to transient and non-steady phenomena is called for, as is analysis of
non-equilibrium phase transitions, semi-analytic approximations, and computational algorithms. The semi-quantitative
exploration of complex systems including life, earth, and beyond is now also possible.
thermodynamics, statistical mechanics, and
condensed matter theory
From Molecular Interactions to Macroscopic Properties
Statistical mechanics describes how the cooperative behaviour of molecules determines macroscopic phenomena, and it
can be used to unravel a multitude of scientific and industrial problems. We explore the properties of condensed matter
at the molecular level using various computational and mathematical techniques, and by collaborative experiments.
We emphasise the development of new methods for the treatment of more complex systems, such as inhomogeneous
and confined liquids, and specific calculations aimed at rationalising measured data and unexplained phenomena, such
as aspects of the interactions of colloidal particles and surfaces. Not only has this resulted in quantitative descriptions
of various phenomena, but it has also advanced the understanding and foundations of thermodynamics and statistical
mechanic.
Theory often consists of the application of pre-existing techniques to specific problems, but we prefer to
develop new techniques and algorithms with a view to their broad use and their application to generic classes of systems.
Obviously this is more challenging but the reward is in the greater impact of the research. To date we have formulated
Monte Carlo and molecular dynamics computer simulation algorithms to obtain the chemical potential, the solvation free
energy, the surface tension, and the properties of fluids under shear. We have also developed mathematical techniques
such as integral equation and asymptotic expansion and applied them to the electric double layer, to polymer melts, and
to near-critical and spinodal fluids. At the continuum level, we have invented mathematical models and algorithms to
characterize deformation and viscoelastic effects on particle interactions.
Fig. 1 First non-equilibrium Monte Carlo simulation. The thermal conductivity of a Lennard-Jones fluid has been obtained
as a function of density using the new non-equilibrium probability density (squares and circles, offset horizontally), and
compared to conventional non-equilibrium molecular dynamics literature results (triangles).
Nonequilibrium Statistical Mechanics
This past year saw us announce a major breakthrough in the study of time-dependent phenomena, namely a general
theory for non-equilibrium thermodynamics and statistical mechanics. Ludwig Boltzmann, who died 100 years ago this
September, invented the equilibrium probability distribution, exp –U /RT. His grave bears the epitaph, S = kB log Ω ,
which gives the entropy of an equilibrium system. Until now neither the entropy nor the probability have been known for
non-equilibrium or time-dependent systems, and the new theory significantly advances the field by providing expressions
for these. The maximisation of the new second entropy generalises the second law of thermodynamics to non-equilibrium
systems. The new theory justifies the regression hypothesis of Onsager, which provided the reciprocal relations, and
contrasts with the principle of minimum entropy production enunciated by Prigogone, another Nobel prize winner. The
significance and generality of the new non-equilibrium theory can be appreciated by its application to the problem of
the origin of life and the direction of its evolution. These are both consistent with the new law of thermodynamics even
though they paradoxically appear to contradict the conventional second law of thermodynamics.
To test and to illustrate the new theory, it was applied to the problem of steady heat flow, which may be
thought of as the canonical non-equilibrium problem. It was shown mathematically that in the linear regime the theory
Selected Publications
1. Attard, P. Thermodynamics and statistical mechanics: Equilibrium by entropy maximisation. Academic Press, London, 448 pages,
2002.
2. Attard, P. Electrolytes and the electric double layer. Adv. Chem. Phys., 92, 1-159, 1996.
3. Attard, P. Friction, adhesion, and deformation: Dynamic measurements with the atomic force microscope. J. Adhesion Sci. Technol.,
16, 753-791, 2002.
4. Stiernstedt, J, Rutland, MW and Attard, P. A novel technique for the in situ calibration and measurement of friction with the
atomic force microscope. Rev. Sci. Instrum., 76, 083710, 2005.
5. Attard, P. Statistical mechanical theory for steady state systems. V. Non-equilibrium probability density. J. Chem. Phys., 124,
224103, 2006.
6. Attard, P. Theory for non-equilibrium statistical mechanics. Phys. Chem. Chem. Phys., 8, 1-26, 2006.
16
School of Chemistry
Annual Research Report
Dr George B Bacskay
Selected Publications
Honorary Staff
Room 315
School of Chemistry, F11
Telephone: +61 2 9351 3777
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_bacskay.html
quantum chemistry
Spectroscopic Properties of C2: Quantum Chemical Computations of Oscillator Strengths and
Radiative Lifetimes Quantum (Kokkin, Schmidt)
C2 is a prominent molecule in flames, but also in protoplanetory nebulae, comets and interstellar molecular clouds. It
is an increasingly important probe of extraterrestrial environments, most recently of the Red Rectangle. The accurate
astrophysical modeling of C2 requires detailed and precise understanding of the photophysics of C2. While experimental
spectroscopy provides much of the basic data, properties such as oscillator strengths are not readily amenable to direct
experimental determination. They can be, however, determined by theoretical approaches, namely by high-level quantum
chemical computations.
The aims of this project have been the computation of oscillator strengths and other spectroscopic properties,
as accurately as currently possible, using state of the art quantum chemical methods, of the d3Pg ← a3Pu Swan band
system, the b3Sg- ← a3Pu Ballik-Ramsay band system, the A1Pu ← X1Sg+ Phillips band system and the d3Pu ← c3Sg+
band system.
The potential energy surfaces of the electronic states of interest were computed using multi-reference
configuration interaction (MR-CI) methods and correlation consistent polarized basis sets ranging from double to
hextuple zeta, viz. aug-pVxZ, x = 2,3,... 6, resulting in a high degree of convergence of the valence correlation energy.
Core and core-valence correlation corrections were calculated by MR-CI, using the aug-cc-pCVQZ basis. Scalar relativistic
corrections were also computed by MR-CI with the cc-pVQZ basis. The bulk of the computations were carried out using
the MOLPRO 2006.1 programs on the SGI Altix AC computer of the Australian Partnership for Advanced Computing
at the National Supercomputing Centre, ANU.
The computed geometries, harmonic frequencies, anharmonicities and rotational constants are in excellent
agreement with experiment, e.g. within 0.1 % in case of the harmonic frequencies and rotational constants. The calculated
radiative lifetimes of the various vibronic states are also in good accord with the available experimental data. Most
importantly, however, this work has yielded a complete series of oscillator strengths for the four band systems studied,
which will enable the development of significantly more accurate astrophysical models of C2.
Spectroscopic Properties of Halocarbenes
The systematic study of halocarbenes in collaboration with A/Prof Kable’s group in the School of Chemistry has been an
on-going research activity for almost a decade. Systems, ranging from HCF to CClBr, CBr2 and CF3CF have been characterized via ab initio quantum chemical techniques with regard to their thermochemistry, spectroscopic constants and
photochemistry in their ground and lowest triplet and singlet excited states3,7. Such studies have provided a theoretical
underpinning to the assignment and interpretation of observed spectroscopic data. This theoretical work is being extended
to iodine containing carbenes. The quantum chemical treatment of such molecules requires special techniques so as to
reliably describe and account for scalar relativistic and spin-orbit coupling effects. To this end, a variety of effective core
potentials and correlation consistent basis sets are explored. Work is in progress on the ICX carbenes (X = F, Cl, Br and
I), with an emphasis on the accurate prediction of geometries, vibrational frequencies and excitation energies.
17
1. Eek, W, Nordholm, S and G. B. Bacskay. The screened atomic potential – a simple explanation of the aufbau model.Chem. Educator,
11, 235-242, 2006.
2. Mackie, JC and Bacskay, GB. Quantum chemical study of the mechanism of reaction between NH (X3S¯) and H2, H2O and CO2
under combustion conditions. J. Phys. Chem. A, 109, 11967-11974, 2005.
~
3. Guss, JS, Bacskay, GB and Kable, SH. Quantum chemical computation of the spectroscopic constants of the X(1A´), ã(3A˝) and
1
Ã( A˝) states of CBrCl and its heat of formation”, Chem. Phys. Letters, 405, 258-264, 2005.
4. Hush, NS, Schamberger, J and Bacskay, GB. A quantum chemical computational study of the relative stabilities of cis- and transplatinum dichloride in aqueous solution. Coord. Chem. Rev., 249, 299-311, 2005.
5. Bacskay, GB and Mackie, JC. Oxidation of CO by SO2: A theoretical study. J. Phys. Chem. A, 109, 2019-2025, 2005.
6. Zhang, F, Bacskay, GB and Kable, SH. Quantum chemical determination of the equilibrium geometries and harmonic vibrational
frequencies of 1,1´-, 1,2´- and 2,2´-binaphthyl in their ground and excited (1La) electronic states. J. Phys. Chem. A, 108, 172-184,
2004.
7. Bacskay, GB. Quantum chemical characterisation of the ground and lowest excited singlet and triplet states of CH3CF and CF3CF
and their photochemical isomerization and dissociation pathways. Mol. Phys., 101, 1955-1965, 2003.
8. Haworth, NL and G B Bacskay: “Heats of formation of phosphorus compounds determined by current methods of computational
quantum chemistry. J. Chem. Phys., 117, 11175-11187, 2002.
18
School of Chemistry
Dr Robert W Baker
Room 516a
School of Chemistry, F11
Telephone: +61 2 9351 4049
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_baker.html
Annual Research Report
19
Metallocene-Based Catalysts for Olefin Polymerisation and Asymmetric Catalysis (Alt,† Schilling†)
Polyolefins are a multi-billion dollar a year industry. Recently, there has been enormous interest in the use of metallocenes
as single-site homogeneous cataysts for the polymerisation of olefins. We have prepared a number of unique fluorenebased metallocenes such as the ansa-zirconocene complexes 9 – 11, which have been used as catalysts (in combination
with methylalumoxane) for the preparation of polyethylene and stereoregular polypropylene; e.g. highly syndiotactic
polypropylene (which cannot be prepared using traditional heterogeneous Ziegler-Natta catalysts) was obtained using
complex 9 as the catalyst. We are also currently investigating the preparation of chiral non-racemic versions of these
complexes (using our axially chiral cyclopentadienyl ligand design) for use as asymmetric catalysts for synthetic organic
transformations.
asymmetric catalysis
Planar-Chiral Metal Complexes for Asymmetric Catalysis (Whitby*)
Asymmetric synthesis, and in particular asymmetric catalysis, remains one of the most active areas of current research
in organic chemistry. Planar-chiral cyclopentadienyl metal complexes feature amongst the most successful asymmetric
catalysts, but they are often very difficult to prepare in enantiomerically pure form. We have devised a new type of chiral
cyclopentadienyl ligand, incorporating axial chirality, which allows the preparation of planar-chiral metal complexes in
enantiomerically pure form. We have recently prepared a wide range of axially chiral chelating indene ligands, such as
1– 6, and are currently exploring the preparation of a number of transition metal complexes (e.g. 7 and 8) using these
ligands. In addition to our ability to prepare these complexes in enantiomerically pure form, we have observed that
the constrained chelation afforded by our ligand design can in some cases generate metal complexes having unusual
coordination environments, and therefore potentially unique reactivity. The screening of these complexes for potential
applications in asymmetric catalysis is underway.
*
†
Southampton University, U.K.
University of Bayreuth, Germany
Selected Publications
1. Baker, RW, Foulkes, MA and Taylor, JA. Axially chiral cyclopentadienyl ligands: stereoselective synthesis of 1-substituted-9-(1′naphthyl)fluorenes and retention of axial chirality in the fluorenyl carbanions. J. Chem. Soc., Perkin Trans., 1, 1047, 1998.
2. Baker, RW, Reek, JNH and Wallace, BJ. Asymmetric synthesis of axially chiral 1-(2′-methyl-3′-indenyl)naphthalenes via prototropic
rearrangements of stable rotamers of 1-(2′-methyl-1′-indenyl)naphthalenes. Tetrahedron Lett., 39, 6573, 1998.
3. Baker, RW and Wallace, BJ. Enantiospecific synthesis of a planar chiral bidentate indenyl-alkoxide complex of zirconium using
an axially chiral indene ligand. Chem. Commun., 1405, 1999.
4. Baker, RW, Foulkes, MA and Turner, P. Enantiospecific synthesis of a planar chiral fluorenylzirconium ansa-metallocene: synthesis
and structures of [1-(9-fluorenyl)- and [1-(1-methyl-9-fluorenyl)-2-(2-indenyl)naphthalene]zirconium dichloride. J. Chem. Soc.,
Dalton Trans., 431, 2000.
5. Baker, RW and Taylor, JA. Synthesis, resolution and rates of racemisation of 1-(2′-methyl-3′-indenyl)-2-naphthylamine and -2naphthol. Tetrahedron Lett., 41, 4471, 2000.
6. Baker, RW, Foulkes, MA, Griggs, M and Nguyen, BN. A new synthesis of 3-substituted-1H-indenes through reaction of o-(bmagnesioalkyl)phenylmagnesium dihalides with carboxylate esters. Tetrahedron Lett., 43, 9319, 2002.
7. Alt, HG, Baker, RW, Dakkak, M, Foulkes, MA, Schilling, MO and Turner, P. Zirconocene dichloride complexes with a 1,2naphthylidene bridge as catalysts for the polymerisation of ethylene and propylene. J. Organomet. Chem., 689, 1965, 2004.
8. Baker, RW, Luck, IJ and Turner, P. Constrained coordination through atropisomerism: Synthesis and structure of an h5:kN-bidentate
N,N-dimethylaniline-functionalised indenylruthenium(II) complex. Inorganic Chemistry Communications, 8, (9), 817-820, 2005.
9. Baker, RW, Rea, SO, Sargent, MV, Schenkelaars, EMC, Tjahjandarie, TS and Totaro, A. Enantioselective synthesis of axially chiral
1-(1-naphthyl)isoquinolines and 2-(1-naphthyl)pyridines through sulfoxide ligand coupling reactions. Tetrahedron, 61, (15), 37333743, 2005.
20
School of Chemistry
Associate Professor James Beattie
Annual Research Report
21
These remarkable surfactant-free emulsions can be reversibly titrated to about pH 5 without breaking. The
pH dependence of their zeta potential implies an isoelectric point of pH~4, independent of the identity of the counteranion, whether chloride, iodide or perchlorate.
Room 454
School of Chemistry, F11
Telephone: +61 2 9351 3797
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_beattie.html
colloids and catalysts
Electroacoustics Of Colloidal Suspensions
(Djerdjev, Franks, Warr)
An electroacoustic effect is created when an alternating
electric field is applied to a concentrated (> 1 vol%)
colloidal suspension. The charge on the particles causes
them to jiggle in the field. Because of their density
difference from the surrounding fluid this oscillatory
motion creates a sound wave of the same MHz frequency
as that of the applied electric field. By measuring the
phase as well as the amplitude of this sound wave a
dynamic mobility spectrum is obtained which can be
analysed to give the mean size of the colloidal particles
as well as their zeta potential. This development, made
in Sydney over the last decade, allows measurements
of the properties of many different concentrated
colloidal suspensions, which previously could only be
studied under dilute conditions by optical methods.
As well, new electroacoustic phenomena continue to
be revealed.
One of these is the direct observation of surface conduction – the conductivity of ions within the stagnant
layer or Stern layer close to the particle surface. When the ionic strength of the supporting medium is high (bottom
curve in Figure) the phase lag of the dynamic mobility spectrum decreases with frequency as normal. But when the ionic
strength is low the applied field is mostly conducted through
the ions in the Stern layer, resulting in the maximum in the
phase angle shown by the upper curves in the Figure.
Our ability to measure concentrated emulsions
has enabled us to confirm quantitatively for the first time the
long-standing belief that the oil/water interface is negatively
charged spontaneously by the autolysis of water and the
preferential adsorption of hydroxide ions. We conducted a
pH-stat experiment in which the increasing surface area of
the emulsion as homogenisation occurred could be correlated
with the hydroxide ion adsorbed on the newly formed
surface. The very large surface area of the concentrated (2
vol%) emulsion led to a measurable pH drop; maintaining a
constant pH gives the total surface charge. Simultaneously
measuring the droplet size with the electroacoustics method
gives to total surface area, allowing calculation of the surface
charge density to be 5 μC cm-2.
Catalysts (Masters, Guo)
Heterogeneous catalysts are superior if they can be as selective as homogeneous catalysts and remain active over many
catalytic cycles. New mixed metal catalysts based on the AlPO-5 and SAPO-5 zeolite structures have been prepared
and tested for activity for cyclohexane oxidation at Delft University of Technology and DSM in The Netherlands. The
mixed metal catalysts prepared for the first time showed superior activity.
Selected Publications
1. Beattie, JK, Hunter, RJ and Zhang, H. Electroacoustic detection of the onset of depletion flocculation of latex dispersions by
hydroxyethyl cellulose. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 275, 83-86, 2006.
2. Beattie, JK. The intrinsic charge on hydrophobic microfluidic substrates. Lab on a Chip, 6, 1409-1411, 2006.
3. Djerdjev, AM, Hunter, RJ and Beattie, JK. Self-depletion flocculation of tetralin oil-in-water emulsions. Langmuir, 22, 84-87,
2006.
4. Rowlands, WN, Beattie, JK, Djerdjev, AM and O’Brien, RW. Ultrasonic attenuation by nanoporous particles. Physical Chemistry
Chemical Physics, 8, 5124-5130, 2006.
5. Whitby, CP, Djerdjev, AM, Beattie, JK and Warr, GG. Nanoparticle adsorption and stabilisation of surfactant-free emulsions.
Journal of Colloid and Interface Science, 301, 342-345, 2006.
22
School of Chemistry
Dr Ronald J Clarke
Room 358
School of Chemistry, F11
Telephone: +61 2 9351 4406
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_clarke.html
biophysical chemistry of membranes
Mechanism of the Na+,K+-ATPase (Pilotelle-Bunner, Cornelius1, Apell2, Sebban3)
The Na+,K+-ATPase, which is found in the plasma membrane of all animal cells, utilizes the free energy derived from
ATP hydrolysis for the transport of Na+ ions out of and K+ ions into the cell. The concentration gradients of Na+ and
K+ thus generated across the cell membrane have numerous important physiological functions, e.g. maintenance of the
resting potential in nerve cells, cell volume regulation and nutrient reabsorption in the kidney. The aim of this project
is to determine the kinetics and thermodynamics of the individual reaction steps of the enzyme’s complex reaction cycle
and thus obtain a deeper understanding of the mechanism of ion pumping and how it is coupled to ATP hydrolysis.
Major tools involved in these investigations are stopped-flow fluorescence spectroscopy, which allows conformational
changes and charge translocation steps of the enzyme to be resolved on the millisecond timescale, and isothermal titration
calorimetry, which can resolve the heat released in individual reaction steps.
Recently we discovered that the Na+,K+-ATPase from kidney occurs in the membrane in dimeric form. This
allows the enzyme to have two gears of ion pumping depending on the ATP concentration. It also improves the efficiency
of the enzyme and reduces ATP consumption by the cell.
Annual Research Report
23
Regulation of the Na+,K+-ATPase (Rasmussen4)
The Na+ concentration gradient built up across the membrane is essential in driving numerous physiological processes,
including heart muscle contraction and glucose uptake. The enzyme has, thus, been implicated in diseases such as
congestive heart failure and diabetes. In order to locate possible mechanisms of in vivo regulation of the enzyme we
have been constructing kinetic models of the enzyme’s steady state activity based on the kinetic constants of its partial
reactions. The results of such theoretical simulations are then compared to experimental data of the enzyme’s activity
obtained from either whole-cell patch clamp measurements performed at the Royal North Shore Hospital on isolated
rabbit heart muscle cells or activity measurements on purified membrane preparations.
Orientational Polarisability of Membrane Surfaces (Le Goff, Vitha5)
The activity of ion pump membrane proteins is known to be very dependent on the composition of the surrounding
lipid membrane. The mechanisms by which lipids interact with membrane proteins are, however, unclear. We propose
a mechanism whereby dipolar or charged residues in the lipid headgroup region reorientate themselves around highenergy intermediates in the reaction cycle of ion pump proteins. To investigate this hypothesis we have developed a
fluorescence method utitilzing the voltage-sensitive probe, di-8-ANEPPS, to measure the orientational polarisability
of lipid membrane surfaces.
Using our fluorescence method we have recently found that an increase in lipid unsaturation decreases the
orientational polarisability, due to a decrease in the polarity at the membrane surface. The incorporation of cholesterol
into the membrane was also found to decrease the orientational polarisability but by a different mechanism. Cholesterol
causes an ordering of the membrane and a decrease in the range of motion of the lipid head groups.
Voltage-Sensitive Fluorescent Membrane Probes (Vitha5)
Voltage-sensitive fluorescent membrane probes can be used to determine the magnitude of electric field strengths
within lipid membranes and in principle within living cell membranes. We have already developed a technique which is
applicable to synthetic lipid vesicles, as a model membrane system. Now our aim is to extend the project to fluorescence
microscopy and measure the spatial distribution of electric field strength across membrane surfaces and the fluorescence
due to single molecules.
University of Aarhus, Denmark
Unversity of Constance, Germany
3
Laboratoire de Chimie-Physique, Universite Orsay, France
4
Department of Cardiology, Royal North Shore Hospital
5
Drake University, USA
1
2
Selected Publications
1. Clarke, R. The dipole potential of phospholipid membranes and methods for its detection. Adv. Colloid Interfac. Sci., 89-90, 263281, 2001.
2. Bamberg, E, Clarke, RJ and Fendler, K. Electrogenic properties of the Na+,K+-ATPase probed by presteady state and relaxation
studies. J. Bioenerg. Biomem., 33, 401-405, 2001.
3. Kong, BY and Clarke, RJ. Identification of potential regulatory sites of the Na+,K+-ATPase by kinetic analysis. Biochemistry, 43,
2241-2250, 2004.
4. Amoroso, S, Agon, VV, Starke-Peterkovic, T, McLeod, MD, Apell, H-J, Sebban, P and Clarke, RJ. Photochemical behavior and
Na+,K+-ATPase sensitivity of voltage-sensitive styrylpyridinium fluorescent membrane probes. Photochem. Photobiol., 82, 495-502,
2006.
5. Starke-Peterkovic, T, Turner, N, Vitha, MF, Waller, MP, Hibbs, DE and Clarke, RJ. Cholesterol effect on the dipole potential of
lipid membranes. Biophys. J., 90, 4060-4070, 2006.
6. Le Goff, G, Vitha, MF and Clarke, RJ. Orientational polarisability of lipid membrane surfaces. Biochem. Biophys. Acta – Biomembr.,
1768, 562-570, 2007.
7. Hansen, PS, Clarke, RJ, Buhagiar, KA, Hamilton, E, Garcia, A, White C and Rasmussen, HH. Alloxan-induced diabetes reduces
sarcolemmal Na+-K+ pump function in rabbit ventricular myocytes. Am. J. Physiol. Cell Physiol., 292, C1070-C1077, 2007.
8. Clarke, RJ, Apell, H-J and Kong, BY. Allosteric effect of ATP on Na+,K+-ATPase conformational kinetics. Biochemistry, in
press.
24
School of Chemistry
Dr Rachel Codd
Room 412c
School of Chemistry, F11
Telephone: +61 2 9351 4233
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_codd.html
Chemical Biology
Metalloproteins from Cold-Adapted Bacteria (Simpson, Richardson)
The extreme temperatures present on Earth, such as those found
in the boiling hydrothermal vents on the ocean floor and in
freezing Polar regions, have forced resident bacteria and archaea
to adapt to these seemingly inhospitable conditions. Proteins
expressed by ‘extremophilic’ life forms have unusual structures
and may have applications in biotechnology. Proteins expressed
by psychrophilic (‘cold-loving’) bacteria (growth temperature <15
°C), for example, have higher glycine contents, compared to the
analogous mesophilic (growth temperature 20-40 °C) proteins.
Proteins which are active at modest temperatures offer a novel
construct for industrial biocatalytic processes by minimising
unwanted side reactions.
We are examining the nature of cold-adapted
metalloproteins expressed by psychrophilic bacteria isolated
from Antarctic sea ice, focusing on metalloproteins that have
been characterised in mesophilic and hyperthermophilic (growth
temperature > 85 °C) organisms. We have isolated the first-ever
characterised cold-adapted redox-active metalloprotein from an
Antarctic bacterium (periplasmic nitrate reductase) and have used
homology modelling to predict the structure (pictured), based
upon our coupled gene sequencing experiments.
Novel Resins for Molecular Capture and Resolution (Ejje, Liu)
We are developing new chromatographic technologies to capture small molecule metabolites from bacterial cultures. Our
technique enables a high-level of control over the types of molecules to be targeted and has wide ranging implications for
natural products screening. We are examining ways to synthesise resins that are tailored toward resolution chemistry by
immobilising coordination complexes onto resins, using standard coupling techniques. These resins will be well suited
toward resolution of many organic ligands, which has increasing significance in pharmaceutical applications, where
resolved (100% e.e.) compounds are required for use in clinical trials.
Bioinformatics in Chemical Biology (Simpson, Ejje)
Ever-expanding genomic data provides an invaluable resource to chemical biologists. This data can be used to predict
protein expression and/or structure and can be used to chart likely biosynthetic pathways of small molecule metabolites.
We are using bioinformatics to map the biosynthetic pathways of both nonribosomal peptide synthetase (NRPS)-dependent
Annual Research Report
25
and NRPS-independent siderophores in bacteria. These studies will enable our judicious selection of bacteria for the
isolation of native novel siderophore molecules (see project below). Our genome mining studies have implications in
the growing field of medical bioinformatics, focussing upon proteins implicated in human disease to improve the design
of therapeutic targets.
“Super-Siderophores” From Cold-Adapted Bacteria
(Pakchung, Liu)
In order to survive in Antarctic regions, resident bacteria must
adapt their biomolecular machinery to remain functional under
cold conditions (refer to project above). In this project, we are
isolating small-molecule organic chelates involved in microbial
Fe(III) uptake (siderophores) from Antarctic bacteria grown
under conditions of low Fe availability. We hypothesise that
cold-adapted siderophores produced by Antarctic bacteria
will have novel structures and extraordinary affinities towards
Fe(III). Further, we are preparing retroisomers of hydroxamateappended macrocycles as models for cyclised siderophores, such
as desferrioxamine E in addition to tagging Fe(III)-siderophore
receptor/transport proteins.
Metal-Sialic Acid Chemistry (Fainerman-Melnikova,
Kiefel)
Sialic acids (e.g., N-acetylneuraminic acid; Neu5Ac) are negatively-charged carbohydrates located at cell surfaces that
play important roles in cell-recognition processes. We have shown that Neu5Ac (both as the free ligand and as a terminal
glycoconjugate) forms complexes with transition metal ions. We are using several spectroscopic techniques to understand
the speciation between transition metal ions and Neu5Ac and to probe the effects that these interactions have upon metalion attenuated glycoconjugate misprocessing, of relevance to neurodegenerative diseases, such as Alzheimers disease. A
family of organic molecules that model specific regions of Neu5Ac are being prepared to assist in the deconvolution of
metal-Neu5Ac speciation profiles.
Selected Publications
1. Pakchung, AAH, Simpson, PJL and Codd, R. Life on Earth. Extremophiles continue to move the goal posts (Invited Opening
Review for Research Frontier on Extremophiles), Environ. Chem., 3, 77-93, 2006.
2. F a i n e r m a n - M e l n i k o v a , M , C l e g g , J K a n d C o d d , R S . A q u a [ b i s ( 2 - p y r i d y l m e t h y l ) a m i n e ] [ c h e l i d o n a t o
(1.5–)]-copper(II) chelidonate(0.5–) monohydrate. Acta Crystallographica Section E-Structure Reports Online, E62,
m3582-m3584, 2006.
3. Fainerman-Melnikova, M, Szabó-Plánka, T, Rockenbauer, A and Codd, R. Coordination modes between copper(II) and Nacetylneuraminic (sialic) acid from a 2D-simulation analysis of EPR apectra. Implications for copper mediation of sialoglycoconjugate
chemistry relevant to human biology. Inorg. Chem., 44, 2531-2543, 2005.
4. Codd, R. Metalloglycomics: A new perspective upon competitive metal-carbohydrate binding using EPR spectroscopy. Chem.
Commun., 2653-2655, 2004.
5. Codd, R. Biomolecules from extremophilic life. In “From Zero to Infinity”. Eds. Nicholls, JA and Pailthorpe, BA, The Science
Foundation for Physics, School of Physics, University of Sydney: Sydney, pp 37-48, 2003.
6. Codd, R, McKenny, TM and Freiberg, JA. Insights into metallo-isoenzyme forms of oxotransferases using chemical and biochemical
approaches. J. Inorg. Biochem., 96, 119, 2003.
7. Simpson, PJL, Nichols, DS and Codd, RA. Cold-adapted metallo-oxotransferase, periplasmic nitrate reductase, from an Antarctic
bacterium. J. Inorg. Biochem., 96, 230, 2003.
26
School of Chemistry
Annual Research Report
27
Dr Mark J Coster
Toward New AIDS Treatments Based on Inhibition of HIV-1 Integrase (Beare, Fischer, Issa,
Burrell*, Li*)
Room 518
School of Chemistry, F11
Telephone: +61 2 9351 2752
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_coster.html
HIV-1 integrase (IN) is responsible for integration of HIV DNA into the host genome, and has recently been identified as
a highly promising, yet largely untapped, target for anti-retroviral therapies. Our research is focused on the development
of new HIV integrase inhibitors based on two natural product structures, integramycin and lithospermic acid. Our
approach to the synthesis of integramycin, for which an ARC Discovery grant was awarded for 2005–7, is modular in
nature and should allow biological evaluation of various structural subunits of the natural product. A simple synthetic
procedure for accessing the tetramic acid portion of this molecule has been developed and is being further explored. A
carbonylative annulation approach to benzofuran analogues of lithospermic acid has proven fruitful and has recently been
extended to provide the dihydrobenzofuran portion of lithospermic acid by benzofuran reduction.
organic synthesis and stereochemistry
Our research interests include: (i) the development of new synthetic methodologies, with a particular emphasis on
stereoselectivity; (ii) application of these methods to the synthesis of complex, biologically active natural products, and;
(iii) design and synthesis of natural product analogues as potential therapeutic agents.
Anti-Cancer Drugs from the Sea: Synthesis of Highly Cytotoxic Marine Macrolides (Cergol, Davidson,
Loke, O’Connor, Pigott, Reynolds, Szczepina)
Many marine-derived natural products exhibit exceptional levels of biological activity, combined with unique modes
of action. However, the pre-clinical and clinical development of marine-derived natural products into pharmaceuticals
is often hampered by a limited supply from the natural source. We are currently engaged in synthetic efforts toward
two promising marine-derived anti-cancer macrolides, (–)-lasonolide A and amphidinolide H, with the aim to develop
efficient syntheses of the natural products and simplified structural analogues for biological evaluation. The lasonolide
project was awarded an ARC Discovery grant for 2005–2007, and the amphidinolide H project is funded by a University
of Sydney Cancer Research grant for 2004–2005. Progress has been made toward the development of synthetic routes
to tetrahydropyran and the dienoate subunits of lasonolide A, while a new metathesis based approach to the difficult
1,3-diene portion of amphidinolide H is under investigation.
The Boron-Mediated Ketone–Ketone Aldol Reaction (Cergol, Bacskay, Turner)
The first examples of the boron-mediated, cross aldol reaction of ketones were demonstrated in 2004. An investigation
of the scope and stereoselectivity of this reaction was completed and efforts are ongoing to complement the experimental
work with quantum computational studies of the various possible transition state structures for reactions where high
diastereoselectivities were observed. Efforts are ongoing to further explore the scope of this reaction and investigate its
potential uses in asymmetric synthesis.
Selected Publications
Towards the Total Synthesis of Abyssomicin C (Labowitch)
The marine-derived natural product, abyssomicin C shows activity against Gram-positive
bacteria, including methicillin-resistant S. aureus (MRSA), via a mechanism of action
involving inhibition of p-aminobenzoate biosynthesis. Progress has been made in exploring
a Diels–Alder based synthetic approach towards the polycyclic core of this molecule.
New PET Imaging Agents (Banister, Gunosewoyo, Moussa, Kassiou)
This collaborative project is aimed at developing new organic molecules for the imaging of
important receptors associated with neurodegenerative disorders, using positron emission
tomography (PET) techniques. Current work is aimed at the synthesis of polycyclic
hydrocarbon derivatives with potential for use in imaging the P2X7 receptor.
1. Issa, F, Fischer, J, Turner, P and Coster, MJ. Regioselective reduction of 3-methoxymaleimides: An efficient method for the synthesis
of 5-hydroxytetramates. J. Org. Chem., 71, 4703-4705, 2006.
2. Cergol, KM, Turner, P and Coster, MJ. The boron-mediated ketone–ketone aldol reaction. Tetrahedron Lett., 46, 1505-1509,
2005.
3. Paterson, I and Coster, MJ. Total synthesis of spongistatin 1 (altohyrtin A): A tale of ten aldols. Strategies and Tactics in Organic
Synthesis, Volume 4, Chapter 8, Harmata, M., Ed., Elsevier: Oxford, pp 211-245, 2004.
4. Paterson, I, Aceña, JL, Bach, J, Chen, DY-K, Coster, MJ. Synthesis and biological evaluation of spongistatin/altohyrtin analogues
– E-ring dehydration and C46 side-chain truncation. Chem. Commun., 462-463, 2003.
5. Banwell, MG, Coster, MJ, Harvey, MJ and Moraes, J. Selective cleavage of N-benzyl protected 2°-amines by triphosgene. J. Org.
Chem., 68, 613-616, 2003.
6. Banwell, MG, Coster, MJ, Karunaratne, OP and Smith, JAA. Chemoenzymatic Synthesis of the Styryllactone (+)-Goniodiol from
Naphthalene. J. Chem. Soc., Perkin Trans., 1, 1622-1624, 2002.
7. Coster, MJ and De Voss, JJ. Medium ring ethers by ring expansion-ring contraction: Synthesis of lauthisan. Org. Lett., 4, 30473050, 2002.
8. Paterson, I and Coster, MJ. Total synthesis of altohyrtin A (spongistatin 1): An alternative synthesis of the CD-spiroacetal subunit.
Tetrahedron Lett., 43, 3285-3289, 2002.
9. Paterson, I, Chen, DY-K, Coster, MJ, Aceña, JL, Bach, J, Gibson, KR, Keown, LE, Oballa, RM, Trieselmann, T, Wallace, DJ,
Hodgson, AP and Norcross, RD. Stereocontrolled total synthesis of (+)-altohyrtin A/spongistatin 1. Angew. Chem. Int. Ed., 40,
4055-4060, 2001.
28
School of Chemistry
Professor Maxwell J Crossley, FAA
Room 514
School of Chemistry, F11
Telephone: +61 2 9351 2751
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_crossley.html
Annual Research Report
29
Synthesis and Photophysics of Models for the Photosynthetic Reaction Centre (P. Sintic, Blake,
McDonald, Brotherhood, Hutchison*, Ghiggino*, Fukuzumi,* Ohkubo*)
Tris-and tetrakis-porphyrin chemical mimics of the chromophore arrangement of the photosynthetic reaction centre
(PRC) have been further studied. It was found that complexation of ligands, especially chloride ion, at the zinc(II) site
can be used to control the redox driving force for charge separation and the lifetimes of the CS states. In this way very
long-lived CS states were observed. The kinetic and thermodynamic properties of the synthetic PRC’s were investigated
using ultrafast and ESR spectroscopy and electrochemistry. Singlet-singlet annihilation studies gave further insight into
energy transfer in these systems. More elaborate models that incorporate an additional C-60 acceptor unit were designed
and synthesised. These are the closest mimics of the natural systems to be developed anywhere.
Electrochemistry of Porphyrins (Bond*, Hogan*, Kadish*, Khoury, E*, P. Sintic)
Exploration of the redox properties of many different porphyrin-containing systems was undertaken and trends
discerned.
synthesis of functional organic molecules
Porphyrin Arrays As Models For Light-Harvesting Systems And Charge Separation Involved In
Photosynthesis (Khoury, Hambly, D’Alessandro, Blake, McDonald, Saito*, Ohkubo*, Fukuzumi*,
Sundström*, Canton*, J. Larsen*, White*)
Light capture is the first step of photosynthesis. Artificial porphyrin systems designed to mimic light capture in Nature
are currently under investigation. These are based on multi-porphyrin arrays assembled on dendrimer cores, designed
to mimic the LH1 and LH2 systems and the light-harvesting arrays of Photosystem I. Use of other dendritic cores in
the synthesis and their effect on the photophysical properties of resultant porphyrin-appended dendrimers is being
explored along with variation of the porphyrin component. Studies of singlet-singlet and triplet-triplet annihilation
were carried out.
New Advanced Materials (Khoury, Blake, Perry,
Fang, Brotherhood, A. Larsen, Chan, Thordarson,
Webb, M. Sintic, Stocks, Reimers, Hush)
The design and synthesis of new advanced materials based
on metalloporphyrins was continued. A novel approach to
rigid extended aromatic systems has been further developed
to include the synthesis of novel polymers with the potential
to behave as electrical conductors and semi-conductors.
Studies in the areas of molecular switching devices and
molecular shift-registers and novel molecular circuitry were
continued. Additional methodology for construction of
porphyrin building blocks that allow up to four attachments of
molecular wire components was established. New ideas for the
development of a non-volatile molecular-scale memory device
were further developed and further work was undertaken on
design and synthesis of these advanced materials. A means by
which multi-directional extension can be made to a porphyrin
nucleus was developed and is exemplied by synthesis of the
compounds 1 and 2.
Porphyrin-Based Photovoltaic Cells (Reimers, Blake, Dastoor*, Fukuzumi*, Hasobe*, Franzon*)
A solid-state and a solution photovoltaic cell were constructed using thin films and nano-clusters of porphyrin arrays on
optically transparent electrodes as light-harvesting units. Both cells were found to have desirable properties for further
investigation. A new approach to aligned donor-acceptor systems was explored. Aggregates formed between porphyrinappended dendrimers and C60 were found to be relatively efficient materials for use in photovoltaic devices.
Molecular Recognition in Novel Chiral Bis-porphyrin Cavities (Brotherhood)
Compounds with highly selective recognition of dicarboxylic acids were prepared and studied in depth.
Porphyrin Analogues as Gingivitis Inhibitors (Simpkins, Yap, Hunter*)
The black-pigment Gram-negative bacterium Porphyromonas gingivalis is an important etiological agent of adult periodontal
disease. This bacterium has been reported to display an absolute requirement for either hemin or hemoglobin as growth
factors. In this year, a second porphyrin-antibiotic conjugate that is recognised by HA2 receptors of the gingipains and
is a highly selective inhibitor of the P. gingivitis bacterium has been designed, synthesised, evaluated and patented.
Porphyrins in Photonic Crystal Fibres (Martelli*, Canning*, Stocks, M. Sintic)
Compounds that form highly ordered monolayers on the interior of optical fibres were synthesised and studied.
Selected Publications
1. Crossley, MJ, Thordarson, P, Hunter, N, Yap, B and Collyer, CA. Porphyrin linked metronidazole for treatment of gum disease
caused by Porphyromonas Gingivalis. PCT Int. Appl. W02006005137, A1 20060119; CAN 144:128797; AN 2006:54402; 85
pp. International Classification: (IPC1-7): C07D403/14, 19th January 2006.
2. Hogan, CF, Harris, AR, Bond, AM, Sly, J and Crossley MJ. Electrochemical studies of porphyrin-appended dendrimers, Phys. Chem.
Chem. Phys., 8, 2058-2065, 2006.
3. Ohkubo, K, Sintic, PJ, Tkachenko, NV, Lemmetyinen, H, E, W, Ou, Z, Shao, J, Kadish, KM, Crossley, MJ and Fukuzumi, S.
Photoinduced Electron-transfer dynamics and long-lived CS states of donor-acceptor linked dyads and a triad containing a gold
porphyrin in nonpolar solvents, Chem. Phys., 326, 3-14, 2006.
4. Martelli, C, Canning, J, Stocks, D and Crossley, MJ. Water-soluble porphyrin detection in a pure-silica photonic crystal fibre, Optical
Letters, 31, 2100-2102, 2006.
5. Cai, Z-L, Crossley, MJ, Reimers, JR, Kobayashi, R and Amos, RD. Density-functional theory for charge-transfer: The nature of
the N-bands of porphyrins and chlorophylls revealed through CAM-B3LYP, CASPT2, and SAC-CI calculations, J. Phys. Chem. B,
110, 15624-15632, 2006.
6. Larsen, J, Brüggemann, B, Polívka, T, Sly, J, Crossley, MJ, Sundström, V, and Åkesson, E. Energy transfer dynamics in Zn-porphyrinappended dendrimers, in Femtochemistry VII: Fundamental Ultrafast Processes in Chemistry, Physics, and Biology, ed. A. Welford Castleman,
Jr., Elsevier: Amsterdam, 113-116, 2006.
7. Armstrong, RA, Foran, GJ, Hough, WA, D’Alessandro, DM, Lay, PA and Crossley, MJ. Spectroelectrochemical evidence for
communication within a laterally-bridged dimanganese(III) bis-porphyrin, Dalton Trans., 4805-4813, 2006.
8. Larsen, J, Brüggemann, B, Sly, J, Crossley, MJ, Sundström, V and Åkesson, E. Solvent induced control of energy transfer with
Zn(II)-porphyrin dendrimers, Chem. Phys. Lett., 433, 159-164, 2006.
9. Brotherhood, PR, Wu, RA-S, Turner, P and Crossley, MJ. Cavity effect amplification in the recognition of dicarboxylic acids by
initial ditopic H-bond formation followed by kinetic trapping, Chem. Commun., 225-227, 2007.
10.Kadish, KM, E, W, Zhan, R, Khoury, T, Govenlock, LJ, Prashar, KJ, Sintic, PJ, Ohkubo, K, Fukuzumi, S and Crossley, MJ.
Porphyrin-diones and porphyrin-tetraones: Reversible redox units being localized within the porphyrin macrocycle and their effect
on tautomerism, J. Am. Chem. Soc., 129, 6576-6588, 2007.
11.Webb, JEA, Crossley, MJ, Turner, P and Thordarson, P. Bisisophthalamide aggregates and their response to anion stimuli, J. Am.
Chem. Soc., 129, 7155-7162, 2007.
12.Hulsken, B, van Hameren, R, Gerritsen, JW, Khoury, T, Thordarson, P, Crossley, MJ, Rowan, AE, Nolte, RJM, Elemans, JAAW
and Speller, S. Real-time single molecule imaging of oxidation catalysis at a liquid-solid interface, Nature Nanotechnolgy, 2, 285-289,
2007.
13. Hulsken, B, van Hameren, R, Thordarson, P, Gerritsen, JW, Nolte, RJM, Rowan, AE, Crossley, MJ, Elemans, JAAW and Speller,
S. Scanning tunneling microscopy and spectroscopy studies of porphyrins at solid-liquid interfaces, Jpn. J. Appl. Phys., 45, 19531955, 2006.
30
School of Chemistry
Emeritus Professor Hans C Freeman
AM, FAA
Honorary Staf
Room 146
School of Chemistry, F11
Telephone: +61 2 9351 4504/16028
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_freeman.html
The structure and function of
metalloproteins
Many biological processes depend on types of protein, whose molecular structure includes one or more essential metal
atoms. Research on the crystal structures of such proteins was initiated in the (then) Department of Inorganic Chemistry
in about 1975. An early success was the structure analysis of plastocyanin, a ‘blue’ copper protein with unusual
spectroscopic properties and an essential electron-transfer function in photosynthesis. Since then, the structures and
amino-acid sequences of plastocyanin from numerous organisms have been reported. A systematic study of these data,
aimed at understanding how the proteins of this type evolved, is in progress.
Current research on metalloproteins is focused on the crystal structures of auracyanin, a ‘blue’ copper protein
from the primitive photosynthetic bacterium Chloroflexus aurantiacus; and copper amine oxidases, a widely distributed class
of copper enzymes. In order to explore the mechanism and specificity of the copper amine oxidases, we are undertaking
crystal structure analyses of complexes of the enzymes with organic inhibitor molecules, and complexes of the enzymes
with electronic ‘wires’. The electronic ‘wires’ are synthetic compounds that can connect a catalytic site buried deep in an
enzyme molecule with the external solvent. In addition. they have been shown to be potent inhibitors of the enzymes’
activity.
The University’s protein structure laboratory, originally located in the School of Chemistry, was Australia’s
first centre for the study of macromolecular crystal structures. It was moved to the Department of Biochemistry (now
the School of Molecular and Microbial BioSciences) in 1995. The study of metalloprotein structures is a continuing
collaboration with Professor J Mitchell Guss, Director of the Protein Crystallography Laboratory.
International collaborators in 2005 included Professor RE Blankenship, Arizona State University, and Dr. M.
C. del Rosario, University of California at San Francisco (auracyanin), Professor DM Dooley, Montana State University
(amine oxidases), and Professor HB Gray, California Institute of Technology (‘wire’ complexes). Collaborators within the
University of Sydney were Dr H. Harris, Chemistry (X-ray absorption spectra), Dr WB Church, Pharmacy (plastocyanin
structural comparisons), Dr LS Jermiin and Professor AWD Larkum, Biological Sciences (plastocyanin phylogenetic
studies).
Selected Publications
1. Freeman, HC. Metalloprotein crystallography. In “Spectroscopic Methods in Bioinorganic Chemistry”, K.O. Hodgson and E.I.
Solomon (Eds.), ACS Symposium Series No. 692, American Chemical Society, Washington, Chapter 4, 62-95, 1998.
2. Wilce, MCJ, Bond, CS, Dixon, NE, Freeman, HC, Guss, JM, Lilley, PE and Wilce, JA. Structure and mechanism of a proline-specific
aminopeptidase from Escherichia coli. Proc. Natl. Acad. Sci. USA, 95, 3472-3477, 1998.
Annual Research Report
31
3. Bond, CS, Bendall, DS, Freeman, HC, Guss, JM, Howe, CM, Wagner, MJ and Wilce, MCJ. The structure of plastocyanin from the
cyanobacterium Phormidium laminosum. Acta Cryst., D55, 414-421, 1999.
4. Shi, D, Hambley, TW and Freeman, HC. Crystal structures of three platinum(II)-dipeptide complexes. J. Inorg. Biochem., 73,
173-186, 1999.
5. Bond, CS, Blankenship, RE, Freeman, HC, Guss, JM, Maher, MJ, Selvaraj, FM, Wilce, MCJ and Willingham, KM. Crystal structure
of auracyanin, a ‘blue’ copper protein from the green thermophilic photosynthetic bacterium Chloroflexus aurantiacus. J. Mol. Biol.,
306, 47-67, 2001.
6. Freeman, HC and Guss, JM. Plastocyanin. In “Handbook of Metalloproteins”, R. Huber, T. L. Poulos and K. Wieghardt (Eds.),
Wiley, Chichester, 1153-1169, 2001.
7. Rooney, MB, Honeychurch, MJ, Selvaraj, FM, Blankenship, RE, Bond, AM and Freeman, HC. A thin-film electrochemical study
of the ‘blue’ copper proteins, auracyanin A and auracyanin B, from the photosynthetic bacterium Chloroflexus aurantiacus: The
reduction potential as a function of pH. J. Biol. Inorg. Chem., 8, 306-317, 2003.
8. Duff, AP, Cohen, AE, Ellis, PJ, Kuchar, JA, Langley, DB, Shepard, EM, Dooley, DM, Freeman, HC and Guss, JM. The crystal
structure of Pichia pastoris lysyl oxidase. Biochemistry, 42, 15148-15157, 2003.
9. Maher, JM, Ghosh, M, Grunden, AM, Menon, AL, Adams, MWW, Freeman, HC and Guss, JM. Structure of the prolidase from
Pyrococcus furiosus. Biochemistry, 43, 2771-2783, 2004.
10. Duff, AP, Trambaiolo, DM, Cohen, AE, Ellis, PJ, Langley, DB, Dooley, DM, Guss, JM and Freeman, HC. Using xenon as a probe
for dioxygen-binding sites in copper amine oxidases. J. Mol. Biol., 344, 599-607, 2004.
11. Sträter, N, Jasper, B, Scholte, M, Krebs, B, Duff, AP, Langley, DB, Han, R, Averill, BA, Freeman, HC and Guss, JM. Crystal
structures of recombinant human purple acid phosphatase with and without an inhibitory conformation of the repression loop. J.
Mol. Biol., 351, 233-246, 2005.
12. Contakes, SM, Juda, GA, Langley, DB, Halpern Manners, NW, Duff, AP, Dunn, AR, Gray, HB, Dooley, DM, Guss, JM and Freeman,
HC. Reversible inhibition of copper amine oxidase activity by channel-blocking ruthenium(II) and rhenium(I) molecular wires.
Proc. Natl. Acad. Sci. USA, 102, 13451-13456, 2005.
13.Duff, AP, Cohen, AE, Ellis, PJ, Hilmer, K, Langley, DB, Dooley, DM, Freeman, HC, Guss, JM. The 1.23Å structure of Pichia
pastoris lysyl oxidase reveals a lysine-lysine cross-link. Acta Cryst., D62, 1073-1084, 2006.
14.Langley, DB, Duff, AP, Freeman, HC, Guss, JM. The copper-containing amine oxidase from Arthrobacter globiformis: refinement at
1.55 and 2.20Å resolution in two crystal forms. Acta Cryst., F62, 1052-1057, 2006.
15.Duff, AP, Shepard, EM, Langley, DB, Dooley, DM, Freeman, HC, Guss, JM. A C-terminal disulfide bond in the copper-containing
amine oxidase from pea seedlings violates the two-fold symmetry of the molecular dimmer. Acta Cryst., F62, 1168-1173, 2006.
32
School of Chemistry
Dr Adrian V George
Room 210/223
School of Chemistry, F11
Telephone: +61 2 9351 4413
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_george.html
synthesis, analysis and education
Detection of Steroid Use in Sport (Brooker,
Cawley)
Dehydroepiandrosterone (DHEA), androst-4-ene3,17-dione (ADIONE), androst-4-ene-3β,17β-diol
(4-ADIOL;) and androst-5-ene-3β,17β-diol (5ADIOL), are naturally produced androgens, that
may be administered by athletes with the aim of
increasing levels of the more active androgens such
as testosterone (T) and dihydrotestosterone (DHT).
The International Olympic Committee (IOC)
prohibits administration of these steroids in athletes;
however their detection remains difficult due to an
incomplete understanding of metabolism as well as
inter-individual variations.
In this study, a marker compound that indicates exogenouse abuse of each of these steroids has been found.
Confirmation of administration can then be made by use of Gas Chromatography-Combustion-Isotope Ratio Mass
Spectrometry (GC-C-IRMS). A study of over 1000 athletes has established a typical range of steroid isotope ratios
observed in athletes of different gender, age and ethnic origin. This has allowed a range of carbon isotope ratios to be
established that indicate steroid abuse.
Improved High-Performance Liquid Chromatography - Tandem Mass Spectrometry (LC-MS/MS) methodology
for the quantification and confirmation of synthetic glucocorticosteroid (GCs) abuse in sport has also been developed and
validated. Utilizing stable isotopically labeled processed internal standards, the method was used to assess excretion
studies from permitted (topical/local) and prohibited (systemic) modes of therapeutic synthetic GC administration.
Results from four forms of topical/local administration (dermal, inhalation, nasal spray, heel injection) of the synthetic GC
triamcinolone acetonide (TA) showed that all TA excretion was completed within 24 hours, except for the injection study
where detection was confirmed for up to four days post-administration. Results from an oral (systemic) administration
of triamcinolone (T) showed that the maximum urinary concentration was greater than 3 µg/mL, or more than 100
times the World Anti-doping Agency (WADA) specified (laboratory) minimum required performance limit. This work
is being extended to the detection of abuse of endogenous steroid hormones by use of isotope ratio mass spectrometry.
Profiling of Synthetic Illicit Drugs (Salouros)
Isotope ratio techniques may be used to detect the origin of opium based illicit drugs. This is not satisfactory for
synthetic drugs based on amphetamine. Trace impurities in clandestine manufactured drugs are the result of a number
of reasons. They can be due to impurities being present in the precursors, solvents and/or reagents which can be carried
Annual Research Report
33
over into the final product unchanged or they can react and be transformed into other products. Impurities can also be
generated as by-products in the drug manufacturing process. Finally the conditions of storage, such as exposure to light
and heat, as well as cutting agents introduced may affect the drug and/or impurities, thus introducing new impurities.
Research is being undertaken to link the impurity profile in a reaction with method and conditions of synthesis. This
will enable a ‘finger print’ of a synthetic approach to be established and, ultimately, provide a method to determine the
origin of batches of seized drugs.
Education in Chemistry (Masters, Read, Schmid, Yeung)
Detailed analysis, both qualitative and quantitative, of examination scripts from some first year chemistry units has
been undertaken. When combined with qualitative data from students about their experiences and perceptions, a
number of interesting questions can be addressed. Firstly, the question of the extent to which the outcomes from our
current assessment system are a reflection of students’ understanding can be examined. Analysis of students’ approaches
to examination questions provides information about both misconceptions held and overall motivations and goals
(performance orientation versus mastery orientation). Such information can be used not only to improve teaching in
areas of student difficulty, but can also inform curriculum design more generally, with the ultimate goal of promoting
deeper student understanding of the material under study. Secondly, the analysis provides data that supports the common
belief that organic chemistry is an area that some students simply ‘don’t get’. The existence of barriers to deeper
understanding of organic chemistry has been proven, and the nature of these barriers examined. Such information has
obvious implications for improving teaching and learning in this fundamental area of chemistry, although more work
in this area is needed. In another project the connection between a person’s learning style (eg whether they prefer to learn in group
situations or ‘go it alone’) and they way they interact with different leaning situations is probed. In particular whether
the personalization of text (where the material is presented in a conversational style) results in different learning outcomes
compared to a more traditional impersonalized presentation.
Organometallic Catalysis (Frey, Gardiner)
The project aim is to use the porphyrinogen and calixpyrrole structure as a ligand for metals engaged in catalysis reactions.
By providing a cavity for the metal we intend to extend the lifetime of the catalyst and have the ability to modify the
reactivity of the metal through a variety of interactions with the calixpyrrole host. Large radii lanthanoid metals, such
as samarium, have been coordinated in the cavity. Syntheses of a range of these cavity materials has been developed.
Selected Publications
1. Cawley, AT, Hine, ER, Trout, GJ, George, AV and Kazlauskas, R. Searching for new markers of endogenous steroid administration
in athletes: “Looking outside the metabolic box”. Forensic Science International, 143 (103), 2004.
2. George, AV, Cawley, AT, Kazlauskas, R, Trout, GJ and Rogerson, JH. Isotopic fractionation of endogenous anabolic androgenic
steroids and its relationship to doping control in sports. Journal of Chromatographic Science, 43 (1), 32-38, 2005.
3. George, AV, Cawley, AT, Kazlauskas, R and Trout, GJ. Determination of urinary steroid sulfate metabolites using ion paired
extraction. Journal of Chromatography B-Analytical Technologies in the Biomedical and Life Sciences, 825 (1), 1-10, 2005.
4. Youl, DJ, Read, JR, George, AV, and Schmid, S. (2006). Bridging courses: Good learning environments for engaging students? 9th
Pacific Rim First Year in Higher Education (FYHE) Conference: ‘Engaging Students’. Griffith University in conjunction with Queensland
University of Technology, Gold Coast, 12-14 July 2006. Available from http://www.fyhe.qut.edu.au. ISBN 0-646-46313-6.
5. Yeung, A, George, AV, King, MM, Schmid, S. (2006) Testing the personalisation hypothesis in pre-laboratory e-learning
environments. In Symposium Proceedings: Assessment in Science Teaching and Learning. Sydney, NSW: UniServe Science, 146 – 152.
Available from http://science.uniserve.edu.au/pubs/procs/2006/yeung.pdf. ISBN 1-86487-865-7.
34
School of Chemistry
Professor Robert G Gilbert, FAA
Room 351
School of Chemistry, F11
Telephone: +61 2 9351 3366
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_gilbert.html
polymer colloids
Polymers and Emulsion Polymerization: Novel Structure and Properties (Castignolles, Sangster,
Vosloo, Thickett, Aungsupravate, Sharma, Koh, Mange, Seabrook, Leswin, Youssef, Taylor, Li).
The relationship between molecular and mesoscopic structure on the one hand and mechanical and other end-use properties
on the other is a major unsolved problem in polymer colloids. The study of how changes at the molecular level affect
physical properties incorporates projects ranging from the preparation of novel nanoparticles to the development of new
methods for living radical polymerization in emulsion systems, including both surface coatings (paints etc.) and barrier
products (surgical gloves, etc.). Other ongoing projects include the preparation of nanoscale particles through emulsion
polymerization, synthesis and characterization of novel polymer colloids with grafted and branched architectures, effects
of molecular architecture on mechanical properties (with University of Queensland and the preparation of next-generation
environmentally-friendly surface coatings (with Dulux Australia). Fundamental investigations have explored the effect
of mobile surfactants and electrosteric stabilizers on the kinetics of particle growth and formation, as well as examining
their effects on the end-use properties of surface coatings derived from polymer latices. Studies have been completed on
the effect of grafted in-situ stabilizer on the effect of entry and exit of monomeric polymeric radicals. Work continues
on the fundamental science of free radical polymerization with a project on reversible addition-fragmentation chain
transfer using emulsion polymerization and involvement in IUPAC initiatives to develop more rigorous protocols for
determination of propagation and termination rate coefficients.
Polymer Colloids in Natural Systems (Gaborieau, Hernandez, Ward, Cuevas, Willoughby, Chang)
The aims of this project are to apply the experimental and theoretical techniques developed for the characterization of
synthetic polymer colloids to natural polymers. This is leading to the development of models for the molecular architecture
of starch hydrocolloids and starch biosynthesis. Theoretical and experimental work is being carried out on obtaining
and interpreting reliable data on branched biopolymers, especially starchesExtensive new knowledge has been produced
on how the molecular weight distribution of starches affects physical properties such as “mouth-feel”, and how these
molecular weight distributions may be used to infer biological pathways in starch synthesis (with the International Rice
Research Institute in Manila, and the CRC for Quality Rice and NSW Agriculture). The last-named work has produced
the exciting discovery which will enable rice breeders to understand why two apparently very similar varieties of rice
grain have very different cooking properties: a result of major importance to farmers.
Selected Publications
1. Castignolles, P, Gaborieau, M, Hilder, EF, Sprong, E, Ferguson, CJ and Gilbert, RG. High-resolution separation of oligo(acrylic
acid) by capillary zone electrophoresis. Macromolecular Rapid Communications, 27, 42-46, 2006.
2. Chang, JC, Gurr, GM, Fletcher, MJ and Gilbert, RG. Structure–property and structure–function relations of leafhopper (Kahaono
montana) silk. Australian Journal of Chemistry, 59, 579-585, 2006.
3. De Bruyn, H, Sprong, E, Gaborieau, M, David, G, Roper, JA, Gilbert, RG. Starch-graft-Copolymer Latexes Initiated and Stabilized
by Ozonolyzed Amylopectin. Journal of Polymer Science: Part A: Polymer Chemistry, 44, 5832-5845, 2006.
Annual Research Report
35
4. Gilbert, RG. Particle formation by self-assembly in controlled radical emulsion polymerizations. Macromolecules, 39, 4256-4258,
2006.
5. Mock, EB, De Bruyn, H, Hawkett, BS, Gilbert, RG and Zukoski, CF. Synthesis of anisotropic nanoparticles by seeded emulsion
polymerization. Langmuir, 22, 4037-4043, 2006.
6. Perry, PA, Fitzgerald, MA and Gilbert, RG. Fluorescence recovery after photobleaching as a probe of diffusion in starch systems.
Biomacromolecules, 7, 521-530, 2006.
7. Prescott, SW, Ballard, MJ, Rizzardo, E and Gilbert, RG. Rate optimization in controlled radical emulsion polymerization using
RAFT. Macromolecular Theory and Simulations, 15, 70-86, 2006.
8. Ratinac, KR, Gilbert, RG, Ye, L, Jones, AS and Ringer, SP. The effects of processing and organoclay properties on the structure
of poly(methyl methacrylate)–clay nanocomposites. Polymer, 47, 6337-6361, 2006.
9. Save, M, Guillaneuf, Y and Gilbert, RG. Controlled radical polymerization in aqueous dispersed media. Australian Journal of
Chemistry, 59, 693-711, 2006.
10.Sprong, E, Leswin, JSK, Lamb, DJ, Ferguson, CJ, Hawkett, BS, Pham, BTT, Nguyen, D, Such, CH, Serelis, AK and Gilbert, RG.
Molecular watchmaking: ab initio emulsion polymerization by RAFT-controlled self-assembly. Macromolecular Symposia, 231, 84-93,
2006.
11.Thickett, SC and Gilbert, RG. Mechanism of radical entry in electrosterically stabilized emulsion polymerization systems.
Macromolecules, 39, 6495-6504, 2006.
12.Thickett, SC and Gilbert, RG. Rate-controlling events for radical exit in electrosterically stabilized emulsion polymerization
systems. Macromolecules, 39, 2081-2091, 2006.
13.van Berkel, KY, Russell, GT and Gilbert, RG. The dissociation rate coefficient of persulfate in emulsion polymerization systems.
Polymer, 47, 4667-4675, 2006.
14.Ward, RM, Gao, Q, de Bruyn, H, Gilbert, RG and Fitzgerald, MA. Improved methods for the structural analysis of the amyloserich fraction from rice flour. Biomacromolecules, 7, 866-876, 2006.
36
School of Chemistry
Professor Trevor W Hambley
Room 412a
School of Chemistry, F11
Telephone: +61 2 9351 2830
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_hambley.html
medicinal inorganic chemistry
Tuning the Chemistry of Platinum(IV) Drugs (Alderden, Callaghan#, New)
Platinum(IV) complexes are more inert than their Pt(II) analogues and
therefore have the potential to be less toxic. Fluorescent tags were attached
at the leaving and non-leaving group positions of Pt(II) complexes, and to
the axial position of a Pt(IV) cisplatin-based complex. The fluorescence of
all fluorophores was quenched partially or fully on binding to platinum. The
axially-substituted complex exhibited a reduction potential in the range of
cytotoxic Pt(IV) complexes, and treatment with cysteine and ascorbic acid
led to an increase in fluorescence, consistent with reduction and release of the fluorophore. This confirms the potential
of such complexes as fluorescent probes of the reduction event.
Annual Research Report
37
Trans-platinum complexes are generally therapeutically inactive, but attachment of bulky amines generates active
complexes. A transplatin analogue containing the fluorophore 7-azaindole was synthesised, and found to have a trans
activating effect. This complex is therefore a suitable fluorescent model for the study of active trans‑platinum complexes.
A2780 ovarian cancer cells were treated with cis­- and trans‑substituted azaindole complexes and visualised by two-photon
confocal fluorescence microscopy. The preliminary images obtained reveal the appearance of fluorescence in cells over a
period of time, suggesting cleavage of the fluorophore from the complex. These results confirm that coordination state
sensitive fluorescence is a promising technique for probing the uptake and metabolism of platinum complexes within
cells, and highlight modifications to the fluorophores which will enable more sensitive studies.
Selective Targeting of Solid Tumours using Cobalt Complexes (Yamamoto)
The goal of our work is to develop new agents that selectively target solid tumours by taking advantage of the differences
between tumours and healthy tissues. The specific aims of this project are to develop new cobalt-based hypoxia-selective
agents and to modify such agents to achieve the desired level of targeting. In order to do this, we are developing new
methods for determining the oxidation state of the hypoxia-selective agents and to investigate their fate in solid tumours
and in models of this environment. The rational development of hypoxia-selective agents has been hampered by a lack
of knowledge of where and when the agent is reduced and the cytotoxic ligand released. We have investigated cobalt
complexes with ligands attached that become fluorescent on release the first time this approach has been used to monitor
the loss of ligands from cobalt complexes. The damping of fluorescence on coordination to cobalt(III) is so great that
the complex is effectively non-fluorescent. The appearance of fluorescence indicates the separation of the ligand from
the complex, either as a result of reduction or ligand loss. In either case, we are able to monitor the critical event in the
delivery of a cytotoxin within a tumour cell by visually monitoring where and when the fluorescence appears. Using
this technique, we have shown that coumarin-343, coumarin-343 hydroxamate and their cobalt(III) complexes have
dramatically different distribution patterns in A2780 ovarian cancer cells. The ability of such fluorescence based methods
to report on the release of ligands in solid tumours and tumour models is the next stage of this study and is expected to
reveal the potential of cobalt complexes to target the hypoxic regions of solid tumours.
The Distribution of Platinum Complexes in Cells and Tumours (Alderden, Whan, Zhang)
The development of new metal-based drugs that reach all regions of a tumour has been limited by our ability to track
the uptake of the complex. However, the use of fluorophore tagged complexes offers a solution to this problem and we
and others have been using anthraquinone tagged platinum complexes to study uptake in cells. These studies show
that the tag modifies the properties of the platinum moiety, resulting in increased uptake into the cell, but perhaps
also increased disposition to subcellular organelles such as lysosomes (below) and modified cytotoxicity. For instance,
Pt1C3 (see right) has the potential to form covalent (coordinate) bonds with DNA in the same way as cisplatin, but can
also bind non-covalently with the anthraquinone intercalated between the DNA bases. MTT cytotoxicity assays with
A2780 human ovarian carcinoma cells reveals that Pt1C3 has a cytotoxicity that is similar to that of cisplatin after 72
h drug exposure, though interestingly it is more active than cisplatin is after 24 h, when its cytotoxicity is similar to
that of 1C3 itself. Thus, Pt1C3 displays the cell killing features of both the intercalator and the platinum moiety which
may be advantageous in achieving high efficacy against a non-uniform cell population. The cell killing properties of
these compounds is reflected in their subcellular distribution which has features associated with both the platinum and
intercalator (below), demonstrating the value of being able to visualize the distribution. What is needed is to establish
whether these same visualization techniques can be used to monitor the uptake in solid tumours and tumour models and
thereby contribute to the optimization of the properties needed to give improved uptake throughout a tumour.
Confocal images of A2780 cells showing: top row; the
fluorescence due to coumarin-343 blue) overlaid with the
fluorescence due to the nuclear stain SYTO® 21 (green)
and bottom row; the fluorescence due to [Co(coumarin343)2(cyclam)]ClO4 (blue) overlaid with the fluorescence
due to the nuclear stain SYTO® 21 (green)
Targeting of Metastatic Tumours using MMP Binding Agents (Doan, Guenther, Kassiou)
Almost all compounds used in the treatment of cancer cause serious side effects because they lack selectivity for tumours.
However, the rapidly increasing knowledge and understanding of the differences between the chemistry and biochemistry
of tumours and healthy tissues means that it is now possible to envisage drugs that act selectively on tumours. Our
work is aimed at developing new agents that selectively target solid tumours by taking advantage of these differences.
An important difference that has emerged relatively recently is the overexpression of matrix metalloproteinases (MMPs)
in metastasising tumours. The synthesis of a range of novel MMP binding agents with the ability to carry therapeutic
and/or imaging radionuclides was begun.
Selected Publications
Confocal images of A2780 cells showing the fluorescence due to [Pt(dien)1C3] (red) overlaid with the fluorescence due to the
nuclear stain SYTO® 21 (green) revealing uptake in lysosomes and limited uptake in the nuclei.
1. A Co(III) complex of the MMP inhibitor marimastat: a potential hypoxia activated prodrug. T.W. Failes, C. Cullinane, C.I. Diakos,
N. Yamamoto, J.G. Lyons, and T.W. Hambley. Chemistry, A European Journal, , 13, 2974-2982, 2007.
2. Cytotoxic efficacy of an anthraquinone linked platinum anticancer drug. R.A. Alderden, H.R. Mellor, S. Modok, T.W. Hambley,
and R. Callaghan. Biochemical Pharmacology, 71, 1136-1145, 2006.
38
School of Chemistry
Professor Margaret M Harding
Honorary Staff
School of Chemistry, F11
Telephone: +61 2 9351 4504
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_harding.html
biological and medicinal chemistry
Annual Research Report
39
cellular uptake relative to other neutral and polar thiol derivatives of molybdocene dichloride previously studied, the
derivative is predicted to show reduced cellular uptake. The results show that incorporation of electron withdrawing
groups on the aromatic rings of thiol ligands is insufficient to achieve hydrolysis within hours, and strongly suggests
that if a lipophilic analogue can be prepared that retains the trifluoroethane thiol fragment, high cell uptake followed
by slow hydrolysis can be achieved in cells.
DNA Nanshuttles (Lee, Saccavini, Rendina)
Molecular clefts derived from the dibenzobicyclo[b,f][3.3.1]nona-5a,6a-diene-6,12-dione framework contain a rigid
angular backbone and a chiral cavity by virtue of the bridgehead structure. Tunable handles in the form of the dione
and aryl groups allow for functionalization and structural modification of these clefts. Synthesis, functionalization and
resolution of some of these clefts have been recently reported. by our group. These structural features provide the ideal
platform for construction of metallosupramolecular nanosquares with tailored or programmed properties.
A range of clefts of varying dimensions with pyridyl groups installed at the distal arms have been designed
and synthesized, using standard cross-coupling methodologies (Suzuki and Sonogashira reactions). The preparation of
water-soluble derivatives (via installation of polyols for example) and the assembly of water-soluble metallomacrocycles
allows entry into a new classs of metallomacrocycles that encircle DNA, a binding mode that is utilised by Nature with
toroidal proteins, but is unprecedented in synthetic chemistry.
Selected Publications
Antifreeze Proteins and Glycoproteins (Turner, Inglis, Price*)
Antifreeze proteins (AFPs) and glycoproteins (AFGPs) permit many species of fish to survive in sub-zero oceans without
freezing. These antifreeze compounds have potential applications in the frozen food industry (eg. maintaining the texture
of ice cream), medical science (eg., cryosurgery) and veterinary science (eg. storage of sperm). Commercial applications are
limited by the amounts of compounds available from fish and the lack of understanding of how these proteins work.
Pulsed Field Gradient Spin Echo NMR Spectroscopy was used to measure diffusion coefficients of the a-helical
type I antifreeze protein from the winter flounder, two synthetic derivatives in which the four Thr residues were replaced
with Val and Ala respectively, and the low molecular weight fraction antifreeze glycoprotein. Under the conditions
studied, the natural type I antifreeze protein and low molecular weight glycoprotein gave diffusion values that were
consistent with the presence of monomeric protein in solution. While significant aggregation of the Ala analogue was
observed (2-10 mM), there was no evidence for aggregation in the Val analogue (1-3 mM). These results correlate well
with solubilitydata and thermal hysteresis data and have important implications for the design of synthetic antifreeze
proteins.
Organometallic Anticancer Agents (Waern, Dillon)
A range of molybdocene derivatives were designed to probe the importance of solubility, charge and the lability of the
Mo-X bond on cell uptake and cytotoxicity and hence to provide fundamental data that is essential to assess whether
Cp2MoCl2, or metal complexes based on this framework, are promising lead compounds for the development of
molybdocene-based anticancer drugs. These first structure activity studies on molybdocene dichloride established that
the labile Mo–Cl bonds in Cp2MoCl2 are a requirement for activity. Incorporation of thiols in place of the halogen ligands
provides access to stable, water soluble derivatives, some of which are able to enter cells, but that lack the cytotoxicity of
the parent complex. Incorporation of the electron-withdrawing fluorinated aromatic rings into the structure resulted in
more labile ligands, though not on a time scale to be relevant inc cells. The distinct cytotoxicity and cell uptake profiles
of Cp2MoCl2 compared with Cp2Mo(GS)2 show that while rapid coordination of Cp2MoCl2 to glutathione occurs in
water at pH 7, this interaction is not significant in cell culture media and that other transport mechanisms are involved
in vitro and in vivo.
The design, synthesis, and hydrolytic stability of thiol derivatives incorporating electron withdrawing
substituents was completed. These derivatives were studied in order to evaluate the effect of the trifluoromethyl groups
on the stability of the Mo–S bond, and thus provide fundamental data needed to guide the design of potential prodrugs
of Cp2MoCl2 that hydrolyze on an hour timescale to release the active “Cp2Mo2+” species in the cell. The hydrolysis
of the trifluoroethane thiol ligands clearly demonstrates that the incorporation of a trifluoromethyl group one carbon
away from the Mo–S bond results in increased lability of the Mo–S bonds in molybdocene derivatives Cp2Mo(SR)2. In
aqueous DMSO, the rate of hydrolysis (approximately 50% in 14 h) is on a time-scale that is potentially useful in the
design of prodrugs of Cp2MoCl2. However as this complex lacks the lipophilic aromatic groups, which exhibited high
1. Liepinsh, E, Otting, G, Harding, MM, Ward, LG, Mackay, JP and Haymet, ADJ. Solution structure of a hydrophobic analogue
of the winter flounder antifreeze protein. European Journal of Biochemistry, 264, 1269-1266, 2002.
2. Fairley, K, Westman, BJ, Pham, LH, Haymet, ADJ, Harding, MM and Mackay, JP. Type I shorthorn sculpin antifreeze protein:
Recombinant synthesis, NMR spectroscopy & ice growth inhibition properties. Journal of Biological Chemistry, 277, 24073-24080,
2002.
3. Tomczak, MM, Hincha, DK, Crowe, JH, Harding, MM and Haymet, ADJ. The effect of hydrophobic analogues of the type I
winter flounder antifreeze protein on lipid bilayers. FEBS Letters, 551, 13-19, 2003.
4. Harding, MM, Anderberg, PI and Haymet, ADJ. “Antifreeze” glycoproteins from polar fish. European Journal of Biochemistry, 270,
1381-1392, 2003.
5. Waern, JB and Harding, MM. Coordination chemistry of the antitumor metallocene molybdocene dichloride with biological ligands.
Inorganic Chemistry, 43, 206-213, 2004.
6. Harding, MM, Waern, JB and Dillon, CT. Organometallic anticancer agents: Cellular uptake and cytotoxicity studies on thiol
derivatives of the antitumor agent molybdocene dichloride. Journal of Medicinal Chemistry, 48, (6), 2093-2099, 2005.
7. Kwan, A-H, Fairley, K, Anderberg, PI, Liew, CW, Hardingm MM and Mackay, JP. Solution structure of a recombinant type I
sculpin antifreeze protein: the effects of supercooling and acetylation. Biochemistry, 44, 1980-1988, 2005.
8. Campbell, KS, Foster, AJ, Dillon, DT and Harding, MM. Genotoxicity and transmission electron microscopy studies of molybdocene
dichloride. Journal of Inorganic Biochemistry, 100, 1194-1198, 2006.
9. Inglis, SR, McGann, MJ, Price, WS and Harding, MM. Diffusion NMR studies on fish antifreeze proteins and synthetic analogues.
FEBS Letters, 580, 3911-3915, 2006.
10.Lee, CKY, Groneman, JL, Turner, P, Rendina, LM and Harding, MM. Synthesis and x-ray crystallographic analysis of chiral pyridyl
substituted carbocyclic molecular clefts. Tetrahedron, 62, 4870-4878, 2006.
11.Waern, JB, Turner, P and Harding, P. Synthesis and hydrolysis of thiol derivatives of molybdocene dichloride incorporating
electron-withdrawing substituents. Organometallics, 25, 3417-3421, 2006.
40
School of Chemistry
Dr Hugh Harris
Room 516
School of Chemistry, F11
Telephone: +61 2 9351 2745
Facsimile: +61 2 9351 3329
Email: [email protected]
Sulfite Oxidase (George*, Rajagopalan*)
Human sulfite oxidase catalyzes the two-electron oxidation of sulfite to sulfate, a vital step in the catabolism of sulfur
containing amino acids. This occurs at a molybdenum centre which is reduced from MoVI to MoIV in the process. The
molybdenum is coordinated by the ene-1,2-dithiolate of the molybdopterin cofactor and a protein based cysteine thiolate
plus two oxo ligands in the MoVI form, one of which is converted to hydroxide or water in the MoIV form. As yet, the
precise functional role of each of the ligands to the metal is not clear. We have combined high resolution EXAFS with
DFT calculations to identify the O-donor ligand in the reduced form as water and not hydroxide.
Oxidized
bioinorganic chemistry
Structure of the Cu-binding Domain of the
Amyloid Precursor Protein (Parker*)
Alzheimer’s disease is thought to be triggered by the
production of the peptide Aβ generated through proteolytic
cleavage of the amyloid precursor protein (APP). APP can
function as a metalloprotein for Cu transport into and out
of cells using its Cu-binding domain (CuBD). Cu binding
to CuBD reduces the production of Aβ. Thus a mimic of Cu
action may have therapeutic potential. We have determined
the structures of the apo, Cu+ and Cu2+ forms of CuBD using
XRD, XAS and EPR. These reveal only small conformational
changes in the Cu-binding site for the Cu-bound forms
compared to the apo structure. The site resembles a Type 2
non-blue Cu centre. We have proposed a model to explain
how Cu binding leads to decreased Aβ production.
Imaging the Biotransformation of Arsenic in a Hyperaccumulating Fern (George*, Pickering*)
The fern Pteris vittata accumulates unusually high levels of arsenic. Using X-ray absorption spectroscopy (XAS) and XAS
imaging, we have revealed the distribution of arsenic species in vivo. Arsenate is transported through the vascular tissue
from the roots to the fronds (leaves), where it is reduced to arsenite and stored at high concentrations. Arsenic-thiolate
species surrounding veins may be intermediates in this reduction. In gametophytes, arsenite is compartmentalized within
the cell vacuole. Arsenic is excluded from cell walls, rhizoids and reproductive areas. This study provides important
insights into arsenic hyperaccumulation and demonstrates the strengths of XAS imaging for distinguishing highly
localized species.
[arsenite]
[arsenate]
41
Annual Research Report
Reduced
Selected Publications
1. Harris, H, Fisher, K and Dance, I. Coordination and dehydrogenation of PH3 by 23 transition metal ions in the gas phase: FTICR
experiments and density functional interpretations. Inorg. Chem., 40, 6972-6982, 2001.
2. Brown, KR. Keller, GL. Pickering, IJ. Harris, HH. George, GN and Winge, DR. Structures of the cuprous-thiolate clusters of
the Mac1 and Ace1 transcriptional activators. Biochemistry, 41, 6469-6476, 2002.
3. George, GN, Pickering, IJ, Harris, HH, Gailer, J, Klein, D, Lichtmannegger, J and Summer K-H. Thiomolybdate causes formation
of copper-molybdenum clusters in an animal model of Wilson’s disease. J. Amer. Chem. Soc., 125, 1704-1705, 2003.
4. Harris, HH, Pickering, IJ and George, GN. The chemical form of mercury in fish. Science, 301, 1203, 2003.
5. Sneeden, EY, Harris, HH, Pickering, IJ, Prince, RC, Johnson, S, Li, X, Block, E and George, GN. The sulfur chemistry of Shiitake
mushroom. J. Amer. Chem. Soc., 126, 458-459, 2004.
6. George, GN, Prince, RC, Gailer, J, Buttigieg, GA, Denton, MB, Harris, HH, and Pickering, IJ. Mercury binding to the chelation
therapy agents DMSA and DMPS and the rational design of custom chelators for mercury. Chem. Res. Toxicol., 17, 999-1006,
2004.
7. Harris, HH, Levina, A, Dillon, CT, Mulyani, I, Lai, B, Cai, Z and Lay, P. Time dependent uptake, distribution and biotransformation
of chromium(VI) in individual human lung cells: Application of synchrotron radiation techniques. J. Biol. Inorg. Chem., 10,
105-118, 2005.
8. Levina, A, Harris, HH and Lay, PA. Binding of chromium(VI) to histones: Implications for chromium(VI)-induced genotoxicity.
J. Biol. Inorg. Chem., 11, 225-234, 2006.
9. Harris, HH, George, GN and Rajagopalan, KV. High-resolution EXAFS of the active site of human sulfite oxidase: Comparison
with density functional theory and x-ray crystallographic results. Inorg. Chem., 45, 493-495, 2006.
10.Milsmann, C, Levina, A, Harris, HH, Foran, GJ, Turner, P and Lay, PA. Charge distribution in chromium and vanadium catecholato
complexes: X-ray absorption spectroscopic and computational studies. Inorganic Chemistry, 4743-4754, 2006.
11.Harris, HH and Dance, IG. Iron-carbon clusters: Geometric structures and interconversions. Polyhedron, 26, 250-265, 2007.
42
School of Chemistry
Professor Peter R Harrowell
Room 316
School of Chemistry, F11
Telephone: +61 2 9351 4102
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_harrowell.html
Annual Research Report
43
Structure and Stability of Ionic Clusters and Reverse Micelles (Wootton)
Small clusters represent a fascinating window onto how atoms and molecules behave at surfaces and the enhanced
possibilities for structures once long range order is no longer necessary. Using computer simulations we are currently
studying the following three questions. i) Can ions form polyhedral clusters that are stable with respect to crystal
fragments? ii) How are ion clusters hydrated by water? iii) What is the structure and phase behaviour of small clusters of
liquid crystal forming molecules? A systematic study of silver halide clusters has indicated that polyhedral clusters (ionic
analogues of buckyballs) are stable when the anion is considerably larger than the cation. A study of clusters of hard sphere
monovalent ions showed how custers convert from polyhedra to crystal fragments as the cluster size increases. Reverse
micelles formed from ionic surfactants are, at low water concentrations, ionic clusters and we are currently working on
resolving the long-standing problem of what determines their equilibrium size in terms of stable ordered structures.
Molecular Walkers (Barrett)
physical chemistry of materials
The binding of macromolecules to surfaces is a key process in many nanotechnology applications. We have been examining
how the degree of structural registry between a molecule and a crystal surface can dramatically alter both its binding
energy and the mobility of the molecule. Using a very generic representation of molecular shape and rigidity, we are
currently preparing a comprehensive mapping of the possible surface behaviour of molecules.
Structure and Dynamics of Amorphous Alloys (Fernandez, Widmer-Cooper, Fynewever)
The theoretical description of the properties of amorphous solids represents a major challenge in both materials science and
the fundamental theory of condensed matter. Our tools are computer simulations of the dynamics of model liquids and the
theoretical methods of statistical mechanics. We have introduced a fundamental new direction to this problem with the
recognition that a meaningful structural description of the amorphous states is an essential prerequisite to a meaningful
explanation of its dynamic behaviour. Our work has focussed on amorphous mixtures, models of the glassy alloys currently
underdevelopment as advanced materials. In seeking to understand the structure of such mixtures, Fernandez and PH
published a major study of the energetic of substitutionally ordered crystals comprising of binary mixtures of atoms. This
study, along with providing a library of possible atomic structures and their associated energetics, offers a ready reference
for designing model mixtures with desired crystal phases for studies of interfaces, phase transitions, etc. We also published
a detailed study of the structure of a glassy alloy, modelled on the Ni-P system. In this work we identified a small set
of coordination clusters that dominated the structure of the glass. We explored the relationship between these clusters,
the structure of the glass and the stability with respect to crystallisation. This work has provided the starting point
to our ongoing efforts to provide a general expression of glass and crystal structure in terms of combinations of generic
structures. Turning to another major theme of our glass work, we (Widmer-Cooper, Fynewever and PH) published a new
perspective on the phenomenon of dynamic heterogeneity in supercooled liquids. Addressing the persistent difficulty in
finding a clear correlation between structure and these spatial variations in dynamics, we proposed that the propensity
for motion rather than the actual motion itself was the more suitable quantity to link with structure. By establishing
exactly what aspect of the dynamics is structurally determined we have provided a much clearer focus to the question of
the structure-dynamics relationship. This work is currently being developed into a clear statement of the glass transition
problem and the form the answer must take.
Lubrication Films and the Statistical Theory of Friction (Petravic, Jabbarzadeh)
Using a combination of nonequilibrium simulations and statistical theory of linear response, we are developing a
comprehensive picture of the molecular level processes responsible for a remarkable range of rheology observed in thin
films of lubricant between smooth crystalline walls. Studying nanometer thin films of dodecane between mica walls we
(Jabbarzadeh, Tanner and PH) have established, in agreement with experiment, that both ultra-low friction films as well
as practically rigid films can be produced depending on film thickness, wall structure and degree of film equilibration.
The ultra-low friction films are associated with a state in which the linear alkane molecules are aligned while the very
high friction state is the result of the formation of a novel ‘mosaic’ structure, quite distinct from anything observed in
bulk crystals. We have also established that decreasing the in-plane order of the walls results in the destablization of both
extremes of the rheological states. This latter result could provide valuable in designing surfaces for nanoscale fluidics.
We (Petravic and PH) are also addressing the fundamental question of surface transport properties, thermal conductivity
and friction, through the development of a new formulation of linear response theory aimed specifically at systems driven
by boundary constraints. The general formalism is complete and was published in 200513 and we are working on using
it to understand the molecular level contributions to these fundamental properties.
Selected Publications
1. Harrowell, P. Glass transitions in plane view. Nature Physics, 2, 157-158, 2006.
2. Jabbarzadeh, A, Harrowell, P and Tanner, RI. Crystal bridge formation marks the transition to rigidity in a thin lubrication film.
Physical Review Letters, 96, 206102, 2006.
3. Jabbarzadeh, A, Harrowell, P and Tanner, RI. Low friction lubrication between amorphous walls: Unraveling the contributions of
surface roughness and in-plane disorder. Journal of Chemical Physics, 125, 034703, 2006.
4. Petravic, J and Harrowell, P. An equilibrium calculation of the thermal transport coefficients between two planes of arbitrary
separation in a condensed phase. Journal of Chemical Physics, 124, 044512, 2006.
5. Petravic, J and Harrowell, P. Crystal-melt coexistence under shear: Interpreting the nonlinear rheology. Journal of Chemical Physics,
125, 124502, 2006.
6. Petravic, J and Harrowell, P. The boundary fluctuation theory of transport coefficients in the linear-response limit. Journal of
Chemical Physics, 124, 014103, 2006.
7. Petravic, J and Harrowell, P. Erratum: Linear response theory for thermal conductivity and viscosity in terms of boundary
fluctuations. Phys. Rev. E., 74, 049903, 2006.
8. Thomas, BS, Marks, NA and Harrowell, P. Inversion of defect interactions due to ordering in Sr1-3x/2LaxTiO3 perovskites: An
atomistic simulation study. Physical Review B, 74, 214109, 2006.
9. Widmer-Cooper, A and Harrowell, P. Free volume cannot explain the spatial heterogeneity of Debye–Waller factors in a glassforming binary alloy. Journal of Non-crystalline Solids, 352, 5098-5102, 2006.
10.Widmer-Cooper, A and Harrowell, P. Predicting the long-time dynamic heterogeneity in a supercooled liquid on the basis of
short-time heterogeneities. Physical Review Letters, 96, 185701, 2006.
11.Harrowell, P and Petravic, J. Linear response theory for thermal conductivity and viscosity in terms of boundary fluctuations.
Physical Review E, 71, (6), 061201-1-061201-6, 2005.
12.Harrowell, P and Widmer-Cooper, A. On the relationship between structure and dynamics in a supercooled liquid. Journal of
Physics Condensed Matter, 17, (49), 4025-4034, 2005.
13.Harrowell, P, Jabbarzadeh, A and Tanner, RI. Very low friction state of a dodecane film confined between mica surfaces. Physical
Review Letters, 94, 126103-1-126103-4, 2005.
14.Widmer-Cooper, A, Fynewever, H and Harrowell, P. How reproducible are dynamic heterogeneities in a supercooled liquid? Phys.
Rev.Lett., 93, 135701, 2004.
15.Wootton,A and Harrowell, P. Inorganic nanotubes stabilized by ion size asymmetry: Energy calculations for AgI clusters. J.Phys.
Chem.B, 108, 8412, 2004.
16.Fernandez, J and Harrowell, P. Ordered binary crystal phases of Lennard-Jones mixtures. J.Chem.Phys., 120, 9222, 2004.
17.Fernandez, J and Harrowell, P. Organisation of coordination polyhedra in an amorphous alloy. J.Phys.Chem.B, 108, 6850, 2004.
18.Butler, S and Harrowell, P. Factors determining the crystal-liquid coexistence under shear. Nature, 415, 1008, 2002.
19.Wootton, A, Thomas, B and Harrowell, P. Radiation-induced densification in amorphous silica: A computer simulation study.
J.Chem.Phys., 115, 3336, 2001.
20.Wild, R and Harrowell, P. Density functional theory of the kinetics of crystallization of hard-sphere suspensions. Coupling structure
to density. J.Chem.Phys., 114, 9059, 2001.
44
School of Chemistry
Dr Toby Hudson
Room 209d
School of Chemistry, F11
Telephone: +61 2 9351 4813
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/~hudson_t
Theoretical Materials Chemistry
Annual Research Report
45
hopping Monte Carlo, attempt to solve this problem by exploring the vast configuration space efficiently. Fundamental
to all of these methods are choices about: the way the system is represented; the mechanisms used for altering it; the ability
to recognize recurring states that have already been tested; and the selection criteria for accepting a change. We developed
a new, highly efficient method for recognizing states represented by discrete parameters [5]. In this vein we adapted
genetic algorithms to use a discrete representation - the bond connectivity matrix - in atomic systems. We developed a
robust procedure to map the system from bonds to Cartesian coordinates. However these genetic algorithms are not yet
competitive in this system. This stems from the fact that when represented by their bonds, high valence networks are
(redundantly) over-constrained. Thus when we try to “breed” pairs of different trial solutions, we get numerous clashing
constraints, so the “child” is almost never a “viable” low-energy structure.
We have also begun data mining the Inorganic Crystal Structure Database with the intention of extracting
common structural motifs and trends for use in structural search. Initial results have found that two commonly occurring
structures, when optimized, can pack binary hard spheres with a particular radius ratio even more densely than the
close-packing the two species can obtain when separated. Only one example of this has previously been found amongst
non-interstitial structures.
Phase Field Models for Nucleation in Eutectic Binary Systems (Clements, Harrowell)
The process of nucleation from the melt is a key determinant of the microstructure of a material, and its crystallization
kinetics. This process is by its nature both small and fast, making it difficult to probe experimentally, but amenable to
simulation. Simple analytic models are available for single-component systems if they are modelled with a single spatial
parameter: crystallinity. However, in multi-component systems there is competition between nuclei of the different solids,
as well as an intricate coordination between structural and compositional ordering. We constructed a phase-field model
able to reproduce the essential features of a binary phase diagram with a eutectic point. This model was then solved for
the case of a spherically-symmetric critical nucleus, allowing us to determine the compositional and structural radial
profiles, together with the free energy of formation. This methodology can be applied to solidification at any temperature
from any liquid composition, which allows us to overlay the phase diagram with measures of the predicted kinetics and
microstructure upon a quench into these solid-solid coexistence regions. We are interested in applying a similar model
to the equilibrium liquid state to investigate the nature of compositional and structural fluctuations.
Amorphous Network Solids (Harrowell, Sutton†, Dwyer†,
Winkelman†, Nguyen-Manh†, Cockayne†)
In amorphous materials, computer modelling has the ability to probe
atomic and topological information directly, whereas experiment
often only gives averages and distributions. Nevertheless, this is
vital to understanding their electronic and structural properties
in applications such as photoelectric amorphous semiconductors.
In contrast to crystals, where relaxation and diffusion mechanisms
are dominated by the motion of individual, well-defined defects
[4,5,8,9,10], amorphous materials often evolve using collective and
unpredictable mechanisms. We developed a systematic series of
topology-altering mechanisms, which can be applied to any network,
and conserve the valence of every atom [1]. The series includes
concerted mechanisms involving multiple bond rearrangements. It
can be used to categorize observed topological changes, or as a broad
set of trial moves that can be used in Monte Carlo simulations of these materials. These mechanisms were tested in
separate MC simulations on a simple tetravalent continuous random network, allowing us to establish their efficiency for
both energetic minimization, and structural sampling [1]. On both measures, we showed that a previously known and
widely used mechanism is indeed optimal at low temperatures, and found other good candidates for use in combination
with it, or for use at higher temperatures.
Structural Search Algorithms (Kummerfeld, Harrowell, Mason†)
In condensed matter systems there are an extremely large number of metastable local energy minima, which confound
easy discovery of the true global minimum. This problem strikes a number of fields, including cluster chemistry, protein
folding, and complex crystals. Stochastic search algorithms such as simulated annealing, genetic algorithms, and basin
Global energy minimum structures of Lennard-Jones clusters LJ-55, LJ-81, and LJ-150, obtained from a
representation in which only the bond connectivity matrix was provided.
†
Co-worker not associated with the University of Sydney.
Selected Publications
1. Hudson, TS and Harrowell, P. A systematic enumeration of local topological relaxation mechanisms in amorphous networks and
their efficiency in network relaxation. Journal of Chemical Physics, 126, 184502, 2007.
2. Hudson, TS, Nguyen-Manh, D, van Duin, ACT and Sutton, AP. Grand canonical Monte Carlo simulations of intergranular glassy
films in b silicon nitride. Materials Science and Engineering A-Structural Materials Properties Microstructure and Processing, 422, 123-135,
2006.
3. Winkelman, GB, Dwyer, C, Marsh, C, Hudson, TS, Nguyen-Manh, D, Doblinger, M and Cockayne, DJH. The crystal/glass interface
in doped Si3N4. Materials Science & Engineering, A: Structural Materials: Properties, Microstructure and Processing, A422 (1-2), 77-84,
2006.
4. Hudson, TS, Caturla, M-J, Dudarev, SL and Sutton, AP. Effects of elastic interactions on post-cascade radiation damage evolution
in kinetic Monte-Carlo simulations. Philosophical Magazine, 85, 661-675, 2005.
5. Mason, DR, Hudson, TS and Sutton, AP. Fast recall of state-history in kinetic Monte-Carlo simulations utilising the Zobrist key.
Computer Physics Communications, 165, 37-48, 2005.
6. Winkelman, GB, Dwyer, C, Hudson, TS, Nguyen-Manh, D, Doblinger, M, Satet, RL, Hoffmann, MJ and Cockayne, DJH. Three
dimensional organization of rare-earth atoms at grain boundaries in silicon nitride. Applied Physics Letters, 87, 1-3, 2005.
7. Winkelman, GB, Dwyer, C, Hudson, TS, Nguyen-Manh, D, Doeblinger, M, Satet, RL, Hoffmann MJ and Cockayne, DJH.
Arrangement of rare-earth elements at prismatic grain boundaries in silicon nitride. Philosophical Magazine Letters, 85, 755-762,
2004.
8. Hudson, TS, Dudarev, SL and Sutton, AP. Suppression of interstitial cluster diffusion by oversized solute atoms. Journal of Nuclear
Materials, 329-333, 971-976, 2004.
9. Hudson, TS, Dudarev, SL and Sutton, AP. Confinement of interstitial cluster diffusion by oversized solute atoms. Proceedings of the
Royal Society of London: Math. Phys. & Eng. Sci., 460, 2457-2475, 2004.
10.Hudson, TS, Dudarev, SL and Sutton, AP. Absence of saturation of void swelling in rate theory with anisotropic diffusion. Journal
of Nuclear Materials, 307-311, 976-981, 2002.
46
School of Chemistry
Annual Research Report
Dr Julia M James
Analytical & Environmental Geochemistry
Our research interests are in the area of environmental geochemistry with special emphasis on the chemical reactions
taking place in caves. Some studies in progress are:
Paleoclimatic Studies From Speleothems And Cave Sediments
We are obtaining paleoclimatic records from speleothems and sediments throughout Australia using uranium/thorium
radionuclide methods. The average temperatures at the time of deposition are established by stable isotope measurements.
Submerged calcite deposits found under the Nullarbor Plain are being studied for their association with bacterial colonies
and the variation in surface temperature and sea level changes over the last 4 million years. These results are important
in modelling future changes in sea-level from the greenhouse effect.
Trace Organics And Trace Metals In Speleothems Studies
Extraction and identification of trace metals and organic materials and their complexes from within the calcite matrix
are being carried out. We have established that amino acids are present in many speleothems and are using amino acid
racemisation dating techniques to study the geochemical record of specimens up to one million years old.
Selected Publications
1. James, JM. Corrosion par melange des eaux dans les grottes de la plaine de Nullarbor, Australie (Mixing corrosion in the caves of
the Nullarbor Plain, Australia). Special issue of Karstologia, Karst et Evolutions Climatics, 332-347, 1992.
2. Contos, AK, James, JM, Heywood, B, Pitt, K and Rogers, P. Morphoanalysis of bacterially precipitated subaqueous calcium
carbonate from Weebubbie Cave, Australia. Geomicrobiology, 18, 331-343, 2001,
3. Holmes, AJ, Tujula, NA, Holley, NM, Contos, AK, James, JM and Rogers, PAW. Phylogenetic structure of unusual aquatic
microbial formations in the Nullarbor Caves, Australia. Environmental Microbiology, 3, (4), 256-264, 2001.
4. Hose, GC, James, JM and Gray, MR. Spiders webs as environmental indicators. Environmental Pollution, 725-733, 2002.
5. James, JM. The crystal gallery. In Beneath the Surface: A Natural History of Australian Caves, edited by Finlayson, B and HamiltonSmith, E, University of NSW Press, 53-86, 2003.
6. James, JM, Contos, AK and Barnes, C. The Nullarbor Caves. In Encyclopaedia of Caves, edited by David Culver, and William White,
WB, New York, Elsevier, 418-426, 2004.7.
7. James, JM. Giant dolines of the Muller Plateau, Papua New Guinea. Cave and Karst Science, 32, 85-91, 2005.
8. Webb, JA and James, JM. Karst evolution of the Nullarbor Plain, Australia, in Harmon, R.S., and Wicks, C., eds. Perspectives
on karst geomorphology, hydrology, and geochemistry — A tribute volume to Derek C. Ford and William B. White: Geological
Society of America Special Paper 404, 65–78, 2006.
Diver sampling rare calcite precipitating microbial mantles in the Weebubbie Lake
Honorary Staff
Room 146
School of Chemistry, F11
Telephone: +61 2 9351 2743
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_james.html
47
48
School of Chemistry
Dr Katrina A Jolliffe
Room 515
School of Chemistry, F11
Telephone: +61 2 9351 2297
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_jolliffe.html
Annual Research Report
49
useful is to get enough 10B to the tumour cells. Cyclic RGD peptides are capable of specifically targeting integrin proteins
which are overexpressed by tumour cells. We are investigating the attachment of 10B-containing agents to these tumour
targeting peptides to enable the selective delivery of 10B to multiple tumour types for BNCT.
Cyclic Peptide Based Anion Receptors (Reynolds, McDonough, Young, Butler)
The selective recognition and sensing of biologically important anions under physiological conditions is of intense current
interest to both chemists and biologists, since this has numerous applications in biomedicine. Backbone modified cyclic
peptides are ideal scaffolds for the construction of molecular anion receptors and we are currently investigating the
synthesis and application of a range of such receptors. Anions such as pyrophosphate (P2O74-, PPi) play important roles
in bioenergetic and metabolic processes. We have recently developed a cyclic-peptide based fluorogenic ‘chemosensing
ensemble’ capable of selectively detecting low concentrations of PPi under physiological conditions.
Organic Synthesis and
supramolecular chemistry
New Methods for the Efficient Cyclisation of Small Peptides (Sayyadi, Leesch, Cochrane)
There has recently been a great deal of interest in the synthesis of small cyclic peptides. Naturally occurring cyclic
peptides exhibit a wide range of biological activities and are often more resistant to enzymatic hydrolysis than their linear
counterparts. Additionally, the restricted conformational flexibility of cyclic peptides allows them to present functional
groups in a spatially well-defined manner and is of use in the study and mimicry of protein folding. However, the currently
available methods for the head-to-tail cyclisation of linear peptides are often slow and low-yielding. We recently developed
a new method for the efficient head-to-tail synthesis of small cyclic peptides and examined its use in a model system.
We have now extended this methodology to the synthesis of novel cyclic peptides incorporating from 4-9 amino acids
and have applied it in the synthesis of the anti-malarial cyclic peptide mahafacyclin B, increasing the cyclisation yield
from 23% to over 60%. Other cyclic peptide targets including Axinellin A, a cyclic peptide with antitumour activity,
and LIF-04a, a cyclic depsipeptide with antifungal activity, are currently being synthesised.
Design and Synthesis of Selective Inhibitors of Fungal Virulence Factors (Obando, Sorrell*,
Widmer*)
Pathogenic fungi are increasingly implicated as a cause of serious and potentially fatal disease, especially in
immunocompromised hosts. Many of these fungi have been found to secrete enzymes that contribute to their virulence
and therefore present new targets for drug discovery. The primary aim of this project is to design and synthesise selective
inhibitors of fungal phospholipases for use as therapeutic agents. We are examining a number of compound classes for
antifungal and phospholipase inhibitory activity and have found that these are correlated, supporting the hypothesis
that the fungal phospholipase is a new target for drug discovery. We have synthesised a number of compounds that
show strong inhibition of the fungal enzyme but do not inhibit mammalian phospholipases and our best compound has
comparable antifungal activity to the currently marketed antifungal drug, Amphotericin B.
Boronated Cyclic Peptides for Cancer Treatment Using BNCT – (Rendina, Ziolkowski)
Boron Neutron Capture Therapy (BNCT) is a new cancer treatment that relies on the remarkable neutron capture
properties of the non-radioactive 10B nucleus. The major problem that needs to be overcome for BNCT to be clinically
Self-Assembled Molecular Capsules (Yuen, O’Malley, Clegg, Lindoy)
Backbone rigidified cyclic peptides are ideal platforms for use in the preparation of nanoscale molecular capsules, as they
allow the functional groups required for self-assembly to be arranged in a spatially well-defined manner and will provide
capsules with a large interior volume. We are investigating the use of azole-heterocycle containing cyclic peptides for
this purpose and have prepared a number of scaffolds, functionalised with ligands, for self assembly upon the addition
of an appropriate metal ion.
Selected Publications
1. Ng, CKL, Singhal, V, Widmer, F, Wright, LC, Sorrell, TC and Jolliffe, KA. Synthesis, antifungal and hemolytic activity of a series
of Bis(pyridinium)alkanes. Bioorg. Med. Chem., 15, 3422-3429, 2007.
2. McDonough, MJ, Reynolds, AJ, Lee, WYG and Jolliffe, KA. Selective recognition of pyrophosphate in water using a backbone
modified cyclic peptide receptor. Chem Commun., 2971-2973, 2006.
3. Di Vittorio, KM, Johnson, JR, Johansson, E, Reynolds, AJ, Jolliffe, KA and Smith, BD. Synthetic peptides with selective affinity
for apoptotic cells. Org. Biomol. Chem., 4, 1966-1976, 2006.
4. Ng, CKL, Obando, D, Widmer, F, Wright, L, Sorrell, TC and Jolliffe, KA. Correlation of antifungal activity with fungal phospholipase
inhibition using a series of bisquaternary ammonium salts. J. Med. Chem., 49, 811-816, 2006.
5. Sayyadi, N, Skropeta, D and Jolliffe, KA. N,O-isopropylidenated threonines as tools for peptide cyclisation: Application to the
total synthesis of mahafacyclin. Org. Lett., 7, 5497-5499, 2005.
6. Jolliffe, KA. Backbone modified cyclic peptides: New scaffolds for supramolecular chemistry. Supramol. Chem., 17, 81-86, 2005.
7. Skropeta, D, Jolliffe, KA and Turner, P. Pseudo-prolines as removable turn inducers: Tools for the cyclisation of small peptides.
J. Org. Chem., 69, 8804-8809, 2004.
50
School of Chemistry
Dr Meredith Jordan
Room 241
School of Chemistry, F11
Telephone: +61 2 9351 4420
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_jordan.html
51
Annual Research Report
Molecular Structure (Chebib,1 Crittenden, Thompson)
We have combined the Grow package with quantum diffusion Monte Carlo methods to allow us to accurately predict
the vibrationally averaged (ground state) structure of relatively large molecules and clusters. We have applied these
methods to ethanediol. H2O, glycine.8H2O, glycyl radical.8H2O and GABA.5H2O. We have also developed the first
chemically accurate PES for the CH5+ system, chemistry’s “cheshire cat”. Representations of some of our molecular
structures are illustrated:
intermolecular interactions
Computational Drug Design (Chebib,1 Crittenden)
γ-aminobutyric acid (GABA) is the major neuro-inhibitor in the brain. Understanding how GABA works aids in
developing drugs to treat diseases such as epilepsy, depression, anxiety and Alzheimer’s disease. We have developed new
computational techniques to study in vivo amino acids and have applied these, together with experiment, to GABA and
a range of GABA analogues. This has enabled us to determine the first Quantitative Structure Activity Relationship
(QSAR) for the GABAC receptor and to characterize the bioactive template molecule, TACA.
below-plane substitution
here tolerated, may possess
either agonist or antagonist
activity
all above-plane substitution
tolerated, with agonist activity
below-plane substitution here
strictly not tolerated
GABA.5H2O
The most probably structure of CH5+
Molecular Reactivity (Crittenden, Kable, Thompson)
We have calculated the first accurate PES for the photodissociation of T1 acetaldehyde, a reaction important in atmospheric
pollution. Dynamical calculations on this PES agree well with experiment and provide the first theoretical demonstration
of reaction dynamics undergoing a transition from impulsive to statistical behaviour in the product state distributions
as excess energy increases. Our calculations have also resolved a number of discrepancies in previous experimental and
theoretical studies of this system.
Faculty of Pharmacy, University of Sydney
Faculty of Medicine, University of Sydney
3
School of Molecular and Microbial Biosciences, University of Sydney
1
2
The Calcium Sensing Receptor (CaSR) (Clifton-Bligh,2 Conigrave,3 Corley)
The CaSR is involved in regulating calcium within the body and is a target for drugs to treat osteoporosis, one of the
major health issues facing Australia. We have modelled the interaction of hydrated Ca2+, Mg2+ and Sr2+ ions with the
amino acid residues implicated in the CaSR showing the importance of acidic and very polar residues together with the
protein backbone group. We have used these models to describe the qualitative and quantitative differences observed
between the binding of the Ca2+ and Mg2+ ions. Our calculations have enabled us to identify a putative binding site
within the extracellular domain of the CaSR.
Putative CaSR binding site:
S147, S170, S171, D190,
Y218, G273, S296, E297
Potential binding
pocket for cation
Molecular Potential Energy Surfaces (Collins,* Thompson, Crittenden)
Molecular potential energy surfaces (PES) describe how the energy of a molecule changes as the positions of its constituent
atoms change. We have developed new interpolation techniques for constructing PES based on highly accurate quantum
chemical calculations. A new computer package Grow has been released making these techniques freely available and we
are currently implementing Grow within the GAMESS quantum chemical program suite.
Selected Publications
1. Crittenden, DL, Park, A, Qiu, J, Silverman, RB, Duke, RK, Johnston, GAR, Jordan, MJT and Chebib, M. Enantiomers of cisconstrained and flexible 2-substituted GABA analogues exert opposite effects at recombinant GABAC receptors. Bioorganic &
Medicinal Chemistry, 14, 447-455, 2006.
2. Thompson, K, Crittenden, DL, Kable, SH and Jordan, MJ. A classical trajectory study of the photodissociation of T1 acetaldehyde:
The transition from impulsive to statistical dynamics. Journal of Chemical Physics, 124, 044302, 2006.
3. Crittenden, DL, Chebib, M and Jordan, MJT. Quantitative structure-activity relationships of GABAC receptor agonists. J. Mol.
Struct., (Theochem), 755, 81-89, 2005.
4. Crittenden, DL, Kumar, RJ, Hanrahan, J, Chebib, M and Jordan, MJT. The stabilisation of zwitterions in solution: Phosphonic
and phosphinic acid GABA analogues. J. Phys. Chem. A, 109, 8398-8409, 2005.
5. Crittenden, DL, Chebib, M and Jordan, MJT. The stabilisation of zwitterions in solution: GABA analogues. J. Phys. Chem. A, 109,
4195-4201, 2005.
6. Thompson, KC, Crittenden, DL and Jordan, MJT. CH5+: Chemistry’s chameleon unmasked. J. Am. Chem. Soc., 127, 4954-4958,
2005.
7. Crittenden, DL, Thompson, KC and Jordan, MJT. On the extent of intramolecular hydrogen bonding in gas-phase and hydrated
1,2-ethanediol. J. Phys. Chem. A, 109, 2971-2977, 2005.
8. Crittenden, DL and Jordan, MJT. Interpolated potential energy surfaces: How accurate do the second derivatives have to be? J.
Chem. Phys., 122, 044102, 2005.
52
School of Chemistry
Associate Professor Scott H Kable
Room 308
School of Chemistry, F11
Telephone: +61 2 9351 2756/3811
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_kable.htm
laser-induced chemistry
Lasers have revolutionised many aspects of chemistry, including our understanding of chemical reactivity, characterisation
of new materials, and all forms of spectroscopy. The reason for this large diversity of applications lies in the range of
effects that intense light has on different materials – breaking bonds, ablating solids, ionising materials, and tickling
molecules to behave in certain ways. The research interests of our group include photochemistry, spectroscopy, mass
spectrometry and theoretical chemistry. More details can be found on our web page.
Photodissociation Dynamics (Jordan, Rowling, Heazlewood)
Chemical reactions are often understood in terms of a specific reaction mechanism or pathway. When two or more
competing mechanisms give rise to the same chemical products, then our ability to predict rates, branching ratios, and
quantum yields is compromised. It is experimentally and theoretically challenging to separate the influence of each
competing pathway to reveal the underlying mechanisms. The photodissociation of H2CO is crucial in the chemistry
of the atmosphere, and exhibits two such competing mechanisms. The production of H + HCO is an example of a
reaction occurring on two different electronic states, which compete in the production of a single set of products. The
ground state (S0) is barrierless, whereas the lowest triplet state (T1) has a small barrier. In 2005, in collaboration with
researchers from Emory University, we identified the fingerprints of these mechanisms (Science, 2006, 311, 1443), and
recently published a full description of the process (J. Chem. Phys, 2007, in press). Reactions on S0 produce HCO with
high rotational excitation (N in figure), and are modelled well by statistical theory of photodissociation. The T1 channel
produces HCO that is rotationally cold. High level trajectory calculations confirm the identification and quantitatively
reproduce the experimental data.
We also examined the photodissociation dynamics
of acetaldehyde and discovered that acetaldehyde reacts to
form the molecular products CO + CH4 via two different
mechanisms. One of these is the traditional “transition state
mechanism” (see right), in which the reaction proceeds via a
well-defined 3-centre transition state. The other proposed
mechanism is via a “roaming”-type pathway, which was
first demonstrated by Suits and Bowman in the case of
formaldehyde. In the roaming mechanism, the reaction
proceeds towards radical products, HCO + CH3 , however,
doesn’t quite make it. The methyl group then roams around
the periphery of the HCO core, then re-reacts with itself,
Annual Research Report
53
abstracting a H-atom from HCO and ends up as extremely hot methane and very cold CO. If proven, then this is only
the second example of roaming in the literature, and the first example of a anything except a H-atom roaming.
Spectroscopy and Structure of Radicals (Bacskay, Schmidt, Reilly)
Free radicals have proven elusive to study because of their inherence reactivity. Consequently, the chemistry and
structure of many radicals remains unknown and has been the subject of active research for many years. In collaboration
with Dr Schmidt in the School of Chemistry, we have turned our attention to radical species that might be found in
the interstellar medium. Many UV-visible absorption and emission bands around and between stars appear to exhibit
molecular fingerprints, yet the majority have not been identified. There are almost as many theories as observations,
but the only way to positively identify these bands is by measuring them in the laboratory (see Dr Schmidt’s page for
more details about the astro-spectroscopy project). In 2005, we installed and tested a new discharge nozzle and in 2006
we generated new spectra of important molecules and discovered new molecules.
Dicarbon (C2) is a textbook example of chemical bonding, alongside N2 and O2. Last year we reported a new
spectroscopic transition and measured a new electronic state of C2 (C2 is of such importance that transitions are usually
named after the discoverers.) This is the only known transition involving this state, and will be crucial for astronomical
models of carbon abundance in space. We have also very recently discovered a new molecule, the phenylpropargyl radical,
that is formed in a benzene discharge. Most intriguingly, this molecule absorbs light at 476 nm, which corresponds to
one of the mysterious, unassigned diffuse interstellar bands that have been taunting astronomers since their discovery
80 years ago.
2-Dimensional Fluorescence Spectroscopy (Schmidt,
Reilly)
The “soup” of unstable and reactive species formed in the discharge is
very rich, and so too is the spectroscopy complicated by overlapping
bands. We have developed a two-dimensional spectroscopic technique
that we use to untangle the many spectral features and verify spectral
bands that belong to the same carrier. This technique was published
in J. Phys. Chem. A and featured on the front cover (right). The
technique allows intuitive association of spectra features that belong
to the same carrier, and also allows the complete separation of two
completely overlapping transitions in the excitation spectrum ,
providing the emission signatures are different. This technique was
indispensable in the discovery of the new C2 bands and the discovery of
the phenylpropargyl radical described above.
Selected Publications
1. Kokkin, DL, Reilly, NJ, Morris, CW, Nakajima, M, Nauta, K, Kable, SH and Schmidt, TW. Observation of the d3pg – c3Su band
system of C2. Journal of Chemical Physics, 125, 231101, 2006.
2. Reilly, NJ, Schmidt, TW and Kable, SH. Two-dimensional fluorescence (excitation/emission) spectroscopy as a probe of complex
chemical environments. Journal of Physical Chemistry A, 110, 12355-12359, 2006.
3. Houston, PL and Kable, SH. Photodissociation of acetaldehyde as a second example of the roaming mechanism. Proceedings of the
National Academy of Sciences of the United States of America, 103, 16079-16082, 2006.
~
~
4. Yin, H-M and Kable, SH. Rotational analysis of the HCO B(2A´ ) – X(2A´ )311 and 312 bands. Journal of Molecular Spectroscopy, 237,
163-173, 2006.
5. Reilly, NJ, Cupitt, GC, Kable, SH and Schmidt, TW. An experimental and theoretical investigation of the dispersed fluorescence
spectroscopy of HC4S. Journal of Chemical Physics, 124, 194310, 2006.
6. Yin, HM, Kable, SH, Zhang, X and Bowman, JM. Signatures of H2CO photodissociation from two electronic states. Science, 311,
1443-1446, 2006.
7. Zhu, H, Zheng, Z, Gao, X, Huang, Y, Yan, Z, Zou, J, Yin, H, Zou, Q, Kable, SH, Zhao, J, Xi, Y, Martens, WN and Frost, RL.
Structural evolution in a hydrothermal reaction between Nb2O5 and NaOH solution: From Nb2O5 grains to microporous Na2Nb2O6
• 2/3H2O fibers and NaNbO3 cubes. Journal of the American Chemical Society, 128, 2373-2384, 2006.
8. Sharp, RG, Reilly, NJ, Kable, SH and Schmidt, TW. Sequence structure emission in the red rectangle bands. Astrophysical Journal,
639, 194-203, 2006.
9. Thompson, K, Crittenden, DL, Kable, SH and Jordan, MJ. A classical trajectory study of the photodissociation of T1 acetaldehyde:
The transition from impulsive to statistical dynamics. Journal of Chemical Physics, 124, 044302, 2006.
54
School of Chemistry
Associate Professor Brendan J Kennedy
Room 458
School of Chemistry, F11
Telephone: +61 2 9351 2742
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_kennedy.html
solid state and materials chemistry
Perovskite-type oxides are the most widely used ceramics for technological applications as a consequence of the rich
variety of physical properties they display that arise as a result of structural phase transitions. Much of our research is
associated with understanding the origins of structural phase transitions and the complex interplay between structure
and physical properties.
Phase Transitions in Perovskite Oxides (Macquart, Zhou, Cheah, Howard1)
The majority of experimental studies conducted over the past year have been directed towards providing experimental
support for the group theoretical study of phase transitions in ordered double perovskites that was published in 2003 (Acta
Cryst 2003 B59, 463-471). Extensive studies were completed on the series of oxides A2NiWO6, where A is an alkaline
earth cation. The structures of the 27 oxides of this type have been determined using synchrotron X-ray powder diffraction
methods, with additional neutron patterns being collected for a smaller number of samples. These studies demonstrated
=1.430
=1.480

→ I 4 / m r

→ Fm 3 m .
the symmetry increases as the average size of the A-site cation, rA increases as follows P 21 / n r
Interest has also centered on the oxides A2LnMO6 where Ln is Pr or Tb and M is Ir or Ru. These oxides exhibit unusual
valence transitions associated with the rare earth cation (Tb or Pr) that can be induced by chemical substitution, or by
changes in temperature or pressure.
In addition to these studies of double perovskites we have completed a detailed analysis of the phase transition
behaviour in PrAlO3. This oxide is extremely unusual in that the Jahn-Tellar distortion associated with the PrIII cation
has the same symmetry as the in-phase tilting of the AlO6 octahedra. Structural and lattice parameter data have
then been used to follow details of octahedral tilting and spontaneous strains associated with the sequence of phase
transitions Pm 3 m ↔ R3 c ↔ Imma ↔ C2/m. These are interpreted in terms of strain/order parameter coupling using
a single Landau free energy expansion for a Pm 3m reference structure with two instabilities ( r+4 and G+3 active). The
Pm 3 m ↔ R3 c transition appears to be second order in character with an extrapolated transition temperature of
1864 ± 31 K. The R3 c ↔ Imma transition is first order in character and can be understood as occurring because coupling
takes place between tilting and electronic order parameter components via a common tetragonal strain. Strains for the
Imma ↔ C2/m transition conform closely to the Landau solution for a proper ferroelastic transition with second order
character and low temperature saturation.
a
a
Structure and Properties of Bismuth Containing Oxides (Macquart, Zhou)
Our studies in this area have been focused on understanding the ferroelectric to paraelectric phase transition in layered
Aurivillius-type oxides such as SrBi2Nb2O9 is reported. Using a combination of high resolution diffraction studies and
group theory we have shown that SrBi2Nb2O9 transforms from the polar orthorhombic structure in space group A21am
to the high temperature paraelectric tetragonal structure (I4/mmm) via an intermediate orthorhombic phase in Amam.
A number of other oxides have also been studies and recent work has been directed towards the preparation of novel
layered Bi oxides that incorporate a paramagnetic ion.
Annual Research Report
55
Neutron and X-Ray Studies of Materials (Saines, Arora, Howard)
The rapid development in high-resolution instruments at advanced neutron and synchrotron facilities has opened up
numerous new fields of chemistry. Two projects that have relied on such advances include the study of long life phosphors
based on lanthanide doped aluminates of the type AAl2O4. Structural studies of these oxides suggest the reason for
the limited solubility of rare earth cations in these oxides. The second area has been in the study of the up-take of
heavy metals, in particular lead, by apatite type minerals. Micro SRIXE measurements have been used to study the
incorporation of lead into teeth during the early stages of their development. These studies suggest an alternate strategy
in monitoring exposure of infants to heavy metals.
1
ANSTO
Selected Publications
1. Arora, M, Kennedy, BJ, Elhlou, S, Pearson, NJ, Walker, DM, Bayl, P and Chan, SWY. Spatial distribution of lead in human primary
teeth as a biomarker of pre- and neonatal lead exposure. Science of the Total Environment, 371, 55-62, 2006.
2. Cheah, M, Saines, PJ and Kennedy, BJ. The Jahn–Teller distortion and cation ordering in the perovskite Sr2MnSbO6. Journal of
Solid State Chemistry, 179, 1775-1781, 2006.
3. Cheah, MCL, Kennedy, BJ, Withers, RL, Yonemura, M and Kamiyama, T. Synthesis, structures and phase transitions in the double
perovskites Sr2-xCaxCrNbO6. Journal of Solid State Chemistry, 179, 2487-2494, 2006.
4. Kennedy, BJ, Howard, CJ, Knight, KS, Zhang, Z and Zhou, Q. Structures and phase transitions in the ordered double perovskites
Ba2BiIIIBiVO6 and Ba2BiIIISbVO6. Acta Crystallographica Section B-Structural Science, 62, 537-546, 2006.
5. Lian, J, Helean, KB, Kennedy, BJ, Wang, LM, Navrotsky, A and Ewing, RC. Effect of structure and thermodynamic stability on
the response of lanthanide stannate-pyrochlores to ion beam irradiation. Journal of Physical Chemistry B, 110, 2343-2350, 2006.
6. Saines, PJ and Kennedy, BJ. Implications of the solubility of trivalent lanthanides in AAI2O4 (A=Ca, Sr, and Ba) for their role in
phosphors. Powder Diffraction, 21, 285-288, 2006.
7. Saines, PJ, Elcombe, MM and Kennedy, BJ. Lanthanide distribution in some doped alkaline earth aluminates and gallates. Journal
of Solid State Chemistry, 179, 613-622, 2006.
8. Saines, PJ, Elcome, MM and Kennedy, BJ. Structural studies of oxygen deficient lanthanide containing double perovskites. Physica
B, 385-386, 187-189, 2006.
9. Somphon, W, Ting, V, Liu, Y, Withers, RL, Zhou, Q and Kennedy, BJ. Local crystal chemistry, structured diffuse scattering and
the dielectric properties of (Bi1-xYx)2(MIIINbV)O7 (M=Fe3+, In3+) Bi-pyrochlores. Journal of Solid State Chemistry, 179, 24952505, 2006.
10.Zhou, Q and Kennedy, BJ. Thermal expansion and structure of orthorhombic CaMnO3. Journal of Physics and Chemistry of Solids,
67, 1595-1598, 2006.
11.Zhou, Q, Kennedy, BJ and Elcombe, MM. Neutron powder diffraction studies of Ca2-xSrxCoWO6 double perovskites. Physica
B, 385-386, 190-192, 2006.
12.Zhou, Q, Kennedy, BJ and Elcombe, MM. Synthesis and structural studies of cation-substituted Aurivillius phases ASrBi2Nb2TiO12.
Journal of Solid State Chemistry, 179, 3744-3750, 2006.
56
School of Chemistry
Professor Cameron J Kepert
Room 456
School of Chemistry, F11
Telephone: +61 2 9351 5741
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_kepert.html
molecular framework materials
Nanoporous Molecular Frameworks (Southon, Yuan, Duyker, Phillips, Weeks, Halder, Bevitt,
Chapman, Faiz, Kolibac)
A range of new framework materials that display reversible guest sorption is being investigated.2 Characterisation of
the dynamic host-guest structures of these phases was explored using two new experimental techniques developed in our
lab, the first involving the in-situ measurement of single crystal X-ray diffraction data during gas and vapour sorption/
desorption1,4,6,7,8,11,13 and the second involving the measurement of diffuse X-ray scattering to provide differential pair
distribution functions (PDFs).10 Following our design and construction of purpose-built capillary flow cells, the uptake of a number of small molecular sorptives into a range of different nanoporous phases has been explored. Gas and
vapour sorption measurements and in-situ powder X-ray diffraction investigations have further enhanced our kinetic,
thermodynamic and structural understandings of the sorption chemistry of these phases.
Hydrogen Storage (Peterson, Southon, Iremonger, Weeks, Chapman,
Bevitt, Kolibac)
The safe and efficient storage of hydrogen gas represents a pivotal challenge in the
development of hydrogen as an alternative energy carrier. Our recent report of a
system in which dihydrogen molecules bind directly to bare metal sites within a
nanoporous molecular framework material (see picture)3 has provided an important
new advance in this area and points the way to hybrid materials in which hydrogen
gas can be loaded and released under non-extreme conditions of temperature and
pressure. A systematic structural characterisation of progressive hydrogen loading
provided a uniquely detailed understanding of the mechanism of pore filling. We
are extending this interest to other systems that may display this novel property.
Continuing investigations of hydrogen sorption in Prussian Blue phases12 has seen
fully reversible dihydrogen uptakes approaching 2 wt%.
Switching Nanoporous Materials (Halder, Amoore, Sciortino,
Robertson, Liu, Neville, Iremonger, Hudson, Murray, Moubaraki,
Toftlund, Letard, Guionneau)
Our incorporation of molecular electronic switches into nanoporous frameworks1
and dinuclear complexes4 is leading to materials and molecules that have unique
physicochemical properties and potential applications in molecular sensing and data
storage. Through the systematic variation of the bridging ligand and counter-ion
we have developed an extensive family of materials of this type, allowing fine-tuning
of guest-exchange (pore size and shape) and switching (transition temperature)
properties. Of particular note is the recent synthesis and characterisation of the
first dinuclear spin crossover complex to be exhibit a full two-step crossover (see
figure). Variation of included guest molecules perturbs the crossover properties of
this complex, converting it from two-step to single-step. Measurements performed
in Bordeaux have demonstrated that a number of our phases may be switched under
laser irradiation at low temperature (the LIESST effect).
Annual Research Report
57
Porous Magnetic Frameworks (Shigematsu, Neville, Chapman, Kurmoo)
As an extension of our efforts to incorporate electronic and magnetic function into nanoporous molecular frameworks we
are designing and synthesising porous materials that display magnetic ordering. Guest-exchange in such materials may
be used to perturb the magnetic properties, thereby providing a unique technique for investigating magnetic structureproperty relationships. Of particular note in this area is our recent discovery of a highly robust nanoporous phase that
converts from an antiferromagnet to a ferromagnet with the reversible removal of unbound water molecules.13
Negative Thermal Expansion (Duyker, Phillips, Kobayashi, Yuan, Chapman, Goodwin, Pretsch,
Kennedy, Withers, Dove, Hagen, Hester, Knight)
Investigations of the anomalous thermal expansion behaviour of metal cyanide frameworks have uncovered a wealth of
novel properties.5,6,8,9 We attribute the unprecedented negative thermal expansion (NTE) in these systems to two different
modes of transverse vibrational motion of the linear cyanide bridge, each one leading to a decrease in the M…M distance
with increasing temperature. Characterisations have been performed at ISIS, Harwell, UK, the Australian National
Beamline Facility, Tsukuba, Japan, and the Advanced Photon Source, Chicago, USA. Data from the latter has led to
the characterisation of metal-5,6 and guest-8 dependent NTE in these phases, and to the first PDF analysis of an NTE
material.9 Investigations of single diamondoid network phases, which includes both neutral and anionic network phases,
has led to detailed understandings of the influence of the guest volume and charge on NTE. Systematic characterisation
of lanthanoid-containing NTE phases have allowed us to decorrelate the influence of metal-cyanide bond energy and
ionic radius on NTE properties.
Porous Mineral Formulations (Yuan, Antill, Green, Matthews, Anderson, Wells)
In this project we are collaborating with an industrial partner on the generation of new technologies for the controlled
release delivery of agrochemicals from porous mineral phases. Recent progress has seen the successful control of release
properties through the modification of surface chemistry. In parallel with this project we are using halloysite nanotubes
(geometric analogues of the more expensive carbon or boron nitride nanotubes) as templates for fabrication of nanostructures
such as nanowires, rods and clusters.
Selected Publications
1. Neville, SM, Moubaraki, B, Murray, KS and Kepert, CJ. A thermal spin transition in a nanoporous iron(II) coordination framework
material. Angew. Chem. Int. Ed., 46, 2059-2062, 2007.
2. Kepert, CJ. Advanced functional properties in nanoporous coordination framework materials. Chem. Commun., 695-700, 2006. 40th
Anniversary Focus Article.
3. Peterson, VK, Liu, Y, Brown, CM and Kepert, CJ. Neutron powder diffraction study of D2 sorption in Cu3(1,3,5-benzenetricarboxylate)2.
J. Am. Chem. Soc., 128, 15578-15579, 2006. Highlighted in C&EN: see http://pubs.acs.org/cen/news/85/i01/8501notw8.html.
4. Amoore, JJM, Kepert, CJ, Moubaraki, B, Murray, KS and Neville, SM. Structural and magnetic resolution of a two-step spincrossover transition in a dinuclear iron(II) pyridyl-bridged compound. Chem. Eur. J., 12, 8220-8227, 2006. VIP Article with cover
picture.
5. Chapman, KW, Chupas, PJ and Kepert, CJ. Compositional dependence of negative thermal expansion in the Prussian Blue analogues
MIIPtIV(CN)6 (M = Mn-Zn, Cd). J. Am. Chem. Soc., 128, 7009-7014, 2006.
6. Pretsch, T, Chapman, KW, Halder, GJ and Kepert, CJ. Dehydration of the nanoporous coordination framework ErIII[CoIII(CN)6]∙
4(H2O): Single crystal to single crystal transformation and negative thermal expansion in ErIII[CoIII(CN)6]. Chem. Commun., 18571859, 2006.
7. G.J. Halder, C.J. Kepert, “Single-crystal-to-single-crystal structural transformations in molecular framework materials”, Aust. J.
Chem., 59, 597-604 (2006). Invited Review with cover picture.
8. Goodwin, AL, Chapman, KW and Kepert, CJ. Guest-dependent negative thermal expansion in nanoporous Prussian Blue analogues
MIIPtIV(CN)6·x{H2O} (0 ≤ x ≤ 2; M = Zn, Cd). J. Am. Chem. Soc., 127, 17980-17981, 2005.
9. Chapman, KW, Chupas, PJ and Kepert, CJ. Direct observation of a transverse vibrational mechanism for negative thermal expansion
in Zn(CN)2: An atomic pair distribution function analysis. J. Am. Chem. Soc., 127, 15630-15636, 2005.
10.Chapman, KW, Chupas, PJ and Kepert, CJ. Selective recovery of dynamic guest structure in a nanoporous prussian blue through
in-situ X-ray diffraction: A differential pair distribution function analysis. J. Am. Chem. Soc., 127, 11232-11233, 2005.
11.Halder, GJ and Kepert, CJ. In-situ single crystal x-ray diffraction studies of desorption and sorption in a flexible nanoporous
molecular framework material. J. Am. Chem. Soc., 127, 7891-7900, 2005.
12.Chapman, KW, Southon, PD, Weeks, CL and Kepert, CJ. Reversible hydrogen gas uptake in nanoporous prussian blue analogues.
Chem. Commun., 3322-3324, 2005.
13.Kurmoo, M, Kumagai, H, Chapman, KW and Kepert, CJ. Reversible antiferromagnetic-ferromagnetic transformation upon
dehydration-hydration in the porous metal-organic framework, [Co3(OH)2(C4O4)2]·3H2O. Chem. Commun., 3012-3014, 2005.
14.Goodwin, AL and Kepert, CJ. Negative thermal expansion and low-frequency modes in cyanide-bridged framework materials.
Phys. Rev. B, 71, 140301, 2005.
58
School of Chemistry
Professor Peter A Lay, FAA
Room 307
School of Chemistry, F11
Telephone: +61 2 9351 4269
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_lay.html
bioinorganic chemistry and
electrochemistry
Chemistry, Biochemistry and Cell Biology of Chromium in Relation to Cr-Induced Cancers and Cr
Dietary Supplements (Bartholomäus, Codd, Foran*, Harris, Levina, Meejoo, Mulyani, Nguyen)
The biochemistry of Cr(VI/V/IV/III), and their effects on cellular biology leading to Cr-induced cancers, have been
studied. New methods have been developed for the synthesis of Cr(V)-diol and sugar complexes and their chemistry
has been studied under conditions that are relevant to Cr-induced cancers. Empirical methods have been developed
for determining the structures of Cr complexes in cells and tissues using linear combinations of XANES from model
complexes that contain all of the ligand donor groups that are expected to be found in biology. These have been used to
ascertain that the purported Cr-containing protein, chromodulin (a protein that is postulated to be involved in glucose
metabolism), is likely to be an artifact of its isolation method. However, a new Cr-binding protein has been identified
from blood serum when Cr(III) dietary supplements are allowed to react with the serum. We have obtained further
evidence that Cr(III) dietary supplements are oxidised to carcinogenic Cr(VI) by certain enzymatic processes and that
Cr(VI) and Cr(V) inhibit the same phosphatase enzymes and, in the same manner, as well-known vanadium anti-diabetic
complexes, whereas the Cr(III) supplements themselves are inactive.
Bioactive Ru and Mo Complexes (Gwee, Levina, Seuring)
Considerable research has been conducted on the biotransformation of Ru anti-cancer drugs and Mo dietary supplements for
the treatment of diabetes. We have used similar methodologies as those use in the Cr project to study the biotransformations
in biological fluids and cells. In the case of molybdenum, molybdate and related species tend to dominate under most
biological conditions, whereas Ru anti-cancer drugs undergo substantial hydrolysis and oligomerisation processes under
physiological conditions and tend to bind with various proteins and cells. These studies are being used to understand
the mode of action of the drugs and in the design of new Ru and Mo drugs.
XAS Studies of Isolated and Intracellular Heme Proteins (Armstrong, Cai*, Cheng, Gell*, Harris,
Lai*, Levina, Mackay*, Rayner*, Rich, Stocker*, Thomas*, Vogt*, Witting*)
Raman and EPR spectroscopic and XAFS studies have shown that NO and CO adducts of a-Hb exhibit only minor
changes to the heme centre on the binding of a-Hb stabilising protein (AHSP), which contrasts with the chemistry
observed for the O2 adduct, which is converted to a low-spin Fe(III) complex with two axial histidines on AHSP binding.
Experiments have been performed on the effects of hypoxia and then exposure to O2 with cardiac myocytes (heart muscle
cells) under conditions that mimic ischemia reperfusion injury (heart damage after heart attacks). There is a general
efflux of metal ions from the cytoplasm, which occurs well before apoptosis and this appears to be important in the initial
damage to the tissues. Similar studies have also been conducted with neurons and these studies have been extended
to develop new potential drugs for the treatment of heart attacks and strokes. Finally, the effect of induction of heme
oxygenase-1 on mammalian cells has been studied in relation to its role in a variety of essential functions.
Annual Research Report
59
Fullerenes: Derivatives, Conjugates and their Complexes (Armstrong, Boyd*, Carter, Gallagher,
Sen Gupta)
New fullerene/porphyrin conjugates have been prepared that have the potential to be powerful anti-cancer drugs and
their physical and spectroscopic properties have been correlated with their biological activities using chemometric
techniques.
Cu Anti-inflammatory Drugs (Bonin, Dillon, Firkin, Hackett*, Hambley, Haque, Kennedy, Kaur,
Kueh, McConaghy*, Nguyen, Reeve*, Rose*, Teo, Weder, Zhou)
Cu-indomethacin and related pharmaceuticals were prepared and characterised by EPR spectroscopy and X-ray
crystallography. The complexes are much less ulcerogenic than indomethacin and cause less renal damage that the muchtouted COX-II inhibitors. New formulations are being used internationally in veterinary applications and are planned
enter human clinical trials for the treatment of inflammation and cancer. Detailed studies of the pharmacology of these
drugs in rats have been undertaken, and new drugs with even higher efficacy and lower side effects have been developed
and a raft of PCT and provisional patent applications have been filed for new compounds and indications.
Cancer Diagnosis in Tissues and Identification of Microbes by Vibrational Spectroscopy (Ali, Armstrong, Carter, Mountford*, Rich, Russell*, Sorrell*, Tam)
Multivariate analysis of microprobe vibrational spectroscopy was used to design new diagnostics for breast cancer, and
in particular pre-cancerous lesions. Strong correlations have been obtained for vibrational spectroscopic diagnosis with
diagnoses obtained form standard pathology studies and NMR techniques and chemometrics studies have been used
to improve the identification of regions of cancer and to improve the diagnostic reliabilities. Vibrational spectroscopic
techniques are also being developed to identify and differentiate pathogenic microorganisms and to examine their
susceptibility to new drugs.
Mushroom Tyrosinase (Gheibi, Levina)
The binding of substrates to Cu in this enzyme have been studied by a number of spectroscopic and kinetic studies, as
well as XAS.
Selected Publications
1. Weder, JE, Dillon, CT, Hambley, TW, Kennedy, BJ, Lay, PA, Biffin, JR, Regtop, HL and Davies, NM. Copper complexes of nonsteroidal anti-inflammatory drugs: An opportunity yet to be realized. Coordination Chemistry Reviews, 232, 95-126, 2002.
2. Levina, A, Codd, R, Dillon, CT and Lay, PA. Chromium in biology: Nutritional aspects and toxicology. Progress in Inorganic
Chemistry, 51, 145-250, 2003.
3. Kim, K-C, Hauke, F, Hirsch, A, Boyd, PDW, Carter, E, Armstrong, RS, Lay, PA and Reed, CA. Synthesis of the C59N+ carbocation.
A monomeric azafullerene isoelectronic to C60. Journal of the American Chemical Society, 125, 4024-4025, 2003.
4. Mulyani, I, Levina, A and Lay, PA. Biological oxidation of chromium(III): Does the anti-diabetic activity of chromium(III) involve
carcinogenic chromium(VI)? Angewandte Chemie, International Edition, 43, 4504-4507, 2004.
5. Feng, L, Gell, DA, Zhou, S, Gu, L, Kong, Y, Li, J, Hu, M, Yan, N, Lee, C, Rich, AM, Armstrong, RS, Lay, PA, Gow, AJ, Weiss,
MJ, Mackay, JP and Shi, Y. Molecular mechanism of AHSP-mediated stabilization of a-hemoglobin. Cell, 119, 629-640, 2004.
6. Levina, A, Armstrong, RS and Lay, PA. Three-dimensional structure determination using multiple-scattering analysis of XAFS:
Applications to metalloproteins and coordination chemistry. Coordination Chemistry Reviews, 249, 141-160, 2005.
7. Lay, PA and Levina, A. Mechanistic studies of relevance to the biological activities of chromium. Coordination Chemistry Reviews,
249, 281-298, 2005.
8. Immoos, CE, Sulc, F, Farmer, PJ, Czarnecki, K, Bocian, DF, Levina, A, Aitken, JB, Armstrong, RS and Lay, PA. Bonding in HNOmyoglobin as characterized by x-ray absorbance and resonance raman spectroscopies. Journal of the American Chemical Society, 127,
814-815, 2005.
9. Ramadan, S, Bonin, AM, Kennedy, BJ, Hambley, TW and Lay, PA. NMR analysis of indomethacin-induced gastric ulcers. Chemical
Research in Toxicology, 18, 123-128, 2005.
10.Harris, HH, Levina, A, Dillon, CT, Mulyani, I, Lai, B, Cai, Z and Lay, PA. Time-dependent uptake, distribution and
biotransformation of chromium(VI) in individual and bulk human lung cells: Application of synchrotron radiation techniques.
Journal of Biological Inorganic Chemistry, 10, 105-118, 2005.
11.Levina, A, Harris, HH and Lay, PA. Binding of chromium(VI) to histones: Implications for chromium(VI)-induced genotoxicity.
Journal of Biological Inorganic Chemistry, 11, 225-234, 2006.
12.Witting, PK, Harris, HH, Rayner, BS, Aitken, JB, Dillon, CT, Stocker, R, Lai, B, Cai, Z, Lay, PA. The endothelium-derived
hyperpolarizing factor, H2O2, promotes metal ion efflux in aortic endothelal cells. Elemental mapping by a hard X-ray microprobe.
Biochemistry, 45, 12500-12509, 2006.
60
School of Chemistry
Emeritus Professor Leonard F Lindoy, FAA
Honorary Staff
Room 146
School of Chemistry, F11
Telephone: +61 2 9351 2734
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_lindoy.html
Annual Research Report
61
cationic tetrahedral cage structures capable of including tetrahedral anions (such as BF4-, PF6- and FeCl4-) have been
constructed, in this case using self assembly techniques.
Molecular Electronics and Sensors (Bray, Wei, Herrmann*, Müller*)
This project is being carried out jointly with the CSIRO Division of Industrial Physics. It is concerned with the synthesis
and investigation of organic cross-linked gold nanoparticle films, with emphasis on their electrical properties. Attention
is being given to both the theoretical consequences of nanoparticle size and cross-linking as well as to the potential
practical applications of these unusual materials
metallosupramolecular chemistry
Metallo-Supramolecular Chemistry: Metal-Directed Synthesis of Molecular Architectures Including
Triangles, Tetrahedra, and Molecular Frameworks (Bray, Clegg, Gloe*, Jolliffe, Meehan*, Murray*,
McMurtrie*)
The synthesis of unusual supramolecular architectures employing metal directed procedures and incorporating linked
β-diketonato ligand systems has been carried out. This project is aimed at using the latent directional and electronic
information in molecules and ions (including metal ions) to assemble new supramolecular materials showing unusual
properties.
Macrocycle Design and Synthesis for Metal Ion Recognition (Bray, Meehan*, Vasilescu*, Wei, )
This project has involved the design and synthesis of new macrocylic systems incorporating mixed donor sets that are
capable of binding selected transition and post-tranistion metal ions selectively.
New Framework Materials: Self-Assembly of New Hydrogen Bonded and Metal-Ion Linked Arrays
(Bishop, Clegg, McMurtrie, Turner)
The project is concerned with the design and synthesis of new molecular architectures incorporating linked macrocyclic
and related systems as structural components – with emphasis being given to the use of hydrogen bonded or metal-donor atom
links in the bridges between macrocyclic rings.. As such, the project represents an extension of our previous studies in which a
number of different macrocyclic rings have been linked covalently by means of conventional organic synthetic procedures.
In particular, the new species are designed to form linked products by means of self-assembly processes - thus offering
synthetic economy in the construction of the novel materials.
New Reagents for Selective Metal Cation, Anion and Metal Salt Extraction and Membrane Transport
(Galbraith, Gloe*, Tasker*)
In this project the design and synthesis of new reagents for use in solvent extraction and bulk membrane transport
experiments is being carried out. Recent results include the successful selective membrane transport of individual anions
and the use of ditopic receptors for metal salt extraction.
New Cage Receptors for Metal Ions and anions (Clegg, Glasson*, Murray*, Meehan*, Perkins,
Turner)
We have undertaken the construction of a range of new cage and cage-like molecules for the selective binding of both
cations and anions. These include an inherently chiral supra-cage. The cage interacts with a single octahedral metal ion
such that a helical twist extends about 22 angstroms along the axial length of the system. In other studies unusual
Selected Publications
1. Lindoy, LF and Atkinson, IM. Self-assembly in supramolecular chemistry. Royal Society for Chemistry, Cambridge UK - a monograph
of 219 pp, 2000.
2. Armstrong, RS, Atkinson, IM, Carter, E, Mahinay, MS, Skelton, BW, Turner, P, Wei, G, White, AH and Lindoy, LF. Self-assembly
directed by NH-O hydrogen bonding: New layered molecular arrays derived from 4-tert-butylbenzoic acid and aliphatic diamines.
Proc. Nat. Acad. Sci., 99, 4987-4992, 2002.
3. Bray, DJ, Liao, L-L, Antonioli, B, Gloe, K, Lindoy, LF, McMurtrie, JC, Wei, G and Zhang, X-Y. Assembly of a tri-silver metallo
capsule – synthesis, X-ray structure and membrane transport behaviour. Dalton Trans., 2082-2083, 2005
4. Bishop, MM, Lindoy, LF, Parkin, A and Turner, P. Towards a system for the systematic structural study of intermolecular interactions
in crystals of transition metal complexes. Dalton Trans., 2563-2571, 2005.
5. Clegg, JK, Lindoy, LF, McMurtrie, JC and Schilter, D. Dinuclear bis-beta-diketonato ligand derivatives of iron(III) and copper(II)
and use of the latter as components for the assembly of extended metallo-supramolecular structures. Dalton Trans., 857-864,
2005.
6. Antonioli, B, Clegg, JK, Bray, DJ, Gloe, K, Gloe, K, Heßke, H and Lindoy, LF. An unprecedented bridging [Ag2(NO3)6]4– anion
as a component of aninfinite silver(I) molecular ladder incorporating a dinuclear cationic silver complex of a bis-dipyridylamine
ligand. Cryst.Eng.Comm., 8, 748-750, 2006.
7. Perkins, DF, Lindoy, LF, McAuley, A, Meehan, GV and Turner, P. Manganese(II), iron(II), cobalt(II) and copper(II) plexes of an
extended inherently chiral tris-bipyridyl cage. Proc. Nat. Acad. Sci., 103, 532-537, 2006.
8. Self-assembled metallo-supramolecular systems incorporating beta-diketone motifs as structural elements. Bray, DJ, Clegg, JK,
Lindoy, L.F and Schilter, D in Advances in Inorganic Chemistry, Eds. van Eldik, R and Bowman-James, K. Academic Press, Volume
59, 1-37, 2007.
62
School of Chemistry
Dr Christopher Ling
Room 455
School of Chemistry, F11
Telephone: +61 2 9351 4780
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_ling.html
neutron scattering and materials science
Incommensurate Misfit-layered Thermoelectric
Cobaltates (Schmid)
Misfit-layered cobaltates are a family of layered ceramic oxides
attracting considerable attention for their excellent properties
as thermoelectrics (allowing the direct conversion of a thermal
gradient into an electrical current for power generation, or vice versa
for heating/cooling applications). Their defining structural feature
is the stacking of alternating layer types: a pseudo-hexagonal
CdI2-type layer of edge-sharing CoO6 octahedra (H subsystem);
and 3 or 4 pseudo-tetragonal rock-salt-type metal oxide layers (RS
subsystem). A lattice mismatch between these two types of layers
means that these oxides must be described crystallographically as
incommensurately modulated composites.
A large number of misfit-layered cobaltates are known, incorporating various solid solutions of metal ions
into the cation sites of the RS subsystem. One of the most intensively studied, [Ca2CoO3]RS[CoO2]H1.61, is notable for its
unusually high thermopower, straightforward synthetic procedure and the presence of only two cation species. Adding to
the interest in this phase are the simultaneous presence of cobalt in three oxidation states (II, III, IV) and observations of
giant magnetoresistance and three magnetic transitions. Recently, it has been found that a significant number of oxygen
vacancies exist in the structure, but their actual location had not been determined. Furthermore, the oxygen content was
found to vary according to synthetic procedure, suggesting a possible means of controlling the physical properties - the
thermoelectric power was found to increase with the number of oxygen vacancies.
In this study [6], we used single crystal X-ray diffraction to locate the oxygen vacancies on the disordered
oxygen site in the central layer of the RS subsystem. As-made samples contain 14(2) % oxygen vacancies on this site,
while a further ~13 % vacancies can be introduced by high-temperature annealing under mildly reducing atmospheres.
Doping Nd3+ for Ca2+ was found to substantially reduce the tolerance of the structure for oxygen vacancies to ~4 % on the
disordered site, while doping Ti4+ for Co2+/3+/4+ was found to decrease the number of oxygen vacancies while maintaining
the same average cobalt oxidation state of 3.13+. Ti4+ was located on the disordered cobalt site in the central layer of the
RS subsystem. The RS subsystem therefore appears to be responsible for all the flexibility of this compound, with the H
subsystem (which shows no sign at all of oxygen vacancies or cation doping) responsible for maintaining its structural
integrity.
Novel Transition Metal Networks Within Stabilised Oxygen-Ion Conductors
The excellent ionic conduction properties of the high-temperature phase of bismuth oxide, δ-Bi2O3, derive from the 25%
oxygen vacancies in its disordered fluorite-type structure. Although only stable above 937 K, its fluorite-type substructure
and ionic conduction can be preserved to room temperature when doped with 5+ or 6+ valent transition metal cations
such as Nb(V), Ta(V), W(VI), or Mo(VI), which localise some of the oxygen vacancies. These doped δ-Bi2O3-related
Annual Research Report
63
phases have extremely complex superstructures that are largely invisible to X-ray powder diffraction (XRD) due to the
dominant X-ray scattering power of Bi over O. In the absence of single crystals, only neutron powder diffraction (NPD)
data can be relied upon to solve and refine these superstructures; however, NPD suffers from the opposite problem to
XRD in that it often contains too much evenly-weighted information, making it hard to find an unambiguous and
reliable solution.
This project concerns the insertion of unpaired d electrons into the unique transition metal networks found in
these superstructures, in order to elicit novel low-dimensional and geometrically frustrated magnetic states. In the first
stage we have revisited some of the most complex of these superstructures that were never previously solved by diffraction
methods. We have found that ab initio quantum calculations, using the localised density approximation (LDA) to density
functional theory (DFT), are remarkably effective at perturbing the fluorite-type oxygen sublattice surrounding dopant
transition metal cations. The structures of Bi14MO24 (M = Cr, Mo, W) [3] and Bi94Nb32O221 [4] could be solved by DFT
geometry optimisation, starting from a simple model based only on the distribution of the dopant metal cations (which
could be unambiguously determined using XRD). The optimised structures almost perfectly fit experimental NPD
data, subsequent Rietveld-refinement leading to atomic shifts of less than 0.1 Å. The figure shows the oxygen atom coordination around M atoms in Bi14MO24 that results from the 8-fold crystallographic disordering of the highly ordered
MO4 tetrahedra identified in the DFT-optimised structure.
Multiferroic Layered Oxides (Kennedy)
Multifunctional crystalline materials, in which several physical properties (magnetic, electronic,
and/or structural) co-exist and interact on the atomic scale, are of great scientific and technological
interest. This project concerns multiferroic oxides that exhibit both ferroelectricity (an electrical
polarisation due to atomic displacements, used in capacitors) and ferromagnetism (a long-range
spin polarisation due to magnetic exchange interactions, used in transformers and data storage).
Multiferroics are of interest for applications as sensors and actuators, particularly in microwave
devices, and as magnetically recordable ferroelectric (non-volatile) data storage media. Very
few materials exhibit truly multiferroic behaviour, because ferroelectricity generally requires d0
transition-metal ions (e.g. Ti4+) while ferromagnetism requires the presence of mobile d electrons, i.e.,
the two properties are mutually exclusive in simple oxides. Most applied research into multiferroics
therefore focuses on layered composites of ferroelectric and ferromagnetic oxides manufactured
by techniques such as chemical vapour deposition. However, such ‘artificially’ layered oxides are
far coarser and less homogeneous than ‘naturally’ layered oxides, the potential of which remains
relatively unexplored.
In this project we are using the naturally layered Aurivillius phase oxides as templates
for multiferroicity. Aurivillius phases consist of ordered intergrowths of α-PbO-type layers of
composition [Bi2O2]2+ and n perovskite-type layers of composition [An-1BnO3n+1]2-, where A is a
large cation such as Bi3+ or Pr3+, and B is a small cation such as Nb5+ or Ti4+. Aurivillius phases are
strongly ferroelectric due to displacements of A and B cations within the perovskite-type layers.
Our goal is to substitute magnetic cations such as Fe3+ and Mn4+ into the B sites of the central
perovskite-type layers (light grey octahedra) in order to make them ferromagnetic, while leaving
non-magnetic cations in the outer perovskite-type layers (white octahedra) so that they remain
ferroelectric. Thus far we have achieved partial layers of Mn4+, Ru4+ and Ir4+ [2]; and Cr3+, Mn3+,
Fe3+ and Co3+.
Selected Publications
1. Ling, CD and Johnson, M. Modelling, refinement and analysis of the “type III” d-Bi2O3-related superstructure in the system
Bi2O3-Nb2O5. Journal of Solid State Chemistry, 177, 1838-1846, 2004.
3. Ling, CD. Solving d-Bi2O3-related superstructures by combining neutron powder diffraction and ab initio calculations. Physica B,
385-386, 193-195, 2006.
5. Hunger, J, Beta, IA, Böhlig, H, Ling, CD, Jovic, H and Hunger, B. Adsorption structures of water in NaX studied by DRIFT
spectroscopy and neutron powder diffraction. Journal of Physical Chemistry B, 110, 342-353, 2006.
1. Ling, CD, Aivazian, K, Schmid, S and Jensen, P. Structural investigation of oxygen non-stoichiometry and cation doping in misfitlayered thermoelectric [Ca2CoO3-x][CoO2]d, d ≈ 1.61. Journal of Solid State Chemistry, 180, 1446-1455, 2007.
2. Sharma, N, Ling, CD, Wrighter, GE, Chen, PY, Kennedy, BJ and Lee, PL. Three-layer aurivillius phases containing magnetic
transition metal cations: Bi2‑xSr2+x(Nb,Ta)2+xM1‑xO12, M = Ru4+, Ir4+, Mn4+, x ≈ 0.5. Journal of Solid State Chemistry, 180, 370-376,
2007.
6. Ling, CD, Avdeev, M and Aivazian, K. Synthesis, structure, and stability of the high-Ttemperature 6H-type perovskite phase
Ba3BaSb2O9. Acta Crystallographica Section B, In Press.
64
School of Chemistry
Dr Nigel T Lucas
Room 516
School of Chemistry, F11
Telephone: +61 2 9351 2745
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_lucas.html
Annual Research Report
65
Large Polycyclic Aromatic Hydrocarbons as π-Ligands (Müllen†, El Hamaoui†)
One of the difficulties in dealing with larger PAHs is that with increasing molecular weight, the solubility of the
compounds decreases, primarily as a result of strong aggregation of the discs through π-π interactions. The processability
of large PAHs can be dramatically improved through the coordination of metal fragments to the disc surface to suppress
the formation of extended aggregates. Additionally, site-selectivity as a result of the multiplicity of available coordination
sites provides information about the electronic properties of the PAH. The [Ru(η5-C5Me5)]+ fragment binds to one of the
peripheral rings of HBC(t-Bu)6 to afford the crystallographically-confirmed sandwich complex 3 as the major product
(triflate anion not shown). The related complex [Ru(η5-C5Me5)(η6-HBC)]OTf (4) affords graphitic nanorods when
subjected to controlled solid-state pyrolysis, serving as both metal catalyst and carbon source.
SYNTHETIC & SUPRAMOLECULAR CHEMISTRY
The identification and subsequent bulk preparation of the fullerenes in the mid- to late-1980’s ignited the rapid growth
of synthetic work on carbon allotropes and new carbon-rich materials. More recently, advances in the synthesis of large
polycyclic aromatic hydrocarbons (PAHs) have allowed the efficient preparation of monodisperse ‘synthetic graphites’
(graphenes) of unprecedented size. When functionalised with long alkyl chains, these soluble disc-like molecules can
self-assemble, through strong π-π interactions, into columnar liquid crystalline mesophases which have shown promise
as semiconductor materials. Our key projects extend on previous work with large PAHs through the investigation of
their coordination chemistry and the characterisation of metal-containing adducts.
Metallographic Discs (Darwish, Müllen†, Wu†)
By varying the number and type of ligated metal centres bound to the graphitic discs, it is possible that the supramolecular
ordering of the discs can be controlled and their molecular physical properties tuned. The most intensively studied of
the PAHs described above is hexa-peri-hexabenzocoronene (HBC, C42H18), and it can be rationally synthesised in good
yield with a wide range of functionalities and substitution patterns. Using an appropriately functionalised precursor
disc, 1-6 ligated metal centres can be introduced around the core periphery. When the ligands are rigid and bulky,
crystalline materials are obtained, whereas the use of ligands with long, flexible, alkyl chains can afford materials with
liquid crystalline properties. Complexes bearing one or two HBC-based ligands with pyridine, bipyridine (1), phosphine
or cyclopentadienyl (2) coordinating groups are have been prepared and characterised.
Assembly and Imaging of Graphitic Molecules at Surfaces (Zareie†, McDonagh†)
Investigations into the self-organization of a wide range of organic compounds at surfaces has been revolutionized by
the direct imaging of chemical species using scanning probe microscopies. To complement the supramolecular studies
of new PAH-based ligands and metal complexes in the bulk, their 2-dimensional self-assembly at highly-ordered
surfaces is being explored using scanning tunnelling microscopy (STM). The relative importance of intermolecular and
molecular-surface interactions are being assessed by systematic variation of the molecular shape and functional group
substitution. For example, the graphite surface assembly of the pyridine-substituted HBC(C12H25)5(4-py) ligand and its
bis-axially substituted Ru(phthalocyanine) derivative are dramatically different.
Immobilisation of Metal Complexes on Oxide Surfaces (McDonagh†, Colbran†, Hook†, Dance†)
Palladium, platinum and tungsten complexes containing the bifunctional ligand (diphenylphosphino)catechol have been
synthesized. The catecholate functionality strongly binds to titanium dioxide nanoparticles allowing the complexes to
be effectively anchored to the TiO2 surface. Solid state 31P NMR spectroscopy has been used to probe the surface-bound
compounds. Diffuse reflectance infra-red spectroscopy provides data on surface-bound tungsten carbonyl complexes.
The palladium phosphine complex [PdBr2{PPh2(4catechol)}2] supported on TiO2 effectively catalyses the
coupling of phenylacetylene with 4-nitroiodobenzene. A
crystal structure of cis-[PtBr2{PPh2(4-catechol)}2]·(ethanol)2
reveals two catechol rings well disposed to act as double
bidentate ligands for adjacent metal atoms on the surface of
a nanocrystal of TiO2 and provides geometric parameters for
the computational modelling of such a process.
† Co-worker not associated with The University of Sydney
Selected Publications
1. Lucas, NT, McDonagh, AM, Dance, IG, Colbran, SC and Craig, DC. cis-[PtBr2{PPh2(4-catechol)}2]: synthesis, crystal structure,
and computational modelling of its binding to nanocrystalline TiO2. Dalton Trans., 680–685, 2006.
2. Cifuentes, MP, Powell, CE, Morrall, JP, McDonagh, AM, Lucas, NT, Humphrey, MG, Samoc, M, Houbrechts, S, Asselberghs, I,
Clays, K, Persoons, A, Isoshima, T. Electrochemical, spectroelectrochemical, and molecular quadratic and cubic nonlinear optical
properties of alkynylruthenium dendrimers. J. Am. Chem. Soc., 128, 10819–10832, 2006.
3. Usher, AJ, Lucas, NT, Dalton, GT, Randles, MD, Viau, L, Humphrey, MG, Petrie, S, Stranger, R, Willis, AC, Rae, AD. Mixedmetal cluster chemistry. 29. Core expansion and ligand-driven metal exchange at group 6-iridium clusters. Inorg. Chem., 45,
10859–10872, 2006.
4. Chow, H, Dean, PAW, Craig, DC, Lucas, NT, Scudder, ML and Dance, IG. The subtle tetramorphism of MePh3P+I3-. New J. Chem.,
27, 704–713, 2003.
5. Samoc, A, Samoc, M, Luther-Davies, B, Freydank, AC and Lucas, NT. Investigation of nonlinear optical chromophores with
femtosecond degenerate four-wave mixing in solutions. J. Nonl. Opt. Phys. Mater., 12, 235–246, 2003.
6. Lucas, NT, Notaras, EGA, Petrie, S, Stranger, R and Humphrey, MG. Mixed-metal cluster chemistry. 22. Synthesis and crystallographic,
electrochemical, and theoretical studies of alkyne-coordinated group 6-iridium clusters linked by phenyleneethylnylene groups.
Organometallics, 22, 708–721, 2003.
7. Lucas, NT, Notaras, EGA, Cifuentes, MP and Humphrey, MG. Mixed-metal cluster Chemistry. 21. Synthesis and crystallographic
and electrochemical studies of alkyne-coordinated group 6–iridium clusters linked by phenylenevinylene groups. Organometallics,
22, 284–301, 2003.
8. Lucas, NT, Blitz, JP, Petrie, S, Stranger, R, Humphrey, MG, Heath, GA and Otieno-Alego, V. Mixed-metal cluster chemistry. 19.
Crystallographic, spectroscopic, electrochemical, spectroelectrochemical, and theoretical studies of systematically varied tetrahedral
group 6–iridium clusters. J. Am. Chem. Soc., 124, 5139–5153, 2002.
9. Lucas, NT, Humphrey, MG and Rae, AD. Mixed-metal cluster chemistry. 16. Syntheses of oligourethanes containing clusters in
the backbone. Macromolecules, 34, 6188–6195, 2001.
66
School of Chemistry
Annual Research Report
Associate Professor John Mackie
Selected Publications
Honorary Staff
Room 146
School of Chemistry, F11
Telephone: +61 2 9351 2734
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_mackie.html
chemical reactions at high temperature
Theoretical Studies in Combustion Chemistry (Bacskay)
Reactions of the NH radical are most important in combustion especially in understanding the mechanism of NOx
formation when air is the oxidant. NH reactions are also important in processes such as the Thermal De-NOx technique
for reduction of NO in combustion systems. NH has been found experimentally to react rapidly with H2, H2O and CO2,
all important components of combustion gases. Using Gaussian techniques we have been investigating the elementary
mechanisms whereby NH reacts with these three species. The reaction between NH and H2 is a straightforward abstraction
reaction to produce NH2 and H. However, the reactions with H2O and CO2 are complex. Several intermediates have been
located on both triplet and singlet reaction potential energy surfaces for NH + CO2 with the occurrence of intersystem
crossing. The NH + H2O surface is also complex with several low energy intermediates having been located on the
singlet surface but with no stable intermediates on the triplet surface.
Conversion of Halons into Useful Chemicals (Dlugogorski*, Kennedy*)
The use of halon fire suppressants such as CHF3 are now banned under the Montreal Protocol because they are significant
ozone depleting agents. There is a pressing need to convert the large stockpiles of halons into useful chemicals. Together
with colleagues at the University of Newcastle, the reaction between CHF3 and methane to produce the valuable industrial
chemical, CH2CF2, is being studied theoretically using Gaussian techniques, and in the laboratory in flow reactors. An
important intermediate reaction in the mechanism leading to the formation of CH2CF2 is the reaction between CH3
radicals and the carbene, CF2. A detailed quantum chemical and kinetic study has revealed that this reaction proceeds
via an intermediate, CH3CF2 via chemical activation. The intermediate is, however, not stable and rapidly fissions of an
H atom producing the desired CH2CF2. Rate constants for the overall mechanism have been derived using a multiwell
kinetic approach.
Dioxins from Combustion of Wood (Dlugogorski*, Kennedy*)
Wood treated by preserving agents incorporating organochlorine pesticides can lead to the emission of the environmentally
harmful polychlorinated dioxins and dibenzofurans upon combustion or incineration. The chemical reaction pathways
leading to dioxin formation are being investigated experimentally in the laboratory using TGA, DSC and mass
spectrometry and theoretically using quantum chemical techniques. Reaction pathways to chlorinated dibenzofuran
from the organochlorine pesticide, permethrin, have been identified by Gaussian techniques and reaction path analysis
carried out. Further quantum chemical studies are being carried out of reaction pathways which can lead to the complete
destruction of dibenzofurans in incineration.
67
1. Hynes, RG, Mackie, JC and Masri, AR. Inhibition of premixed hydrogen-air flames by 2-H heptafluoropropane. Combust. Flame,
113, 554-565, 1998.
2. Bacskay, GB, Martoprawiro, M and Mackie, JC. The thermal decomposition of pyrrole: An ab initio quantum chemical study of the
potential energy surface associated with the hydrogen cyanide plus propyne channel. Chem. Phys. Letters, 300, 321-330, 1999.
3. Hynes, RG, Mackie, JC and Masri, AR. A shock tube study of the pyrolysis of the halon replacement molecule, CF3CHFCF3.
J. Phys. Chem. A, 103, 54-61, 1999.
4. Martoprawiro, M, Bacskay, GB and Mackie, JC. Ab initio quantum chemical and kinetic modeling study of the pyrolysis kinetics
of pyrrole. J. Phys. Chem. A, 103, 3923-3934, 1999.
5. Haworth, NL, Smith, MH, Bacskay, GB and Mackie, JC. Heats of formation of hydrofluorocarbons obtained by gaussian-3 and
related quantum chemical calculations. J. Phys. Chem. A, 104, 7600-7614, 2000.
6. Haworth, NL, Bacskay, GB and Mackie, JC. The role of phosphorus dioxide in the H+OH recombination reaction: Ab initio
quantum chemical computation of thermochemical and rate parameters. J. Phys. Chem. A, 106, 1533-1541, 2002.
7. Mackie, JC, Bacskay, GB and Haworth, NL. Reactions of phosphorus-containing species of importance in the catalytic recombination
of H + OH: Quantum chemical and kinetic studies. J. Phys. Chem. A, 106, 10825-10830, 2002.
8. Haworth, NL, Mackie, JC and Bacskay, GB. An ab initio quantum chemical and kinetic study of the NNH + O reaction potential
energy surface: How important is this route to NO in combustion? J. Phys. Chem. A, 107, 6792-6803, 2003.
9. Bacskay, GB and Mackie, JC. Oxidation of CO by SO2: A theoretical study. J. Phys. Chem. A, 109, 2019-2025, 2005.
10.Mackie, JC and Bacskay, GB. Quantum chemical study of the mechanism of reaction between NH (X 3S) and H2, H2O, and CO2
under combustion conditions. J. Phys. Chem. A, 109, 11967-11974, 2005.
11.Hai Yu, Mackie, JC, Kennedy, EM and Dlugogorski, BZ. Experimental and quantum chemical study of the reaction CF2 + CH3
↔ CF2CH3 → CH2:CF2 + H: A key mechanism in the reaction between methane and fluorocarbons. Ind. Eng. Chem. Res., 45,
3758-3762, 2006.
68
School of Chemistry
Professor Thomas Maschmeyer
Room 303
School of Chemistry, F11
Telephone: +61 2 9351 2581
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_maschmeyer.html
green chemistry/processes, functional
nano-materials and high throughput
experimentation
General
The world is standing at the technological threshold of a revolution that is
driven by the need for truly sustainable (industrial) processes. At current rates
of resource usage, a world population operating with Australian standards
of living would require between 4 – 6 planets (depending on the method of
calculation). Clearly, this is untenable and, from a chemical viewpoint, the
inherent challenges can only be met by devising strategies for waste reduction,
energy optimisation and process intensification as outlined in the 12 principles of “Green
Chemistry”. Our group aims to tackle these issues by generating and using new fundamental
insights on the molecular and nanoscopic level to develop feasible leads for the design of
new catalytic chemical routes and processes that will enhance sustainability.
Examples of project areas:
• New ionic liquids (supported and/or chiral) as catalytic and synthesis
media.
• Preparation, characterisation and testing of ceramic nanoparticles
stabilised and supported in mesoporous hosts as catalysts and functional
materials.
• Micro-wave assisted synthesis for green chemistry.
• Functional coatings on microstructured reactors.
• Chemistry in supercritical solvents.
• Converting biomass to biofuel.
• Hydrogen generation from water.
Annual Research Report
69
Brief Curriculum Vitae
In 1994, as Australian Bicentennial Fellow, Thomas Maschmeyer went to the Royal Institution, London. Subsequently,
he was made Assistant Director of their Davy Faraday Laboratories and also Associate Lecturer and Affiliated Fellow
(Peterhouse) at the University of Cambridge. In 1998, at the age of 31, he was appointed Professor and Head of the
Department of Industrial Organic Chemistry at the Delft University of Technology, making him the youngest Professor
of Chemistry in Europe at that time. Additionally, in 2000, Thomas became Vice-Chairman of the Delft Institute of
Chemical Technology. During this time he was also advisor to the Dutch Federal Ministry of Finance and Economic
Affairs. He returned to his alma mater in late 2003, when he commenced his new positions as Federation Fellow and
Professor of Chemistry.
Recent highlights include: his founding role in ‘Avantium’ (a Dutch spin-off company with ca. 100 employees,
specialising in High-Throughput Experimentation Research), the design of the ‘grafting approach’ (leading to highly
selective catalysts via the use of molecularly confined spaces) and the design of new types of mesoporous materials. Both
design approaches lead to catalysts that are superior to their industrial counterparts and are part of on-going industrial
development/up-scaling programmes. He also devised and commissioned ceramic membrane reactors that represent
new technological solutions to many chemical process problems, as they allow conversion and separation to occur
simultaneously, with the added benefit of being able to operate beyond the reaction equilibrium.
Selected Publications
1. Maschmeyer, Th, Rey, F, Sankar, G and Thomas, JM. Heterogeneous catalysts obtained by grafting metallocene complexes onto
mesoporous silica. Nature, 378, 159-162, 1995.
2. Oldroyd, RD, Thomas, JM, Maschmeyer, Th, MacFaul, PA, Snelgrove, DW, Ingold, KU and Wayner, DDM. The titanium(IV)
catalysed epoxidation of alkenes by tert-alkyl hydroperoxides. Angewandte Chemie, IEE., 35, (23/24), 2787-2789, 1997.
3. Maschmeyer, Th, Oldroyd, RD, Sankar, G, Thomas, JM, Shannon, IJ, Klepetko, JA, Masters, AF, Beattie, JK and Catlow, CRA.
Designing a solid catalyst for the selective low-temperature oxidation of cyclohexane to cyclohexanone. Angewandte Chemie, IEE.,
36, (15), 1639-1642, 1997.
4. Shephard, DS, Maschmeyer, Th, Johnson, BFG, Thomas, JM, Sankar, G, Ozkaya, D, Zhou, W, Oldroyd, RD and Bell, RG. Bimetallic
nanoparticle catalysts anchored inside mesoporous silica. Angewandte Chemie, IEE., 36, (20), 2242-2245, 1997.
5. Zhou, W, Thomas, JM, Shephard, DS, Johnson, BFG, Ozkaya, D, Maschmeyer, Th, Bell, RG and Ge, Q. Ordering of ruthenium
cluster carbonyls in mesoporous silica. Science, 280, (5364), 705-708, 1998.
6. Shephard, DS, Zhou, W, Maschmeyer, Th, Matters, JM, Roper, CL, Parsons, S, Johnson, BFG and Duer, MJ. Site directed surface
derivatisation of MCM 41 – Use of high-resolution transmission electron-microscopy and molecular recognition for determining
the position of functionality within mesoporous materials. Angew. Chem. Int. Ed. Eng., 37, (19), 2719-2723, 1998.
7. Nowotny, M, Maschmeyer, Th, Johnson, BFG, Lahuerta, P, Thomas, JM and Davies, JE. Heterogeneous dinuclear rhodium(II)
hydroformylation catalysts – performance evaluation and silsesquioxane-based chemical modeling. Angewandte Chemie, IEE., 40,
(5), 955-958, 2001.
8. Pescarmona, PP, Van der Waal, JC, Maxwell, IE and Maschmeyer, Th. A new efficient route to titanium-silsesquioxane epoxidation
catalysts developed using high-speed experimentation techniques. Angewandte Chemie, IEE., 40, (4), 740-743, 2001.
9. Shan, Z, Gianotti, E, Jansen, JC, Peters, JA, Marchese, L and Maschmeyer, Th. One-step synthesis of a highly Active mesoporous
titanium-containing silica by using bifunctional templating. Chemistry – A European Journal, 7, (7), 1437-1443, 2001.
10.Nowotny, M, Pedersen, LN, Hanefeld, U and Maschmeyer, T. Increasing the ketone selectivity of the cobalt-catalyzed radical chain
oxidation of cyclohexane. Chemistry – A European Journal, 8, (16), 3724-3731, 2002.
11.Maschmeyer, T. Assembled catalysts – just interesting, or maybe important? Topics in Catalysis, 24, 29-36, 2003.
12.Pescarmona, PP, Van der Waal, JC and Maschmeyer, T. Silsesquioxane-based homogeneous and heterogeneous epoxidation catalysts
developed by using high-speed experimentation. Chemistry – A European Journal, 10, (7), 1657-1665, 2004.
13.Pescarmona, PP, Van der Waal, JC and Van de Water, LGA. Parallel approaches to the synthesis and testing of catalysts for liquidphase reactions, in: High throughput screening in chemical catalysis. Eds. Hagemeyer, A, Strasser, P and Volpe jnr., AF, Wiley-VCH
Verlag GmbH & Co. KGaA, Weinheim, 211-237, ISBN: 3-527-30814-8, 2004.
14.Simons, C, Hanefeld, U, Arends, IWCE, Sheldon, RA and Maschmeyer, T. Noncovalent anchoring of asymmetric hydrogenation
catalysts on a new mesoporous aluminosilicate: Application and solvent effects. Chemistry – A European Journal, 10, (22), 5829-5835,
2004.
15.Simons, C, Hanefeld, U, Arends, I, Minnaard, AJ, Maschmeyer, T and Sheldon, RA. Efficient immobilisation of Rh-MonoPhos
on the aluminosilicate AlTUD-1. Chemical Communications, (24), 2830-2831, 2004.
16. Klomp, D, Djanashvili, K, Svennum, NC, Chantapariyavat, N, Wong, C-S, Vilela, F, Maschmeyer, T, Peters, JA and Hanefeld, U.
Combined epimerization and acylation: Meerwein-Ponndorf-Verley-Oppenauer catalysts in action. Organic & Biomolecular Chemistry,
3, (3), 483-489, 2005.
17.Veum, L, Kanerva, L, Halling, PJ, Maschmeyer, Th and Hanefeld, U. Optimization of the enantioselective synthesis of cyanohydrin
esters. Advanced Synthesis & Catalysis, 347, (7&8), 1015-1021, 2005.
18.Simons, C, Hanefeld, U, Arends, IWCE, Maschmeyer, Th and Sheldon, RA. A one-pot enantioselective chemo-enzymatic synthesis
of amino acids in water. Advanced Synthesis & Catalysis, 348, (4&5), 471-475, 2006.
19.Hamdy, MS, Berg, O, Jansen, JC, Maschmeyer, Th, Moulijn, JA and Mul, G. TiO2 nanoparticles in mesoporous TUD 1: Synthesis,
characterization and photocatalytic performance in propane oxidation. Chemistry – A European Journal, 12, (2), 620-628, 2006.
70
School of Chemistry
Dr Craig P Marshall
Room LG82a, Madsen Building F09
School of Chemistry, F11
Telephone: +61 2 9351 3994
Facsimile: +61 2 9351 3329
Email: [email protected]
Annual Research Report
71
obtained from the bitumen indicated similarities with hydrothermal petroleum generated in the Guaymas Basin (Gulf
of California) where hot waters permeate organic-rich sediments and generate oil with a distinctive chemistry. We have
found a closely comparable suite of hydrocarbons in the McArthur River deposit. Determining the taxonomic affinities
of microbes in the mesophilic zone surrounding the orebody has been very successful. Significantly we have discovered
a dinoflagellate affinity for some of the micro-eukaryote fossils. Furthermore, we are currently developing a new line of
investigation to elucidate the biological affinities of these enigmatic microfossils by the application of synchrotron IR
micro-spectroscopy at NSRRC Taiwan. This is the first application of synchrotron techniques applied to micro-eukaryote
fossils. The project was awarded an ARC Discovery Project in 2004. A comparable study of Early Archaean hydrothermal
deposits in the Pilbara region has also been undertaken. We have also started investigating modern hydrothermal deposits
in Yellowstone National Park.
Contemporary Ancient Analogue Micro-Organisms of Palaeobiological Significance (Neilian8,
Burns8)
Biogeochemistry
Our current research interests cover a number of projects which investigate the diversity and timelines of the early forms
of life from the fossil record. In addition, interpretation is maximized when careful observations on ancient populations
are combined with actualistic studies of microbial populations in comparable modern environments.
Although many geochemical reactions may be affected by microbial metabolism in geothermal environments the
interactions between microbes and geothermal solutions are poorly understood. Experiments are been conducted that
hope to investigate at the molecular level, the interaction between a polymerizing silica solution and metallic solutions
that simulate processes occurring in near-Earth surface geothermal systems. Silicification and metal sorption experiments
are been conducted on filamentous cyanobacteria Calothrix sp., Phormidium sp. and halophilic archaea Halobacterium sp.
These micro-organisms are isolated and cultured from commonly occurring microbes in stromatolites from Shark Bay
(Western Australia). The silicification and metal sorption experiments are performed on healthy cultures in growth phase
by adding solutions of SiO2, Cu2+, Fe2+, and Pb2+. The extent of sorption and characterisation of the biological-mineral
interfaces will be determined by Raman micro-spectroscopy, FTIR and SR FTIR micro-spectroscopies.
1
Tracing the Origins of Life in Earth’s Oldest Sedimentary Rocks (Love 1, Summons2, Allwood3,
Walter4)
Examining remnants of organic material in Earth’s oldest sedimentary rocks is an essential part of tracing the origins of life
on our plant and important for developing techniques to search for traces of life on other plants. Accordingly, carbonaceous
materials in Early Archaean (3.2-3.5 billion year old) sedimentary rocks are coming under scrutiny to determine whether
evidence of biology can be elucidated. The Archaean Pilbara Craton, Australia, is the best place in the world to study
the early Earth – it has a geological history from >3.5 through to 2.4 billion years old, preserved at low metamorphic
grade with low strain rocks that contain Earth’s oldest hydrothermal systems. The aim of this project is to elucidate the
macromolecular structure of the carbonaceous materials in these rocks and hence determine any molecular biomarkers
which may provide evidence for either a biological or and non-biological origin of these materials. The research so far
has resulted in 5 papers including one published in Nature in 2006 (ref 1).
2
3
UC Riverside, USA
MIT, USA
NASA, USA
Macquarie University, Australia
WHOI, USA
6
University of Liege, Belgium
7
Harvard University, USA
8
UNSW, Australia
4
5
Selected Publications
A New Approach in Deciphering Early Protist Paleobiology and Evolution (Olcott , Javaux ,
Knoll7)
5
6
Acritarchs are organic walled microfossils of unknown biological affinities. They are conventionally interpreted as
algal cysts but most probably include a larger range of organisms such as prokaryotic sheaths, heterotroph protists or
even parts of multicellular beings. Biologists easily differentiate between prokaryotic and eukaryotic organisms using
molecular and cell biology, but these characters rarely survive fossilization. Identifying the biological affinities of these
microscopic organisms will clarify Proterozoic (2.5 Ga to 5.5 Ma) microbial paleobiology. It will also contribute to
phylogenetic reconstructions, and improve our understanding of early evolutionary mechanisms and patterns, and the
early interactions between environment and life. New approaches are necessary to elucidate their paleobiology. Single
microfossils are being investigated by Raman and infrared spectroscopy.
The Role of Microbes and Organic Matter in the Formation of Ore Deposits (Walter4)
The main aims of this project were to determine the palaeo-temperature of McArthur Pb-Zn-Ag orebody, characterise
organic matter from orebody and host sediments, and determine the biological affinities of microfossils in the surrounding
sediments. The palaeo-temperatures represented by the ore fluid pathway are poorly understood. However, our studies
using Raman spectroscopy of organic matter associated with the ore indicates a palaeo-temperature of the mineralizing
fluids of 120-220ºC. This has significant impact on mineral exploration models for this style of deposit. The major issue
was to resolve whether the ore sulfides formed within the sediment pile or in the overlying water body. Our results
1. Allwood, AC, Walter, MR, Kamber, BS, Marshall, CP and Burch, IW. Stromatolite reef from early Archaean era of Australia.
Nature, 441, 714-718, 2006.
2. Marshall, CP, Love, GD, Snape, CE, Hill, AC, Allwood, AC, Walter, MR, Van Kranendonk, MJ, Bowden, SA, Sylva, SP and
Summons, RE. Structural characterization of kerogen in 3.4 Ga Archaean cherts from the Pilbara Craton, Western Australia.
Precambrian Research, 155, 1-23, 2007.
3. Allwood, AC, Walter, MR and Marshall, CP. Raman spectroscopy reveals thermal palaeoenvironments of c.3.5 billion-year-old
organic matter. Vibrational Spectroscopy, 41, 190-197, 2006
4. Marshall, CP, Carter, EA, Leuko, S and Javaux, EJ. Vibrational spectroscopy of extant and fossil microbes: Relevance for the
astrobiological exploration of Mars. Vibrational Spectroscopy, 41, 182-189, 2006.
72
School of Chemistry
Dr Malcolm D McLeod
Room 517
School of Chemistry, F11
Telephone: +61 2 9351 5877
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_mcleod.html
organic synthesis
Our research interests include the development of new synthetic methods and the chemical synthesis of biologically
active natural products and their analogues.
Enantioselective Total Synthesis of the Cytotoxic Macrolide (–)-Dactylolide (Louis, Hungerford)
Annual Research Report
73
Chemistry and Biology of Nicotinic Acetylcholine Receptors (nAChRs) (Halliday, Lin, Collins*)
Nicotinic acetylcholine receptor (nAChR) chemistry and biology is currently of enormous interest in the field of drug
development. The receptors have been implicated as playing a role in conditions such as epilepsy, Alzheimer’s disease and
schizophrenia. However, few compounds differentiate between the different nAChR subtypes. Methyllycaconitine is a
selective and potent α7 nAChR antagonist but the size and complexity of this natural product render it unsuitable as a
therapeutic agent in its own right. We have recently developed new methods for the double-Mannich annulation reaction
that increase the yield and decrease the number
of steps needed to access analogue structures (Ref
3). Testing of our analogues completed has shown
that they act as antagonists at a number of different
nAChR subtypes but they have different modes of
action at each receptor subtype (Ref 4). Current
research aims to improve the activity and selectivity
of the class of ligands under investigation by
varying their structure. The project was awarded
an ARC Discovery Project Grant in 2005.
Synthesis and Analysis of Anabolic Steroid Metabolites (Bain, Hungerford, Pu, Wilkinson,
McKinney*, Stenhouse*)
This project is conducted in collaboration with the Australian Racing Forensic Laboratories located in Randwick and
aims to develop new methods for illicit drug detection in thoroughbred and harness and greyhound racing. The project
was awarded two ARC Linkage Project Grants in 2002 and research is currently focused on three main areas: 1) the
development of high throughput assays based on immunoassays for the rapid preliminary screening of race day samples
(Ref 5); 2) the chemical synthesis of phase II metabolites and the development of direct methods for their detection
(Ref 6) , and; 3) new methods that use genetically engineered enzymes called glycosynthases for the synthesis of steroid
glucuronide conjugates.
We reported enantioselective total synthesis of the cytotoxic marine natural product
(–)-dactylolide in Organic Letters in early 2006 (Ref 1). This complex natural product
contains a 20-membered macrocyclic ring with a high degree of unsaturation and a
complex array of stereochemistry. A notable feature of the synthesis is a sequence of
substrate controlled reactions to efficiently introduce the remote C19-stereochemistry
present in the target. This allows for the absolute stereochemistry of the molecule to
be derived in one catalytic asymmetric step using a hetero-Diels-Alder reaction. The
total synthesis was published.
Total Synthesis of the Microsclerodermins: Anti-fungal
Cyclic Peptides (Stewart, Shuter, Hutton*)
Our aim is to discover new anti-fungal treatments for drug-resistant
pathogenic fungal infections based on the microsclerodermin family
of natural products. A synthesis route is required as the small quantity
available from the natural environment hampers the development
of anti-fungal agents from this natural product. Innovative
synthetic methods are being developed to prepare large quantities
of microsclerodermins and related compounds for biological testing,
thereby furthering the development of this promising class of
anti-fungal drugs. The project was awarded an ARC Discovery
Project in 2003 (with Dr Craig Hutton). The development of
substrate controlled Asymmetric Aminohydroxylation (AA) and
Asymmetric Dihydroxylation (AD) reactions has led to the synthesis
of unusual amino acid components of microsclerodermins such as the
pyrrolidinone, APTO and GABOB (Ref 2). Current work is directed
to remaining unusual amino acid components of the target such as
the chlorotryptophan residue and assembly of the macrocycle.
Selected Publications
1. Louis, I, Hungerford, NL, Humphries, EJ and McLeod, MD. Enantioselective total synthesis of (–)-dactylolide. Org. Lett., 8, 11171120, 2006.
2. Harding, M, Bodkin, JA Hutton, CA and McLeod, MD. Substrate control in the asymmetric aminohydroxylation of monosubstituted
alkenes: the enantioselective synthesis of GABOB and homoserine derivatives. Synlett, 18, 2829-2831, 2005.
3 Halliday, JI, Chebib, M, Turner, P, McLeod, MD Double-Mannich annulation of cyclic ketones using N,N-bis(ethoxymethyl)alky
lamine reagents. Org. Lett., 8, 3399-3401, 2006.
4. Barker, D, Lin, DH-S, Carland, JE, Chu, CP-Y, Chebib, M, Brimble, MA, Savage, GP and McLeod, MD. Methyllycaconitine
analogues have mixed antagonist effects at nicotinic acetylcholine receptors. Bioorg. Med. Chem., 13, 4565-4575, 2005.
5. Hungerford, NL, Sortais, B, Smart, CG, McKinney, AR, Ridley, DD, Stenhouse, AM, Suann, CJ, Munn, KJ, Sillence, MN and
McLeod, MD. Analysis of anabolic steroids in the horse: development of a generic ELISA for the screening of 17α-alkyl anabolic
steroid metabolites. J. Steroid Biochem. Mol. Biol., 96, 317-334, 2005.
6 Hungerford, NL, McKinney, AR, Stenhouse, AM, McLeod, MD. Selective manipulation of steroid hydroxyl groups with boronate
esters: Efficient access to antigenic C-3 linked steroid-protein conjugates and steroid sulfate standards for drug detection. Org.
Biomol. Chem., 4, 3951-3959, 2006.
74
School of Chemistry
Annual Research Report
75
Dr Damian Moran
Room 209a
School of Chemistry, F11
Telephone: +61 2 9351 5358
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/~dmoran/
computational predictions concerning
structure, stability and mechanism
The application of modern theoretical methods now provides a “green” alternative
to the laboratory for the study of chemistry. While traditionally limited to relatively
small molecules, the present explosive developments in computer hardware have
guaranteed that the frontiers of computational chemistry are rapidly expanding.
My research involves the application of computational chemistry to problems of
chemical interest, including predictions concerning structure, stability and reaction
mechanism. Recent research highlights include the discovery that several well
established and commonly employed computational-chemistry methods incorrectly
predict that planar aromatic molecules are bent (J. Am. Chem. Soc. 2006, 128,
9342). The impact of this discovery is demonstrated by noting that it featured in
the highlights section of Science (2006, 313, 149) and of Nachrichten aus der Chemie
(2006, 54, 842).
Peptide Radical Rearrangements
As part of a major collaboration, a broad computational investigation of neutral
polypeptide radicals and their rearrangements is being undertaken. My recent efforts
have included an investigation of the mass spectrometric fragmentation patterns
of complexes between sodium ions and neutral peptide radicals. The structures of
these cation complexes are complicated, which in turn convolutes interpretations
concerning their fragmentation mechanisms. In this regard, computations have
proven to be extremely helpful, particularly with respect to learning about the
barriers to intramolecular radical rearrangement prior to fragmentation (Chem.
Commun. 2006, 4233).
Selected Publications
1. Hemelsoet, K, Van Speybroeck, V, Moran, D, Marin, GB, Radom, L and Waroquier, M. Thermochemistry and kinetics of hydrogen
abstraction by methyl radical from polycyclic aromatic hydrocarbons. J. Phys. Chem. A, 110, 13624–13631, 2006.
2. Moran, D, Jacob, R, Wood, GPF, Coote, ML, Davies, MJ, J. O’Hair, RA, Easton, CJ and Radom, L. Rearrangements in model
peptide-type radicals via intramolecular hydrogen-atom transfer. Helv. Chim. Acta, 89, 2254–2272, 2006.
3. Wee, S, Mortimer, A, Moran, D, Wright, A, Barlow, CK, J. O’Hair, RA, Radom, L and Easton, CJ. Gas-phase regiocontrolled
generation of charged amino acid and peptide radicals. Chem. Commun., 4233–4235, 2006.
4. Moran, D, Simmonett, AC, Leach, FE, Allen, WD, Schleyer, PvR and Schaefer, HF. Popular theoretical methods predict benzene
and arenes to be non-planar. J. Am. Chem. Soc., 128, 9342–9343, 2006.
5. Hemelsoet, K, Moran, D, Van Speybroeck, V, Waroquier, M and Radom, L. An assessment of theoretical procedures for predicting
the thermochemistry and kinetics of hydrogen abstraction by methyl radical from benzene. J. Phys. Chem. A, 110, 8942–8951,
2006.
6. Corral, I, Mó, O, Yáñez, M, Salpin, JY, Tortajada, J, Moran, D and Radom, L. An experimental and theoretical investigation of
gas-phase reactions of Ca2+ with glycine. Chemistry - Eur. J. 12, 6787–6796, 2006.
7. Barlow, CK, Moran, D, Radom, L, McFadyen, WD and O’Hair, RAJ. Metal-mediated formation of gas-phase amino acid radical
cations. J. Phys. Chem. A, 110, 8304–8315, 2006.
8. Goh, SW, Buckley, AN, Lamb, RN, Rosenberg, RA and Moran, D. The oxidation states of copper and iron in mineral sulfides,
and the oxides formed on initial exposure of these sulfides to air. Geochim. Cosmochim. Acta, 70, 2210–2228, 2006.
76
School of Chemistry
Dr Klaas Nauta
Room 315
School of Chemistry, F11
Telephone: +61 2 9351 3777
Facsimile: +61 2 9351 3329
Email: [email protected]
superfluid helium droplets
Helium nanodroplet spectroscopy is a new and exciting field in physical chemistry. Helium droplets are formed by
expanding high pressure helium at low temperatures into vacuum. This produces a beam of helium droplets with a size
range of several hundred to several hundreds of thousands atoms or, on average, a few nanometers in diameter. They are
extremely small, significantly smaller than, e.g., atmospheric aerosoles (micrometers), but still large enough to capture
and dissolve several molecular species. It is the ease with which the droplets can be ‘doped’ with molecules that makes
them a very useful experimental tool. Dopant species are introduced by passing the droplets through a small scattering
region where a slightly elevated background pressure of the compound of interest is maintained. The beam of doped
helium droplets can then be probed via laser spectroscopy and mass spectrometry.
Annual Research Report
77
Unique Stuctures
Because individual molecules are each dissolved in their
own helium droplet, from which they cannot escape,
helium droplets have sometimes been termed ‘nanoscales
laboratories’. Where more than one molecule dissolves
in a single droplet, the dopant species combine to form
a van der Waals complex whose structure is governed
by relatively long range forces, e.g. dipole-dipole
interaction. The internal temperature of the droplets,
and hence the dopant molecules, has been measured
at 0.37+/-0.03 K. At these temperatures, even small
barriers on the potential energy surface can be enough
to prevent rearrangement of one structural isomer into
another. Studies have shown that unique van der Waals
complexes are indeed formed inside helium droplets
and often the resulting structures closely resemble the
structural motif of the corresponding bulk (liquid or
solid) phases of the dopant species. An example is the
observation of a cyclic water hexamer, the structural
motif of plain water ice and an isomer of water6 that is
not stable by itself in the gas phase.
Reactions at Zero Kelvin
Well, not exactly 0 K, but close enough. The extremely low temperature inside helium droplets and the facility with
which they can be doped with a wide variety of species opens up the possibility to capture and stabilise molecular
complexes that in another medium, or in the gas phase, at higher temperatures, would not be stable. A famous example
is the dimer of the OH radical which theory predicts should be stable but has yet eluded experimental observation.
Helium droplets might be used to bring two cold (0.37 K) OH radicals together to form a weakly bound, metastable
complex that cannot react (too cold!) without being externally triggered. Once formed, the complex may be excited
via laser radiation to give it just enough energy to overcome the barrier to rearrangement, and reaction. Many radicalradical and radical-molecule reactions exist in nature and often these are very hard to study due to the transient nature
of the intermediate complexes.
Spectroscopy of Molecular Ions
Over the past year the helium droplet apparatus was fitted with a time-of-flight mass spectrometer. The spectrometer was
successfully tested by measuring the gas phase spectra of naphthalene-argon clusters, incidentally revealing the correct gas
phase structure of naphthalene dimer for the first time. It is our goal, as part of the joint astro-chemistry project in the
laser spectroscopy group, to use the combined helium-droplet/mass-spectrometry apparatus to measure the optical spectra
of large molecular ions trapped in helium droplets. Molecular ions, e.g. PAH cations, have been frequently postulated
as one of many possible carriers of absorption bands in the interstellar medium, but it has proven exceedingly difficult
to measure their spectra in the laboratory. Helium droplet spectroscopy provides an elegant way of bypassing many of
the problems associated with measuring the spectra of molecular cations.
Selected Publications
Superfluid Dynamics
One unique property of liquid helium droplets is that they are superfluid. A result of this superfluidity is that a molecular
dopant can rotate freely inside the helium. Although the helium will attempt to move with the molecule (and thus
affect its moment of inertia), no energy is exchanged between the dopant molecule and the surrounding solvent. The
motion is non-dissipative as opposed to motion in a classical liquid which is rapidly frictionally dampened. Studying
the spectroscopy of various molecular species in helium droplets can teach us much about the nature of superfluidity at
the microscopic level and how it interacts with and is affected by the presence of the molecule.
1. Nauta, K and Miller, RE. The spectroscopy of molecules and unique clusters in superfluid helium droplets. Campargue, R (editor),
Springer-Verlag, Berlin, Atomic and Molecular Beams, 775-792, 2001.
2. Scoles, G and Lehmann, KK. Molecular spectroscopy - Nanomatrices are cool. Science, 287, 2429, 2000.
3. Nauta, K and Miller, RE. Nonequilibrium self-assembly of long chains of polar molecules in superfluid helium. Science, 283,
1895, 1999.
4. Nauta, K and Miller, RE. Formation of cyclic water hexamer in liquid helium: The smallest piece of ice. Science, 287, 293,
2000.
5. Grebenev, S, Toennies, JP and Vilesov, AF. Superfluidity within a small helium-4 cluster: The microscopic Andronikashvili
experiment. Science, 279, 2083, 1998.
6. Lugovoj, E, Toennies, JP and Vilesov, A. Manipulating and enhancing chemical reactions in helium droplets. J. Chem. Phys, 112, 8217,
2000.
78
School of Chemistry
Professor Leo Radom, FAA
Room 309
School of Chemistry, F11
Telephone: +61 2 9351 2733
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_radom.html
computational quantum chemistry
Chemistry is traditionally an experimental science. However, recent advances in computer technology and the development
of highly efficient computer algorithms have opened the way for a viable alternative approach to chemistry: chemistry
by computer. We use such computer calculations, based on the laws of quantum mechanics, to determine the structures
of molecules and to help understand how molecules react with one another.
Enzyme-Catalysed Reactions (Sandala, Durbeej, Smith§,
Coote†, Marsh‡, Golding‡)
Vitamin B12 is one of nature’s essential vitamins. We have used
ab initio quantum chemistry calculations to model reactions
mediated by coenzyme B12 (also known as adenosylcobalamin or
AdoCbl). Although these reactions have been extensively studied
experimentally, there is certainly no consensus as to how they
Figure 1
proceed. We have proposed mechanisms involving partial-protontransfer (donation or acceptance) provided by enzymatic hydrogen bonding. Supporting evidence for our proposals has
come from site-directed mutagenesis experiments. These and other recent examples provide strong encouragement for
the use of such computer calculations in a predictive manner in the study of enzyme reactions. Our most recent work
has been concerned with suicide inactivation, involving the inactivation of B12 enzymes by substrate analogues. We
have found that the inactivation is associated with the formation of highly stable radicals, impeding the regeneration of
Ado• radicals and leading to disruption of the catalytic cycle (see Figure 1).
Annual Research Report
Development of Improved Theoretical Procedures (Wood, Merrick, Moran, Petersson‡)
The ability to predict reliable thermochemistry represents a very important application of ab initio quantum chemistry.
We have recently been designing and assessing methods that are suited for predicting accurate thermochemistry for free
radicals because these represent particular challenges for theoretical investigation. Our latest work has been concerned
with developing an improved procedure for examining radicals within the complete-basis-set (CBS) formalism, designated
ROCBS-QB3. In separate work, we have been deriving scale factors that may be used to transform calculated harmonic
vibrational frequencies to useful thermodynamic quantities for a wide variety of theoretical procedures.
Interaction of Metal Ions With Biological Systems (Moran, Corral§, Yanez§, Mo§, Tortajada‡)
Metal ions are of great importance in biological function. We have embarked on a broad-based theoretical study to
probe the interaction of metal ions with prototypical biological molecules. Our initial investigations have focussed on
the interaction of calcium dications with simple model systems in order to establish suitable theoretical procedures
that can be applied to larger molecules. Calculations on the interaction of calcium dication with urea and glycine have
been carried out in parallel with experimental mass spectrometric studies, and used to help interpret the observed mass
spectrometric fragmentation patterns.
Hydrogenation (Chan, Zhong, Miller, Smith§)
Hydrogenation is a very important process in chemical systems. It is generally brought about by transition metal or heavy
metal catalysts. However, in recent years it has been demonstrated that catalytic hydrogenation can also be accomplished
in the absence of such metals. We are using theory to try to design systems in which metal-free hydrogenations can
occur with low energy requirements. Our initial studies have involved the acid- and base-catalysed hydrogenation of
ethene and other doubly-bonded systems, as well as catalysis by zeolites. As part of such studies, we have designed
a new class of zeolites that show the potential to
transform carbon dioxide to methanol at a low
energy cost. In separate work on the hydrogenation
of aromatic hydrocarbons, we have found examples
where kinetics do not follow thermodynamics, e.g.,
in the production of 1,4- and 1,3-cyclohexadiene
from benzene (see Figure 2). In the area of transfer
hydrogenation, we have found that for the prototype
reaction of ethane with ethene a concerted pathway
is preferred over a stepwise pathway that involves
Figure 2
free radicals.
§
†
Fundamentals of Free Radical Chemistry (Menon, Ivanic, Wood, Moran, Taylor, Sandala, Durbeej,
Hemelsoet§, Coote†, Easton†, Henry†, Van Speybroeck‡, Warochier‡)
Radicals are ubiquitous in chemistry, biology, and polymer science. Because they are reactive species, they are often
difficult to study experimentally and therefore theory has a potentially useful role to play in their characterisation. We
have been using theory to determine radical stabilisation energies, with the important aim of seeing how individual
substituents stabilise or destabilise a radical centre. We have also been examining the details of addition, abstraction and
rearrangement reactions of radicals. These are very important in biological chemistry and polymer chemistry. We have
been particularly interested in hydrogen-atom abstraction by the methyl radical from polycyclic aromatic hydrocarbons.
Finally, in the context of the radical abstraction reactions, we have been examining quantum mechanical tunneling and
isotope effects.
Peptide Radical Chemistry (Wood, Moran, Barlow§, Wee§, Gordon§, Jacob†, Coote†, Easton†, Rauk‡,
Davies‡, O’Hair‡)
An understanding of the oxidation of proteins by free radicals is of great importance because of its implication in a
number of human disorders such as Alzheimer’s disease, atherosclerosis, and diabetes, as well as aging. We have been
using high-level quantum chemistry calculations to address the problem. Initial targets have included the cleavage of
the peptide backbone following radical formation, and migration of the radical site within the peptide, both with and
without attachment to a metal ion. We have also examined solvation effects.
79
‡
Current or former Visiting Scholar/Professor in the School of Chemistry.
Current/former member of Research School of Chemistry, ANU.
Coworker not associated with University of Sydney or ANU.
Selected Publications
1. Miller, DJ, Smith, DM, Chan, B and Radom, L. Transfer hydrogenation between ethane and ethene: A critical assessment of
theoretical procedures. Mol. Phys., 104, 777–794, 2006.
2. Sandala, GM, Smith, DM, Coote, ML, Golding, BT and Radom, L. Insights into the hydrogen-abstraction reactions of diol
dehydratase: Relevance to the catalytic mechanism and suicide inactivation. J. Am. Chem. Soc., 128, 3433–3444 (2006).
3. Chan, B and Radom, L. Design of effective zeolite catalysts for the complete hydrogenation of CO2. J. Am. Chem. Soc., 128,
5322–5323, 2006.
4. Moran, D, Jacob, R, Wood, GPF, Coote, ML, Davies, MJ, O’Hair, RAJ, Easton, CJ and Radom, L. Rearrangements in model
peptide-type radicals via intramolecular hydrogen-atom transfer. Helv. Chim. Acta, 89, 2254–2272, 2006.
5. Wood, GPF, Radom, L, Petersson, GA, Barnes, EC, Frisch, MJ and Montgomery, JA. A restricted-open-shell complete-basis-set
model chemistry. J. Chem. Phys., 125, 094106-1–094106-16, 2006.
6. Wood, GPF, Easton, CJ, Rauk, A, Davies, MJ and Radom, L. The effect of side chains on competing pathways for b-scission
reactions of peptide-backbone alkoxyl radicals. J. Phys. Chem. A, 110, 10316–10323, 2006.
7. Hemelsoet, K, Van Speybroeck, V, Moran, D, Marin, GB, Radom, L and Waroquier, M. Thermochemistry and kinetics of hydrogen
abstraction by methyl radical from polycyclic aromatic hydrocarbons. J. Phys. Chem. A, 110, 13624–13631, 2006.
8. Wee, S, Mortimer, A, Moran, D, Wright, A, Barlow, CK, O’Hair, RAJ, Radom, L, and Easton, CJ. Gas-phase regiocontrolled
generation of charged amino acid and peptide radicals. Chem. Comm., 4233–4235, 2006.
9. Sandala, GM, Smith, DM and Radom, L. In search of radical intermediates in the reactions catalyzed by lysine 2,3-aminomutase
and lysine 5,6-aminomutase. J. Am. Chem. Soc., 128, 16004–16005, 2006.
80
School of Chemistry
Professor Jeffrey R Reimers
Room 546
School of Chemistry, F11
Telephone: +61 2 9351 4417
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_reimers.html
Annual Research Report
81
important as it provided the first observed direct molecular dependence of the current; it also allows for understanding
the effects of heating of practical devices. A general theory has been developed7 and implemented in the circuit
simulator fREEDA that allows molecular components to be simulated in solid-state devices of the complexity of say the
Pentium® processor. A major research program funded by INTEL is also in progress, concerned with the development
of a molecular memory for computers.
Fundamentals (Cai)
Fundamental research is performed in areas such as solvation, quantum chemistry, and quantum mechanics in order
to determine effective means for dealing with both simple and complex chemical systems. In 2006 two Special
Issues of the Journal Chemical Physics were produced highlighting electron transfer in chemistry, biology, and
nanotechnology5-6. An explanation was also provided3 for the nature of the N-band absorptions of porphyrins and
chlorophylls. While the spectroscopy of these molecules is usually dominated by the typically lower energy Q and Soret
ban systems, we identify the nature of the N bands as charge-transfer states, see figure. These are shown to interact
strongly with their environment, including chemical substituents, having profound effects for oligoporphyrin-based
molecular wires. This work also established the first efficient a priori computational scheme capable of describing the
excited states of porphyrins and chlorophylls.
molecular electronics, Photosynthesis
Photosynthesis and Photovoltaics (Canfield, Hush,
Crossley)
The conversion of optical to chemical energy by plants is central
to most forms of life on this planet. We have computational
quantum chemistry2 to optimize the structure of the 150000-atom
Photosystem-I from green plants and used this to form a model
for optical energy flow from the antenna pigments to the “special
pair” responsible for the conversion of optical to electrical energy.
One third of this optimized structure is shown in the figure. In
addition, the actual solar-energy conversion process in purple
bacteria has been studied9 in great detailed through prediction
of the Stark spectra of a range of reaction centres produced and
studied experimentally by Boxer (Stanford). This shows how to
control the output voltage both in natural photosynthesis and in
organic photovoltaic devices.
Molecular Electronics (Solomon, Cafe, Chin, Larson, Wang, Ren, Hush, Crossley)
A rather large research field has opened in the area of molecular electronics, the exploitation of the electrical conductivity
properties of single molecules, with much research now performed by companies such as IBM, HP, Bell Labs, and
Hitachi. We have been involved in the development
of the field since its first conception. During 2006
we determined the mechanism for the physisorption
of aromatic molecule on noble metal surfaces 8 and
assembled a comprehensive review1 of the cycloaddition
reactions of alkenes with the silicon (100) surface. A
major theory was presented4,10-13 to explain the recently
observed Inelastic Electron Conduction Spectroscopy
of molecules such as alkaendithiols chemisorbed to
span two gold electrodes. As shown in the simulated
spectra presented in the figure, this technique allows
the molecular vibrational spectrum to be measured from
the second derivative of the current (I) passing through
the molecule as a function of bias voltage (V). This is
Selected Publications
1. Bilic, A, Reimers, JR and Hush, NS. Functionalization of semiconductor surfaces by organic layers: Concerted cycloaddition versus
stepwise free-radical reaction mechanisms. Properties of Single Organic Molecules on Crystal Surfaces, 333-360, 2006.
2. Canfield, P, Dahlbom, MG, Hush, NS and Reimers, JR. Density-functional geometry optimization of the 150 000-atom photosystemI trimer. Journal of Chemical Physics, 124, 24301, 2006.
3. Cai, Z-L, Crossley, MJ, Reimers, JR, Kobayashi, R and Amos, RD. Density functional theory for charge transfer: The nature of the
N-bands of porphyrins and chlorophylls revealed through CAM-B3LYP, CASPT2, and SAC-CI calculations. Journal of Physical
Chemistry B, 110, 15624-15632, 2006.
4. Solomon, GC, Gagliardi, A, Pecchia, A, Frauenheim, T, Di Carlo, A, Reimers, JR and Hush, NS. Understanding the inelastic
electron-tunneling spectra of alkanedithiols on gold. Journal of Chemical Physics, 124, 094704, 2006.
5. Reimers, JR, Ulstrup, J, Meyer Thomas, J and Solomon, GC. Special Issue: The molecules and methods of chemical biochemical,
and nanoscale electron transfer – Part 2 in honour of Noel S. Hush on his 80th birthday. Chemical Physics, 324, 2006.
6. Reimers, JR, Ulstrup, J, Meyer Thomas, J and Solomon, GC. Special Issue: The molecules and methods of chemical biochemical,
and nanoscale electron transfer – Part 2 in honour of Noel S. Hush on his 80th birthday. Chemical Physics, 326, 2006.
7. Kriplani, NM, Nackashi, DP, Amsinck, CJ, Di Spigna, NH, Steer, MB, Franzon, PD, Rick, RL, Solomon, GC and Reimers, JR.
Physically based molecular device model in a transient circuit simulator. Chem. Phys., 326, 188, 2006.
8. Bilic, A, Reimers, JR, Hush, NS, Hoft, RC and Ford, MJ. Adsorption of benzene on copper, silver, and gold surfaces. Journal of
Chemical Theory and Computation, 2, 1093-1105, 2006.
9. Kanchanawong, P, Dahlbom, MG, Treynor, TP, Reimers, JR, Hush, NS and Boxer, SG. Charge delocalization in the special-pair
radical cation of mutant reaction centers of Rhodobacter sphaeroides from stark spectra and nonadiabatic spectral simulations.
Journal of Physical Chemistry B, 110, 18688-18702, 2006.
10.Solomon, GC, Gagliardi, A, Pecchia, A, Frauenheim, T, Di Carlo, A, Reimers, JR and Hush, NS. Molecular origins of conduction
channels observed in shot-noise measurements. Nano Letters, 6, 2431-2437, 2006.
11.Solomon, GC, Gagliardi, A, Pecchis, A, Frauenheim, T, Di Carlo, A, Reimers, JR and Hush, NS. The symmetry of single-molecule
conduction. Journal of Chemical Physics, 125, 184702, 2006.
12.Pecchia, A, Gagliardi, A, Solomon, G, Di Carlo, A, Frauenheim, T and Reimers, JR. Incoherent tunnelling and heat dissipation
in moecular bridges. J. Phys. Conf. Ser., 2006.
13.Gagliardi, A, Solomon, G, Pecchia, A, Di Carlo, A, Frauenheim, T, Reimers, JR and Hush, NS. Simulations of inelastic tunnelling
in molecular bridges. In Nonequilibrium Carrier Dynamics in Semiconductors (Eds: Saraniti, M and Ravaioli, U), Springer-Verlag:
Berlin, 110, 183-186, 2006.
82
School of Chemistry
Dr Louis M Rendina
Room 518
School of Chemistry, F11
Telephone: +61 2 9351 4781
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_rendina.html
synthesis & bio-coordination chemistry
Platinum-Carborane Complexes as New Agents for Boron Neutron Capture Therapy (Ching, Coderre*, Crossley, Fisher)
The principal goal of this research program is to expand the clinical efficacies of platinum chemotherapy and radiotherapy
by coupling the potent DNA-binding characteristics of certain platinum compounds with the remarkable neutron capture
properties of the non-radioactive 10B nucleus that have been exploited in an experimental cancer treatment known as Boron
Neutron Capture Therapy (BNCT). BNCT is currently undergoing Phase I/II clinical trials in several countries for the
treatment of the brain tumour glioblastoma multiforme and malignant melanoma. The therapy utilizes 10B-containing
drugs and thermal neutrons of low kinetic energy (< 0.025 eV), although epithermal neutrons allow for deeper tissue
penetration. The very large, effective nuclear cross-section of the 10B nucleus (3837 barns, natural abundance = 19.8%)
makes it highly amenable to the neutron capture process. The major (94 %) reaction is shown in eq. 1:
B
10
+
1
n
→
[11B*] →
He2+
4
+
Li+
7
+ γ
+
2.4 MeV
(eq. 1)
The primary nuclear fission products that are produced in the neutron capture reactions have a high rate of linear energy
transfer and they cover a short range (ca. 10 µm, or one cell diameter). As a result, the immense amount of energy derived
from the nuclear reaction is dissipated in a very small volume and the selective destruction of tumour cells becomes
feasible with this type of therapy. 10B compounds that are localised near key cellular components such as chromosomal
DNA cause maximum cell damage in the presence of thermal neutrons. The proof-of-principle for the synthesis, DNAbinding, and tumour cell uptake of the archetypal Pt-carborane complexes has already been established in our laboratory
and the complexes represent two new classes of DNA-binding agents for potential use in BNCT.
We have investigated the deboronation reactions of closo-carborane derivatives to afford the corresponding
anionic nido-carborane species, which in some cases easily react with acetone to afford boron-rich dithioether carborane
ligands containing 18 boron atoms. We have also prepared novel dodecaborate(12) derivatives, e.g. [B12H11O(CH2)4SH]2–,
as these should possess significantly enhanced aqueous solubility and boron content compared to the corresponding
closo-carboranes analogues. Finally, we have prepared simple boronic acid derivatives of platinum(II) metallointercalator
complexes. These species readily undergo acid-base chemistry and we have commenced studies into their sugar-boronate
ester derivatives which should afford hydrophilic complexes possessing interesting biological properties.
*Department of Nuclear Science and Engineering, MIT.
Tumour-Targeted Boronated Phosphonium Salts as a New Class of Agents for Boron Neutron
Capture Therapy (Ioppolo)
It has been previously shown that phosphonium salts including triphenylmethylphosphonium (TPMP) represent a
promising class of delocalised lipophilic cations (DLCs) for use in tumour targeting and imaging. It is known that the
tumour selectivity and retention of TPMP in animal models is at least one order of magnitude greater than for clinical
agents currently used in BNCT. The incorporation of boron into DLCs such as TPMP would potentially result in the
selective delivery of this nucleus to the tumour site, notably by exploiting the key differences in the mitochondrial
membrane potential between cancerous and healthy cells. This is a highly significant innovation in the area of BNCT and
the expected outcomes include the development of new agents for the treatment of high-grade gliomas. We have recently
Annual Research Report
83
prepared the first examples of boronated arylphosphonium salts. These compounds
exhibit exquisite uptake in SF268 human glioblastoma cells in vitro. In some cases, e.g.
when 1,2-carborane is used, the phosphonium salt undergoes facile deboronation in polar
solution to afford the corresponding zwitterionic species containing a nido-carborane
cage (Fig. 1) and may thus be considered to be a “masked” phosphonium salt. This
work was recently the subject of a Provisional Patent (Ref. No. 2007900804) filed by
The University of Sydney.
Boronated RGD Cyclic Peptides as a New Class of Tumour-Specific Agents
for Boron Neutron Capture Therapy (Jolliffe, MacKay, Ziolkowski)
The primary goal of this project is to design and synthesise a series of boronated cyclic
peptides that will have the capacity to target over-expressed integrin proteins involved
Figure 1
in tumour angiogenesis and metastasis. In this project, there exists the potential of
delivering boron selectively to the tumour site and greatly improving the efficacy of
BNCT. Recent work has focussed on the synthesis of boronic acid derivatives of cyclic RGD (Arg-Gly-Asp) peptides,
and the syntheses of the first prototype compounds are now close to completion. We have also established comprehensive
in vitro cytotoxicity assays involving a series of tumour cell lines.
DNA Nanoshuttles (Harding¶, Mulcahy, Saccavini, Schilter)
A key feature that characterises the structure of toroidal DNA-binding proteins such as the DNA sliding clamp is the
central hole (~35 Å) which is large enough to accommodate double-helical nucleic acid with little steric hindrance for
B-DNA (~20 Å diameter). In general, the DNA-protein interaction is purely topological, and it is greatly stabilised
by powerful electrostatic interactions between the polyanionic phosphodiester backbone of DNA and a region of high
positive potential that surrounds the inner surface of the toroid. In this research program, we have sought to answer
whether linear DNA can thread nanoscale cationic macrocycles of platinum that we have termed DNA Nanoshuttles.
The interaction of nanoscale metal complexes with DNA is unprecedented and it would represent a significant advance
in the field of metal-DNA chemistry.
Recent work has focussed on (i) the synthesis of highly water-soluble N-donor ligands for incorporation
into molecular squares and polygons and (ii) the generation of a cationic macrocycle with a cavity size of ca. 3 nm by
the reaction of the labile precursor complexes [Pt(bpy)(NO3)2] or [Pd(bpy)(NO3)2] and PEG diamine ligands. ESI-MS
analysis of the platinum(II) product revealed the presence of ions distributions centred at m/z = 1310, 1247 and 624;
these are assigned to the ions [M – NO3–]+, [M – 2NO3– – H+]+ and [M – 2NO3–]2+, respectively. With the corresponding
palladium(II) precursor, the unique species was formed in almost quantitative yield and the ESI spectra featured two
prominent isotopic distributions centred at m/z = 1222 and 579. The envelopes are consistent with ions incorporating
one palladium(II) ion and correspond to [M – NO3–]+ and [M – 2NO3–]2+,
respectively. Complex has also been analysed by ESI-FT-ICR-MS and these
high resolution results are in complete accord with the low-resolution spectra.
Importantly, there is no evidence of higher nuclearity species in either case,
e.g. [2+2] species or catenanes. Importantly, this reaction was found to
be completely reproducible and the complexes are very water-soluble. An
analogous organo-soluble species containing a chelating phosphine ligand
was also prepared and fully characterized. We are now in a strong position
to commence comprehensive DNA-binding studies with selected complexes
in 2007.
¶
School of Chemistry, UNSW.
Selected Publications
1. Ioppolo, JA, Clegg, JK and Rendina, LM. Dicarba-closo-dodecaborane(12) derivatives of phosphonium salts: Formation of nidocarborane phosphonium zwitterions. Dalton Trans., 1982-1985, 2007.
2. Ching, HYV, Clegg, JK and Rendina, LM. Synthesis and preliminary DNA-binding studies of diimineplatinum(II) complexes
containing 3- or 4-pyridineboronic acid. Dalton Trans., 2121, 2007.
3. Crossley, EL, Ziolkowski, EJ, Coderre, JA and Rendina, LM. Boronated DNA-binding compounds as potential agents for boron
neutron capture therapy. Mini Rev. Med. Chem., 7, 303-313, 2007.
4. Lee, CKY, Groneman, JL, Turner, P, Rendina, LM and Harding, MM. Synthesis and X-Ray crystallographic analysis of chiral
pyridyl substituted carbocyclic molecular clefts. Tetrahedron, 62, 4870-4878, 2006,
84
School of Chemistry
Dr Siegbert A Schmid
Room 223
School of Chemistry, F11
Telephone: +61 2 9351 4196
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_schmid.html
INORGANIC SOLID STATE CHEMISTRY
and CHEMISTRY EDUCATION
Research in my group focuses on two major areas – Inorganic Solid State Chemistry and Education in Chemistry.
Research projects in the former area encompass a wide range of both synthetic chemistry and characterisation techniques,
in particular X-ray and neutron powder and single-crystal diffraction as well as electron microscopy using in-house
equipment as well as instrumentation at major national and international research facilities. In Chemistry Education
projects were geared towards an understanding of how we best support student learning, e.g. by using Information &
Communications Technology.
Modulated Structures of Oxopyroborates
A family of non-centrosymmetric oxo pyroborates, AMOB2O5 (A = K, Rb, Cs, Tl; M = Nb, Ta), have recently attracted
considerable interest owing to their potential use as nonlinear optical materials. Previously the structure of KNbOB2O5,
that adapts an eight-fold superstructure, was successfully solved and refined using a mixed conventional and superspace
approach. Using average structure positions and refined atomic modulation functions it was possible to calculate and
refine accurate atomic positional parameters in a superstructure model. This approach avoids problems in the refinement
caused by often large numbers of either weak or unobserved satellite reflections and might be used more generally. For
both KNbOB2O5 and the previously refined structure of RbNbOB2O5 (Schmid et al., 2000) apparent valence calculations
show, that potassium and rubidium, respectively, are satisfactorily bonded, providing a key to understanding the cause
of the modulation. Caesium, the largest A ion in this family, forms an unmodulated structure. The undistorted channels
formed by the framework, however, are too large to provide the smaller ions with an adequate bonding environment.
Instead the modulation reduces the size of the channels to fit those smaller ions. Temperature dependent X-ray powder
diffraction patterns for some members of the family were collected at the Photon Factory, Tsukuba, Japan, with a view
to better understand the driving forces that cause commensurate or incommensurate modulation.
The Personalisation Hypothesis in Pre-Laboratory E-Learning Environments (Yeung, George,
King†)
There has been much research activity investigating best practices for design of multimedia instructional materials and
for establishing effective e-learning environments. One area of such study has concerned the personalisation hypothesis,
first proposed by in 2000. The hypothesis is that student learning in virtual environments is better facilitated by the
use of personalised text forms (first person, more conversational style) than by non-personalised text forms (third person,
more formal style). Findings supporting the hypothesis have been based on students’ performance on both retention and
transfer tests, with most of the testing having been carried out in e-learning environments in the domains of physics
and biology.
This work set out to test the personalisation hypothesis using first year university students studying chemistry.
The e-learning environments chosen involved compulsory pre-laboratory activities, used to prepare students to carry
out experiments in acid-base chemistry. Approximately 600 students took part in the project, covering a range of levels
of prior knowledge within the domain. Retention and transfer tests were carried out immediately after students’ had
completed the pre-laboratory work and academic performance in this topic in the end-of-semester examination was
Annual Research Report
85
also investigated. The importance of factors such as gender, language background, and learning style preferences were
considered.
Li-Intercalation and Solid State Batteries (Barisic)
Compounds that can reversibly intercalate lithium have the potential to be used as cathodes in rechargeable lithium
ion batteries. Two characteristics, the availability of interstitial or defect sites for the incorporation of lithium and the
presence of reducible cations are found in some defect perovskites. The aim of this study is to synthesise a number of
defect perovskites, which might be useful as host materials for Li intercalation, and investigate their structures using
X-ray and neutron powder diffraction.
Phases in the SrO-ZrO2-Nb2O5 system were
investigated. Samples across the Sr0.7-xZr0.4-2xNb0.6-2xO3,
0.02 ≤ x ≤ 0.30, composition range have been prepared
from starting oxides (Zr, Nb) and carbonates (Sr) in
stoichiometric quantities. Samples were heated at 1400°C
in air and repeatedly reground. It was found that the
solid solution field extends from ~0.02 < x ≤ 0.3. Figure
1 shows the relationship between the cell dimensions
and the composition (Sr content) of the sample. X-ray
diffraction patterns have shown that all compositions
adopt a cubic perovskite sub-structure but that the correct
symmetry is lower in all cases. The resulting tetragonal
Figure 1. Composition dependence of the lattice
and orthorhombic space groups are indicated in Figure 1
parameters of Sr0.7+xZr0.4+2xNb0.6-2xO3, with a normalised
as well.
c value, c/√2. For the two-phase sample the I4/mcm c
Neutron powder diffraction data were collected
value is the larger of the two c values and the a value
from four samples prepared in 15 g batches. After careful
is the smaller of the two a values.
characterisation of the structures for the Li free samples,
these exact samples were then chemically intercalated
with Li (via the butyl-lithium route). Lithium intercalation was carried out chemically on three samples of the
Sr0.7+xZr0.4+2xNb0.6-2xO3 series with compositions x = 0.05, 0.10, and 0.15. Subsequently neutron diffraction patterns were
collected for two of these samples at RT. It was found that only subtle changes were detectable in the neutron diffraction
patterns. All the same reflections were present, at the same relative intensities. However, on closer inspection, it was
evident that there were some distinct and fundamental differences between the two patterns, e.g. a reversal of intensity
in some split peaks. The reversal results from a change in symmetry to a space group which has the a and c lattice
parameters switched, i.e. Imma. The best fit was obtained using a two-phase Imma and I4/mcm model, with Imma being
the predominant phase. The lowering in symmetry is possibly due to the fact that the lithium ions are extremely small
and the oxygen octahedra need to tilt more in order to satisfy their bonding requirements. Given that intercalation of
lithium results in the reduction of Nb5+ to Nb4+, the increased size of Nb4+ could be another reason behind the phase
change.
†
Collaborators from outside the School of Chemistry
Selected Publications
1. Norén, L, Withers, RL, Schmid, S, Brink, FJ and Ting, V. Old friends in a new light. “SnSb” revisited. J. Solid State Chem. 179,
404–412 (2006).
2. Schmid, S, Elcombe, M and Rhode, M. Defect perovskites in the SrO-ZrO2-Nb2O5 system. Australian Institute of Physics, Conference
Proceedings ‘Wagga Wagga 2006’. On-line at http://www.aip.org.au/wagga2006/TP15_Schmid.pdf.
3. Yeung, A, George, A, Schmid, S and King, M. Testing the personalization hypothesis in pre-laboratory e-learning environments.
Proceeding of the Assessment in Science Teaching and Learning Symposium. Sydney, NSW: UniServe Science, 146-152, 2006.
4. Schmid, S and T. The structure of KNbOB2O 5 – a commensurately modulated structure. Acta Crystallogr., B61,
361–366, 2005. Wagner,
5. Schmid, S and Yeung, A. The influence of a pre-laboratory work module on student performance in the first year chemistry laboratory.
Research and Development in Higher Education, 28, 471– 479, 2005.
6. Yeung, A, Read, J and Schmid, S. Students’ learning styles and academic performance in first year chemistry. In Merrett, D (Ed.).
Proceedings of Blended Learning in Science Teaching and Learning Symposium. Sydney, NSW: UniServe Science, 137–142, 2005.
7. Schmid, S. Early transition metal compounds with modulated structures. Habilitationsschrift (Habilitation Thesis), University
of Tübingen, 2002.
8. Withers, RL, Schmid, S and Thompson, JG. Compositionally and/or displacively flexible systems and their underlying crystal
chemistry. Prog. Solid State Chem., 26, 1–96, 1998.
86
School of Chemistry
Dr Timothy Schmidt
Room 457
School of Chemistry, F11
Telephone: +61 2 9351 2781
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_schmidtt.html
Annual Research Report
87
Polycyclic Aromatic Hydrocarbons
A possible class of molecules responsible for the DIBs are the large polycyclic aromatic hydrocarbon (PAH) molecules or
their radicals. By obtaining gas phase excitation spectra of large PAH radicals and neutrals we are able to compare the
absorption positions to the DIBs. Our current focus is a special class of PAH molecule called the all-benzenoid PAHs, a
series of PAHs in which the structures may be drawn such that the electrons reside in benzenoid rings joined by “single
bonds”. Indeed, these “single” bonds are longer by approximately 0.05Å compared to the intra-benzenoid bonds.
We obtained the R2C2PI-TOF, laser-induced fluorescence and dispersed fluorescence spectra of triphenylene in 2006.
The spectrum was analyzed in terms of Herzberg-Teller coupling, a breakdown of the crude Born-Oppenheimer
approximation.
The Red Rectangle (Rob Sharp, AAO)
MOLECULAR SPECTROSCOPY AND
QUANTUM THEORY
The inner workings of molecules may be elucidated
by performing sophisticated laser spectroscopic
experiments, probing their electronic structure
and nuclear dynamics. Experiments performed in
the purest environment available, high vacuum,
allow us to interrogate exotic molecules with a
view to answering questions about molecules in
similar environments, such as outer space, or very
different environments, such as the condensed
phase. Molecules in the interstellar medium and
The group logo above shows a 2-D joint laser induced
those invoked as molecular electronic devices share
fluorescence / dispersed fluorescence spectrum of the
in common the motif of conjugation. By exploiting
Swan bands of C2 that looks uncannily like a comet trail,
this link we are able to apply our fundamental
in which C2 has been also observed.
astrophysical research to applied problems in
molecular electronics.
The interpretation of our experimental
data is guided by a set of computational tools. By testing our available quantum mechanical computational techniques
against rigorous spectroscopic data, we can then apply these techniques with a degree of confidence to problems beyond
the scope of direct measurement.
Astrophysics and Molecular Spectroscopy
The oldest unsolved problem in molecular spectroscopy is that of
the identity of the carriers of the Diffuse Interstellar Bands (DIBs),
a series of 300 diffuse absorption features exhibited in the spectra
obtained of stars occluded by diffuse interstellar clouds. The
carriers of the DIBs are widely believed to be conjugated carbon
molecules with strong optical transitions. In 2006 we made the
startling discovery of a molecular radical absorbing coincident
with the diffuse interstellar band at 476 nm. The radical is the
brightest fluorescent radical in a benzene discharge after C2 and
C3. While this radical is likely to be aromatic, its exact chemical
nature has so far eluded us and awaits investigation by resonant
2-colour 2-photon ionization time-of-flight mass-spectroscopy
(R2C2PI-TOF).
In late 2004, using the 8m Very Large Telescope of the European Southern
Observatory, we obtained the highest-yet resolution spectra of the Red
Rectangle, a nearby biconical proto-planetary nebula. The Red Rectangle
exhibits a number of unidentified emission features which are presumably
molecular. Modelling of the spectra suggests a large PAH carrier exhibiting
sequence structure. We believe that discovery of the identity of the carrier
of the Red Rectangle Bands will provide a “foot in the door” to the
discovery of the DIB carriers. In the course of analyzing these spectra we
identified the C2 molecule fluorescing in the walls of the nebula’s bicones.
We have been able to model the behaviour of C2 and in doing so construct
constraints on the carrier of the unidentified emission bands. In late 2006,
Damian Kokkin and Rob Sharp obtained more C2 Swan spectra from the
Red Rectangle which is currently under analysis.
A New Band System of C2 (Kable, Nauta)
Inspired by the observation of C2 in the Red Rectangle, and wishing to fully understand this phenomenon,
we undertook an all-out assault on the C2 molecule using sophisticated quantum theory. Our results agreed
to about 0.1% with experiment and have resulted in an upwards 21% revision of the abundance of C2 in the
interstellar medium. One electronic state was seemingly ill-calculated. Closer inspection revealed that it
has never been directly observed. We undertook to observe the d-c transition of C2 for the first time, finally
revealing the true character of the c state. The original calculations were vindicated.
Femtosecond Spectroscopy
In collaboration with others, principally Ned Ekins-Daukes from the School of Physics, we obtained funding in 2005 for
a femtosecond laser system. This is being installed in new laboratories 2007 and will open up a world of time-resolved
and high-intensity laser experiments.
Selected Publications
1. Kokkin, DL, Troy, TP, Nauta, K, Schmidt, TW. Gas phase spectra of all-benzenoid polycyclic aromatic hydrocarbons: Triphenylene.
J. Chem.Phys., 126, 019708, 2007.
2. Kokkin, DL, Bacskay, GB and Schmidt, TW. Oscillator strengths and radiative lifetimes forC2: Swan, Ballik-Ramsay, Phillips
and d3Pg← c3Su+ systems. J. Chem.Phys., 126, 304707, 2007.
3. Kokkin, DL, Reilly, NJ, Morris, CW, Nakajima, M, Nauta, K, Kable, SH and Schmidt, TW. Observation of the
d3Pg ← c3S+u band system of C2. Journal of Chemical Physics, 125, 231101, 2006.
4. Reilly, NJ, Schmidt, TW and Kable, SH. Two-dimensional fluorescence (excitation/emission) spectroscopy as a probe of complex
chemical environments. Journal of Physical Chemistry A, 110, 12355-12359, 2006.
5. Troy, TP and Schmidt, TW. A theoretical treatment of the absorption spectra of all-benzenoid hydrocarbons. Monthly Notices of the
Royal Astronomical Society, 371, L41-L44, 2006.
6. Reilly, NJ, Cupitt, GC, Kable, SH and Schmidt, TW. An experimental and theoretical investigation of the dispersed fluorescence
spectroscopy of HC4S. Journal of Chemical Physics, 124, 194310, 2006.
7. Kokkin, DL and Schmidt, TW. On the electronic properties of dehydrogenated polycyclic aromatic hydrocarbons. Journal of Physical
Chemistry A, 110, 6173-6177, 2006.
8. Sharp, RG, Reilly, NJ, Kable, SH and Schmidt, TW. Sequence structure emission in the red rectangle bands. Astrophysical Journal,
639, 194-203, 2006.
88
School of Chemistry
Emeritus Professor Sever Sternhell, FAA
Honorary Staff
Room 146
School of Chemistry, F11
Telephone: +61 2 9351 4421
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_sternhell.html
areas of interest:
Mechanochemistry
Mechanical processes, e.g., ballmilling, can provide the energy needed for chemical reactions to proceed. Initial results
indicate that rather unexpected reactions (e.g., transfer of hydrogen atoms) occur under such conditions and the primary
aim of this project is to investigate them in a systematic manner. Practical possibilities include the destruction of persistent
environmental pollutants, such as DDT.
Induction of Chirality in Mesophases
Mesophases, i.e., forms of matter intermediate between crystalline solids and liquids, may be made chiral by addition
of small amounts of chiral inducers or dopants. Initial results gave a number of desirable structural characteristics for
efficient dopands and include the most powerful dopands yet reported. Practical possibilities include better materials
for liquid-crystal based display panels.
Selected Publications
1. Cheung, J, Field, LD, Regaglia, FM and Sternhell, S. Synthesis of helical molecules based on 5,6,6a,7,8,12b-hexahydrobenzo[c]phenanthrene-5,8-diones. Aust. J. Chem., 48, 1707-1725, 1995.
2. Cheung, J, Field, LD, Hambley,TW and Sternhell, S. Inversion of helical molecules based on 5,6,6a,7,8,12b-hexahydrobenzo[c]phenanthrene-5,8-diones. Aust. J. Chem., 48, 1727-1740, 1995.
3. Field, LD, Sternhell, S and Kalman, JR. Organic Structures from Spectra. Second Edition, John Wiley & Sons, 1995.
4. Field, LD, Sternhell, S and Wilton, HV. Mechanochemistry of some hydrocarbons. Tetrahedron, 53, 4051-4062, 1997.
5. Cheung, J, Field, LD, Hambley, TW and Sternhell, S. Synthesis of chiral molecular template based on trans-5,6,6a,12b-hexahydro1,12-dimethylbenzo[c]phenanthrene-5,8-dione. J. Org. Chem., 62, 62-66, 1997.
6. Cheung, J, Field, LD and Sternhell, S. Highly efficient chirality inductors based on (5RS,8RS)-trans-5,6,6a,7,8,12b-hexagtdriveb
zo[c]phenanthrene-5,8-diol. J. Org. Chem., 62, 7044-7046, 1997.
7. Field, LD, Sternhell, S and Wilton, HV. Mechanohydrogenation. Tetrahedron letters, 39, 115-116, 1998.
8. Park, JJ, Sternhell, S and Vonwiller, SC. Highly efficient chirality inducers based on steroid-derived 2,6,9-trioxabicylco[3.3.1]n
onanes. J. Org. Chem., 63, 6749-6751, 1998.
9. Kalman, JR, Morgan, J, Pinhey, JT and Sternhell, S. Electrophilic metal-alkyl bond cleavage in tetraorganosilicon and tetraorganotin
compounds by lead tetracarboxylates and aryllead tricarboxylates. Tetrahedron, 55, 3615-3624, 1999.
10. Field, LD, Sternhell, S andKalman, JR. Organic structures from spectra. Third Edition, John Wiley & Sons, 2002.
Annual Research Report
89
90
School of Chemistry
Annual Research Report
Emeritus Professor Walter C Taylor, OAM
Selected Publications
Honorary Staff
Room 146
School of Chemistry, F11
Telephone: +61 2 9351 2748
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_taylor.html
areas of interest:
Research centres on chemical and biological aspects of natural products. The aims are:
(i) to study the constituents of plants in relation to their taxonomy (chemotaxonomy) and identify intermediates including novel products in biogenetic pathways;
(ii)
to isolate and study useful substances including pharmacologically active compounds.
(a)
The plant Schefflera leucantha (Araliaceae) is used widely in Thailand and China as an antiasthmatic. The
active bronchodilator principle is a mixture of saponins; the pure components have been isolated in
order to establish the structures and to study the biological properties.
(b)
The seeds of the Indonesian plant, Chydenathus sp. contain significant quantities of saponins which
are toxic to fish. The pure saponins are being isolated and their structures elucidated by NMR and MS
studies.
(c) Members of the Guttiferae family [e.g. Garcinia mangostana (mangosteen)] are rich in xanthone derivatives,
some of which have been found to be active as antibacterial/antifungal agents. Other members of
the Guttiferae occurring in southern Thailand are being examined with a view to developing useful
compounds.
(d) Antiviral constituents of Clinacanthus nutans and anti-hypotensive constituents of Tacca chantrieri are
being studied.
Extensive collaborations exist with universities in Indonesia, Myanmar, Nepal, Thailand and Vietnam with botanists,
chemists and biologists studying local floras used in traditional medicine. Eight papers were published in 2006.
Current Projects:
•
•
•
•
•
•
Bronchodilator constituents of Schefflera leucantha, and anti-hypertensive constituents of Tacca chantrieri.
Antiviral constituents of Clinacanthus nutans
Constituents of Garcinia spp.; antibacterial derivatives of mangostin
Constituents of Thai medicinal plants
Constituents of medicinal plants of Myanmar
Constituents of endophytic fungi
91
1. Nguyen, MC, Taylor, WC and Sung, TV. A new cyclobutane lignan from Cinnamomum balansae. Natural Product Letters, 15, 331338 2001.
2. Tuntiwach-wuttikul, P and Taylor, WC. New rearranged clerodane diterpenes from Tinospora baenzigeri. Chem. Pharm. Bull., 49,
854-857 2001.
3. Tuchinda, P, Reutrakul, V, Claeson, P, Pongrayoon, U, Sematong, T, Santisuk, T and Taylor, WC. Anti-inflammatory cyclohexenyl
chalcone derivatives in Boesenbergia pandurata. Phytochemistry, 59, 169-173, 2002.
4. Rukachaisirikul, V, Sukpondma, Y, Jansakul, C and Taylor, WC. Isoflavone glycosides from Derris scandens. Phytochemistry, 60,
827-834, 2002.
5. Nguyen, MC, Tran, VS and Taylor, WC. Biological activity of glypetoline, a sulfur-containing indole alkaloid from Glycosmis
petelotii. J. Materia Medica Hanoi, 7, 24-27, 2002.
6. Rukachaisirikul, V, Ritthiwigrom, T, Pinsa, A, Sawangchote, P and Taylor, WC. Xanthones from the stem bark of Garcinia
nigrolineata. Phytochemistry, 64, 1149-1156, 2003.
7. Tuntiwach-wuttikul, P, Rayanil, K and Taylor, WC. Chemical constituents from the flowers of Nyctanthes arbor-tristis. ScienceAsia,
29, 21-30, 2003.
8. Rukachaisirikul, V, Painuphong, P, Sukpondma, Y, Koysomboon, S, Sawangchote, P and Taylor, WC. Caged-triprenylated and
-tetraprenylated xanthones from the latex of Garcinia scortechinii. Journal of Natural Products, 66, 933-938, 2003.
9. Rukachaisirikul, V, Kamkaew, M, Sukavisit, D, Phongpaichit, S, Sawangchote, P and Taylor, WC. Antibacterial xanthones from
the leaves of Garcinia nigrolineata. Journal of Natural Products, 66, 1531-1535, 2003.
10.Tuntiwachwuttikul, P, Pootaeng-on, Y, Pansa, P, Srisanpang, T and Taylor, WC. Sulfur-containing compounds from Clinacathus
siamensis. Chemical and Pharmaceutical Bulletin Japan, 51, 1423-1425, 2003.
11.Rukachaisirikul, V, Pailee, P, Hiranrat, A, Tuchinda, P, Yoosook, C, Kasit, J, Taylor, WC and Reutrakul, V. Anti-HIV-1 protostane
triterpenes and digeranylbenzophenone from trunk bark and stems of Garcinia speciosa. Planta Medica, 69, 1141-1146, 2003.
12.Deachathai S, Mahabusarakam W, Phongpaichit S and Taylor WC. Phenolic compounds from the fruit of Garcinia dulcis.
Phytochemistry, 66, 2368-75. 2005,
13.Mahabusarakam W, Chairerk P and Taylor WC. Xanthones from Garcinia cowa Roxb. latex. Phytochemistry, 66, 1148-53, 2005.
14. Rukachaisirikul, V, Phainuphong, P, Sukpondma, Y, Phongpaichit, S and Taylor, WC. Antibacterial caged-tetraprenylated xanthones
from the stem bark of Garcinia scortechinii. Planta Medica, 71,165-70, 2005.
15. Son, PT, Giang, PM and Taylor, WC. NMR studies of darutoside, a rare ENT-pimarane glucoside. Natural Product Research, 19,
503-7, 2005.
16.Deachathai, S, Mahabusarakam, W, Phongpaichit, S, Taylor, WC, Zhang, Y-J and Yang, C-R. Phenolic compounds from the flowers
of Garcinia dulcis. Phytochemistry, 67, 464-469, 2006.
17.Mahabusarakam, Nuangnaowarat, W and Taylor, WC. Xanthone derivatives from Cratoxylum cochinchinense roots. Phytochemistry,
67, 470-474, 2006.
18.Pittaya, T, Photchana, P, Yupa, P and Taylor, WC. Chromones from the branches of Harrisonda perforata. Chemical & Pharmaceutical
Bulletin, 54, 44-47, 2006.
19.Pittaya, T, Photchana, P, Yupa, P and Taylor, WC. Chemical constituents of the roots of Piper Sarmentosum. Chemical &
Pharmaceutical Bulletin, 54, 149-151, 2006.
20.Taechowisan, T, Wanbanjob, A, Tuntiwachwuttikul, P and Taylor, WC. Identification of Streptomyces sp Tc022, an endophyte in
Alpinia galanga, and the isolation of actinomycin D. Annals of Microbiology, 56, 113-117, 2006.
21.Mahabusarakam, W, Kuaha, K, Wilairat, P and Taylor, WC. Prenylated xanthones as potential antiplasmodial substances. Planta
Medica, 72, 912-916, 2006.
22.Panthong, K, Pongcharoen, W, Phongpaichit, S and Taylor, WC. Tetraoxygenated xanthones from the fruits of Garcinia cowa.
Phytochemistry, 67, 999-1004, 2006.
23.Willis, AC, O’Connor, PD, Taylor, WC and Mander, LN. The absolute stereochemistry of the Galbulimima alkaloids. Australian
Journal of Chemistry, 59, 629-632, 2006.
92
School of Chemistry
Dr Pall Thordarson
Room 509a
School of Chemistry, F11
Telephone: +61 2 9351 4456
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_pall.html
biomimetic chemistry and nanotechnology
The most complex and elegant examples of “nanotechnology” come from Nature. In our group we first look to Nature for
inspiration when it comes to solving the problems we are currently dealing with in nanotechnology (e.g., biosensors or
tissue engineering). Methods to direct the assembly of functional molecules are of particular interest to us as are methods
to analyse nanostructures, e.g. by the use of scanning probe microscopy (AFM and STM).
Light-Activated Bioconjugates (Peterson, Prasad, Smith*)
We are developing novel ways to control the function of redox proteins using light as the external input signal. The focus
will be on using synthetic chromophores, conjugated either to proteins (direct activation) or to biological co-factors such
as NAD—nicotinamide adenine dinucleotides— (indirect activation). In the first project we have synthesized a series
of bioconjugates between synthetic donor chromophores (Ru-terpyridines) and a redox acceptor protein (cytochrome
c). Using laser spectroscopy, we have been able to demonstrate that photoinduced electron transfer (see figure – below)
takes place between the donor and protein-acceptor upon excitation of the Ru-terpyridine. In the second project, we
have shown that our photocatalyst is capable of reducing NAD and we are now currently optimising its performance by
synthesizing NAD modified with our photocatalyst. We will continue to develop the application of these conjugates in
three areas: biosensing, synthesis, and single-molecule research.
Annual Research Report
93
bio-mimetic ECM materials for applications in tissue engineering and drug delivery. We recently discovered a novel
family of LMOG 1 (see figure – below) that form gels in hexanes and other non-polar solvents that collapse upon addition
of small anions such as Cl- and Br-. We are now investigating how we can utilize the unique properties of our LMOG 1
to create a new type of “smart”gels for biomedical applications (e.g., cancer therapy).
Nanostructural Microscopy (Chin, Crossley, Hush, Larsen, Reimers, Braet*, Elemans*)
To analyse chemical structures on the nanoscale (1-100 nm), we can no longer rely on traditional techniques such as
NMR spectroscopy. We need to resort to the use of high-resolution microscopy, and we have several on-going projects
in this area.
The largest of these is on the creation of a molecular memory in collaboration with Intel Inc. that the Molecular
Electronics Group (Crossley, Hush, Reimers and Thordarson) is currently undertaking. This project received an ARC
Linkage grant in 2004 and work is now on-going to develop the microscopy techniques (AFM and STM) that are necessary
to characterise the molecular memory components.
Other projects our group is working on within this area are: Single molecule imaging (see figure – below) of
catalytic porphyrins (Crossley, Elemans) and electron microscopy (TEM and SEM) studies of self-assembled gels from
small molecules (Braet).
Selected Publications
Self-Assembled Gels (Tong, Webb, Braet*)
The extra-cellular matrix (ECM) outside the cell in multi-cellular organisms is a gel-like material, consisting mostly of
proteins such as elastin and collagen. Bio-mimetic materials that resemble the ECM are of particular interest as they can
be designed to interact favourably with the surrounding tissue, e.g., by stimulating a particular type of cell growth.
Self-assembed gels formed from low molecular-mass organic gelators (LMOG) seem to be superior to polymeric gels as
1. Thordarson, P, Bijsterveld, EJA, Rowan, AE and Nolte, RJM. Epoxidation of polybutadiene by a topologically linked catalyst.
Nature, 424, 915-8, 2003.
2. Scanning Tunneling Microscopy and Spectroscopy Studies of Porphyrins at Solid-Liquid Interfaces. B Hulsken, R van Hameren,
P Thordarson, J W Gerritsen, R J M Nolte, A E Rowan, M J Crossley, J A A W Elemans and S Speller, Jpn. J. Appl. Phys., 45,
1953-5, 2006.
3. Developments in using Scanning Probe Microscopy to study Molecules on Surfaces – From Thin Films and Single-molecule
Conductivity to Drug-living Cell Interactions. P Thordarson, R Atkin, W H J Kalle, G G Warr and F Braet, Aust. J. Chem., 59,
359-75, 2006.
4. Well-defined Protein-Polymer Conjugates – Synthesis and Potential Applications. P Thordarson, B Le Droumaguet and K Velonia,
Appl. Microbiol. Biotechnol., 73, 243-54, 2006.
5. Real-Time Single Molecule Imaging of Alkene Oxidation by Manganese Porphyrins at a Liquid-Solid Interface. B Hulsken, R van
Hameren, J W Gerritsen, T Khoury, P Thordarson, M J Crossley, A E Rowan, R J M Nolte, J A A W Elemans and S Speller, Nature
Nanotechnology, 2, 285-9, 2007.
94
School of Chemistry
Dr Matthew Todd
Room 545
School of Chemistry, F11
Telephone: +61 2 9351 2180
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_todd.html
Chemical Biology of Schistosomiasis
Schistosomiasis (Bilharzia) is one of the most burdensome of the neglected
tropical diseases, affecting more than 400 million people worldwide.4 The drug
used to treat this disease, Praziquantel (rac-3), is currently being administered
in mass chemotherapy programs in Africa. This will inevitably lead to the
development of resistance, and no back-up drugs exist for the treatment
of schistosomiasis. With an international group of collaborators, we seek
new drugs for this disease through the synthesis of analogues and through
discovering the as-yet unknown in vivo target of PZQ.5
Pictured right: The Biomphalaria snail, the intermediate host of the
parasite principally responsible for Bilharzia in Africa, Schistosoma mansoni.
Biosensing and Molecular Recognition
Synthesis and chemical biology
Two projects are currently underway in collaboration with Lisa Hall
at Cambridge and Mike Watkinson at Queen Mary, London. We are
building macromolecular constructs for biosensing applications.
These consist of metal complexes of aza-macrocycles attached to a
molecular recognition scaffold which in our model studies is either
biotin or a mimic of a tripeptide sequence (RGD) known to be
important in cell adhesion. The molecular recognition events are
designed to be detected either electrochemically (with scoprionlike complexes shown here) or with surface plasmon resonance, and
are easily variable, making them useful for a the early detection
and diagnosis of various disease states.
We have an interest in synthesising small organic molecules in interesting ways, as well as using them to probe various
biological processes.
Nonlinear Effects in Asymmetric Catalysis
It is reasonable to expect a linear relationship between the enantiomeric excess
(e.e.) of a catalyst employed in a chemical reaction and the e.e. of the product of
that reaction. There are many cases known where this is not the case.1 Sometimes
a very high excess of one enantiomer can arise from a nearly racemic catalyst. Such
‘Nonlinear Effects’ (NLEs) may have wide use in industrial synthesis, as well as
playing some role in the origin of asymmetry in life. We are aiming to understand
such effects in several model systems with a combination of experimental and
computational approaches in asymmetric catalysis, so that we might develop a
predictive model of when NLEs occur.
Pictured left: Minimised Structures for Noyori’s DAIB Ligands Displaying
High Asymmetric Amplification by a Positive NLE.
95
Annual Research Report
Open Source Research Methods
We have recently become involved with a group of biologists, lawyers and
computer scientists known as The Synaptic Leap.6 We are interested in
whether open source methods, which have produced such enormous successes
in computer science (Linux, Firefox, Wikipedia etc) can be extended more
generally to biomedical research.7 Current projects focus on the tropical diseases
schistosomiasis and malaria.
Asymmetric Organocatalysis
Several small organic molecules have in recent years been shown to be very effective at catalysing constructive organic
reactions in aqueous, metal-free systems. For example the amino acid proline can catalyse the aldol reaction with
remarkable efficiency and stereoselectivity.
We are seeking to understand such reactions
and have begun with a study of asymmetric
catalysis in the aza-Henry reaction (1 to 2),
for the synthesis of the active enantiomer
of the important anti-parasitic drug
Praziquantel (3).2
Heterocyclic Methodology
The enediamides (e.g. 4) are a novel class of heterocyclic compounds
we have discovered and investigated.3 They display interesting reactive
characteristics we are exploiting for the construction of small molecule
mimics of peptide secondary structure such as β-turns (6). We have shown
that the chemistry of the double bond contained in these heterocycles is
highly stereoselective, directed by the stereocentre from the amino acid
used in the ring synthesis.
Selected Publications
1. Todd, MH. Asymmetric autocatalysis: Product recruitment for the increase in the chiral environment (PRICE). Chem. Soc. Rev.,
31, 211-222, 2002.
2. El-Fayoummy, S, Mansour, W and Todd, MH. Solid phase synthesis of praziquantel. Tetrahedron Lett., 47, 1287-1290, 2006.
3. Todd, MH, Ndubaku, CO and Bartlett, PA. Amino acid-derived heterocycles: Lewis acid-catalyzed and radical cyclizations from
peptide acetals. J. Org. Chem., 67, 3985-3988, 2002.
4. Fenwick, A, Savioli, L, Engels, D, Bergquist, R and Todd, MH. Drugs for the control of parasitic diseases: Current status and
development. Schistosomiasis. Trends in Parasitology, 19, 509-515, 2003.
5. Kusel, JR, Oliveira, FA, Todd, M, Ronketti, F, Lima, SF, Mattos, ACA, Reis, KT, Coelho, PMZ, Thornhill, JA and Ribeiro, F. The
effects of drugs, ions, and poly-l-lysine on the exretory system of Schistosoma mansoni. Instituto Oswaldo Cruz, Rio de Janeiro,
101, 293-298, 2006.
6. http://www.thesynapticleap.org/
7. a) Kepler, TB, Marti-Renom, MA, Maurer, SM, Rai, AK, Taylor, G and Todd, MH. Open source research – the power of us.
Aust. J. Chem., 59, 291-294, 2006; b) Todd, MH. Open access and open source in chemistry. Chemistry Central Journal, 1:3,
2007.
8. Tamanini, E, Watkinson, M and Todd, MH. Improved synthesis of the valuable peptidomimetic intermediate 3-azido-4-hydroxy
cyclopentanoic acid. Tetrahedron: Asymmetry, 17, 2235-2239, 2006.
9. Ismail, MAH, Barker, S, Abou El Ella, DA, Abouzid, KAM, Toubar, RA and Todd, MH. Design and synthesis of new tetrazolyl- and
carboxy-biphenylylmethyl-quinazolin-4-one derivatives as angiotensin II AT1 receptor antagonists. J. Med. Chem., 49, 1526-1535,
2006.
96
School of Chemistry
Professor Gregory G Warr
Room 310
School of Chemistry, F11
Telephone: +61 2 9351 2106
Facsimile: +61 2 9351 3329
Email: [email protected]
http://www.chem.usyd.edu.au/about/staff_warr.html
Annual Research Report
Self-Assembly of Block Co-oligomers (Blom, Hawkett, Ganeva)
We have prepared a range of novel amphiphilic block co-oligomers using controlled radical
polymerization (RAFT) in which the hydrophobic and hydrophilic block structure and
composition are systematically varied. These amphiphiles lie in a little-understood composition
range between surfactants and block copolymers, where the relaxation time for self-assembly is
one of the key parameters. Using a combination of small-angle x-ray and neutron scattering
and optical microscopy, we have investigated the structure and stability of micelles, vesicles
and liquid crystal phases they form in aqueous solution under various solution conditions, and
how the relaxation dynamics can be used to tune the equilibrium structure, and also manipulate
the system between equilibrium and kinetically-trapped states. The living nature of RAFT
polymerization gives us the added capability to further grow the polymer chains in situ, leading
to new polymeric nanostructures.
Emulsion Structure and Stability (Beattie, Djerdjev, Jain, Hawkett, Whitby)
soft matter and surfaces
Our research is aimed at understanding the behaviour of amphiphilic compounds in bulk phases (solutions, liquid
crystals, complex fluids), in colloidal systems (emulsions, foams, dispersions), and at interfaces. In a wide range of projects
we examine the structure and dynamics of bulk phases and dispersions using techniques including neutron and x-ray
scattering, optical microscopy, rheology and calorimetry, and interfacial structure by neutron reflectometry, adsorption
isotherms, atomic force microscopy, and surface force measurements. By combining these techniques we are discovering
new structures formed when surface-active molecules adsorb at the solid/liquid interface or when complex fluids abut an
interface, and use this to design new nanostructured materials.
Polymerisable Surfactant Nanostructures (Topp, Chatjaroenporn, Kurihara,* Schwering*)
Polymerisable surfactants – surfmers – have the potential to capture and render permanent the complex nanostructures
formed by amphiphilic self-assembly. Our two projects in this area address bulk self-assembly structure and ultra-thin
polymerisable films. We have discovered a new controlled polymerisation mechanism by which we can prepare surfactant
oligomers or polymers with tunable properties, thereby kinetically trapping polymeric surfactant aggregates to preserve
the spontaneous self-assembly structure of the surfmer (Topp). This mechanism, as well as conventional free-radical
photopolymerisation is being used to polymerise adsorbed layers of surfmers into ultra-thin, laterally nanostructured
films as permanent coatings on various solid substrates (Chatjaroenporn, Schwering, Kurihara).
Structure and Self-Assembly in Ionic Liquids (Araos, Atkin, McAlpine, Hernandez*)
We have prepared several new ammonium nitrate, formate and thiocyanate room-temperature ionic liquids, i.e. salts that
melt below room temperature, and shown that surfactants can self-assemble into micelles and liquid crystals and can
form microemulsions in these compounds as well as commercial ionic liquids, and can also form structured aggregates
at ionic liquid/solid interfaces.
The micellar structure is weakly sensitive to the chemical composition of the ionic liquid, but the phase
behaviour strongly depends on the hydrogen-bonding network.(McAlpine, Hernandez) The structure and stability of
microemulsions closely parallels water-based systems, with a structure that evolves from ol continuous through bicontinous
to ionic liquid continuous with increasing temperature. Small-angle neutron scattering has revealed unusual ordering
of the oil and ionic liquid domains within bicontinuous microemulsions. (Atkin)
The alignment and orientation of the constituent ions of these unusual liquids at solid surfaces has been shown
by atomic force microscopy. Electrostatic and dispersion interactions within the liquid compete with the solid substrate
to determine cation binding and orientation. (Atkin)
We use water-in-oil emulsions containing magnetic nanoparticles (aqueous ferrofluid emulsions)
to investigate the colloidal forces that stabilise them by magnetic chaining. The magnetic
nanoparticles align in an external field, leading to strings of evenly-spaced droplets. As the
field strength is changed, so does the separation between droplet surfaces and the droplets may
deform. The changing structure of the dispersion is revealed by small-angle neutron scattering (see
scattering patterns at right). By changing emulsifier type and concentration, and the composition
of the continuous phase, we gain new insights into the factors that enhance emulsion stability.
This work has also led to advances in the design of stable, aqueous ferrofluids. (Jain, Hawkett)
We have also used small-angle and ultra-small-angle neutron scattering to probe the
structure of oil-in-water emulsions that are believed to be stabilized by a nanoparticle adsorbed
layer in the droplet surface. (Whitby, Djerdjev, Beattie)
Emulsion Structure and Stability (Blom, Atkin, Zana)
Our ongoing investigations of the adsorbed layer structure of surfactants on solid surfaces in
equilibrium with aqueous (or ionic liquid) solutions has continued, principally using neutron
reflectometry and atomic force microscopy. The growth of well-defined adsorbed bilayers has
been shown to occur by quite distinct mechanisms for different double-chained ionic surfactants.
The gradual breakup of such adsorbed bilayers induced by uptake of a more soluble surfactant
has been observed. Whereas on mica this occurs via a well-defined progression of aggregate
curvature through a mesh into cylinders and globular adsorbed aggregates, this is far less clear
on quartz. The essential role of surfactant packing and aggregate curvature on mica has also been
demonstrated in mixtures of soluble surfactants. (Blom)
The relationship between molecular structure of monomeric and gemini surfactants and
their adsorbed layer morphologies has been investigated, and this will continue as we investigate
oligomeric and polymerized adsorbed surfactant films. (Zana)
Selected Publications
1. Vesiculated Polymer Particles. Australian Provisional Patent number 12844010, October 2006
2. Atkin, R and Warr, GG. Structure in confined room temperature ionic liquids. J. Phys. Chem. C, 111,
5162-68, 2007.
3. Whitby, CP, Djerdjev, AM, Beattie, JK and Warr, GG. In situ determination of the size and polydispersity
of concentrated emulsions. Langmuir, 23, 1694-1700, 2007.
4. Blom, A, Warr, GG and Wanless, EJ. Growth of adsorbed layers of double-chained cationic surfactants
on mica. Aust. J. Chem., 59, 381-385, 2006.
5. Blom, A and Warr, GG. Structure and composition of cationic-nonionic surfactant mixed adsorbed layers
on mica. Langmuir, 22, 6787-6795, 2006.
6. Whitby, CP, Djerdjev, AM, Beattie, JK and Warr, GG. Nanoparticle adsorption and stabilization of
surfactant-free emulsions. J. Colloid Interface Sci., 301, 342-345, 2006.
7. Duval, FP, Zana, R and Warr, GG. Adsorbed layer structure of cationic gemini and corresponding
monomeric surfactants on mica. Langmuir, 22, 1143-1149, 2006.
97
98
School of Chemistry
Research
Centres
100
School of Chemistry
Annual Research Report
Key Personnel in the OSC are:
Director:
Dr Mal D McLeod (School of Chemistry)
Director:
Dr Malcolm McLeod
The Organic Synthesis Centre
within the School of Chemistry, Building F11
Room 517
Telephone: +61 2 9351 5877
Facsimile: +61 2 9351 6650
Email: [email protected]
http://osc.chem.usyd.edu.au/
Deputy Director:
Dr Kate A Jolliffe (School of Chemistry)
Executive Officer:
Dr Pat J Stamford (School of Chemistry)
Mr Matthew Fitzhenry and
Dr Paulo Da Silva
S
ynthetic Organic Chemistry has been a focal point and a real strength in the School of Chemistry for more than 50
years and the School has hosted some of Australia’s foremost synthetic chemists. Over this period, many members
of the School have willingly provided chemical expertise and specialised organic synthesis, not only to the research
community within the University, but also to external agencies requiring these services. This demand provided the
platform for the formation of the Sydney Organic Synthesis Unit in 1999 which specialised in custom synthesis, contract
research and consultancy. By 2003, growing demand for contract synthesis provided the impetus to formally adopt the
Unit as a Centre within the University.
In 2003, the University of Sydney and the School of Chemistry invested in new equipment for the Organic
Synthesis Centre (OSC) and by August 2004 building works on dedicated OSC laboratories and offices were completed.
The OSC now occupies a modern, state-of-the-art organic chemistry laboratory. Beside these recent investments, the OSC
draws on the extensive expertise of the academic and research staff within the School of Chemistry and the exceptional range
of research facilities available within the Centre, the School of Chemistry and the University of Sydney as a whole.
The aims of the OSC are to provide focus and support for synthesis-related research programs in the University,
provide an opportunity for contract synthesis to Government Organisations and to Industry, develop relationships with
Industry and to establish funded research programs. In providing professional services to industry and the chemical
research sector the OSC acts as one of the commercial enterprises of the School of Chemistry.
Over the last 12 months, the OSC has been able to provide a wide and unique range of services to many
agencies both public and private. These have included: (i) the synthesis of high quality specialist organic chemicals for the
pharmaceutical, biotechnology and materials industries in quantities from milligrams to kilograms; (ii) the development
and formulation of synthetic strategies for new compounds as well as assessment and optimisation of synthetic schemes;
(iii) the active involvement in research programs through the design and provision of novel compounds for various
applications; (iv) consultancy and the provision of expert witnesses; (v) the provision of expertise to support applications
for research funding where there is a need for professional organic synthesis; and (vi) the provision of research assistance
(on a contract or long-term basis) in research programs that require the on­going synthesis of organic compounds.
The OSC also provides a service to the wider Australasian Organic Chemistry community through the
development and hosting of OrgNet Australasia. OrgNet is a free email network regulated by the OSC for Australasian
Organic Chemists to enable the rapid dissemination of important messages and information.
In addition to the professional services offered by the OSC, members of the OSC staff are also involved in
primary research activities. This research is either co­operative (i.e. where OSC participates in a program collaboratively
with other research groups within the University) or more fundamental (e.g. developing new practical methods for
molecular synthesis). Current programs of research include investigations into expanding the synthetic toolbox available
to practicing chemists through the re-evaluation of many long-established synthetic methodologies together with related
aspects of biomimetic and chemo-enzymic synthesis (Dr Pat Stamford).
101
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School of Chemistry
Annual Research Report
103
Research grants and publications by members of the CHMR are presented in the School publication and are not separately
listed here.
Acting Director:
Professor Peter Lay
The Centre for Heavy Metals Research
within the School of Chemistry, Building F11
Room 307
Telephone: +61 2 9351 4269
Facsimile: +61 2 9351 3329
Email: [email protected]
http://chmr.chem.usyd.edu.au/
T
he Centre for Heavy Metals Research (CHMR) is based in the School of Chemistry with linkages to other units
within the University, as well as to participating institutions both within and outside Australia. It has as its
major goal the instigation and development of a substantial research program in the chemistry of heavy metals
and to develop interactions with industry, hospitals and government institutions. The Centre is the first of its kind to
be established in Australia.
The CHMR builds on a long tradition of internationally recognised expertise within the University on the
chemistry of the ‘heavy’ metals. Through its three research interests, designated respectively as Bio-Metals, IndustryMetals, and Environ-Metals, it places emphasis on the social and economic benefits of such research to areas of Health,
Industry and the Environment. Individual projects range from the discovery of novel metal-based human and veterinary
pharmaceuticals or the development of new industrial catalysts to methods for recovery and recycling metal-containing
waste streams and to modelling the fate and transport of heavy metals in the natural environment. This represents an
identifiable grouping of many of the established research activities of the Centre’s academic staff.
A selection of current CHMR projects include the synthesis and characterisation of new porous materials that display
reversible exchange of molecular guests for use in separation processes (Dr Cameron Kepert), negative-thermal expansion
materials that are generating commercial interest (Dr. Cameron Kepert), hydrocarbon oxidation catalysts (Dr James
Beattie, A/Prof. A. F. Masters and collaborators in the Netherlands), the distribution of metal ions in synthetic clays
(Assoc. Prof. Brendan Kennedy), metal-based drugs, nutritional supplements and metal-induced cancers (Prof. Peter
Lay), heme proteins (Assoc. Prof. Robert Armstrong and Prof. Peter Lay), Pt and Co anti-cancer drugs (Prof. Trevor
Hambley, and studies of metallo-proteins expressed by extremophilic microorganisms and their potential applications
in biotechnology (Dr Rachel Codd).
The CHMR underwent a review in 2006 that was chaired by the Pro-Vice Chancellor (CST), Professor Beryl
Hesketh. The Centre received a favourable review from the committee and it was recommended that it should continue
as a Centre, but some discussions would be held within the School to appoint a new director and to determine whether
changes in direction and name were desirable. These discussions have been ongoing during the latter half of the year.
Commercialisation
Professors Hambley and Lay were involved in the commercialisation of metal anti-inflammatory drugs both as veterinary
and human pharmaceuticals with Nature Vet Pty Ltd and Medical Therapies Ltd through an ARC Linkage grant and a
substantial research contract from Medical Therapies. Commercialisation of Professor Kepert’s negative thermal expansion
research has continued through UCOM-10, a University start-up company that has been funded by venture capital.
Key Personnel in CHMR are:
Acting Director:
Professor Peter A Lay, FAA
School of Chemistry
Associate Director (Bio-Metals):
Professor Peter A Lay
School of Chemistry
Associate Director (Industry-Metals and Environ-Metals):
Associate Professor James K Beattie
School of Chemistry
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School of Chemistry
Annual Research Report
105
has plagued the characterization of polymers worldwide: that of band broadening in size-exclusion (gel-permeation)
chromatography.
We have among the world’s best equipment for the synthesis and characterization of polymer colloids, thanks to
ARC LIEF grants and through generous support from the University of Sydney, as well as specialist equipment provided
by industry.
Director:
Professor Gregory G Warr
Key Centre for Polymer Colloids
within the School of Chemistry, Building F11
Room 310
Telephone: +61 2 9351 2106
Facsimile: +61 2 9351 8651
Email: [email protected]
http://www.kcpc.usyd.edu.au/
I
n its eighth year, the KCPC con­tinues to be one of the most dynamic research centres in Australia, and is recog­nized
internationally as a world leader in research into emulsion polymer­ization and related fields. We have made sub­
stantial contributions to in­ternational science in our publications, training, in­dustry collabora­tion, and out­reach.
This would not have been possible without the high levels of profes­sionalism and expertise of our staff.
The Centre’s researchers have come from every continent, and reflect our emphasis on cultural diversity. We
continued to enjoy strong links with aca­demic, govern­ment, and industrial research­ers in Australia, and also in Ger­many,
France, Thai­land, Malaysia, the US and South Africa.
Our research covers a wide range of basic and applied aspects of polymer colloids in synthetic and natural
systems. In emulsion polymer­ization, breakthroughs in 2006 have led to an understanding of radical entry and exit in
(electro)sterically stabilized particles.
In a project sponsored by the ARC and our industry partner Dulux, we have developed a model for particle
formation in RAFT mediated ab initio emulsion polymer­ization systems that paves the way for the preparation of very
small (< 20 nm) monodisperse latex particles without free surfactant. Also in this project, work has continued on i)
our new approach to miniemulsion polymerization that avoids the use of labile surfactant and the use of a hydrophobic
stabilizer; ii) using reversible addition fragmentation chain transfer (RAFT) controlled radical processes to achieve the
individual coating of paint pigment particles with binder polymer, where we have made very significant breakthroughs
that have resulted in two patents so far; iii) a study of self assembly processes in block copolymers that can lead to
polymerizable hollow particles.
In a project sponsored by the ARC and Dyno Nobel we are investigating the mechanisms for the generation
and control of gas bubbles in explosive emulsions.
In a project sponsored by the ARC and Sirtex Medical we are exploring the use of superparamagnetic
nanoparticles in the hyperthermia treatment of liver cancer and other biomedical applications. Making use of the
technology developed in the Dulux project we have perfected techniques to individually coat magnetic nanoparticles
with polymer.
In collaboration with the International Rice Re­search Institute (Manila), we have made advances in applying to
starch key tech­niques that were developed in the field of syn­thetic polymer colloids for character­ization and understanding
form­ation mecha­nisms. This has led to a powerful new method to probe the enzymatic processes in starch biosynthesis
for rice and other grains. Each enzymatic step can now be as­sociated with par­ticular regions in the mo­lecular weight
distribu­tions of the starch. We have also developed new methods for characterizing and interpreting the size distribution
of starch and other polysaccharides. These methods have enormous potential in food science. We have developed methods
for obtaining rate coefficients for starch biosynthesis from in-vitro synthesis, again from the evolution of mo­lecular weight
distribution during polymer growth. This work has led to a widely applicable method for overcoming a prob­lem that
Director:
Professor Gregory G Warr
School of Chemistry F11
Telephone: +61 2 9351 2060
Faximile: +61 2 9351 3329
Email:[email protected]
Deputy Director and Development Manager:
Dr Brian S Hawkett
School of Chemistry F11
Telephone: +61 2 9351 6973
Faximile: +61 2 9351 8651
Email: [email protected]
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School of Chemistry
Research
Facilities
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School of Chemistry
Summary of Facilities and Techniques
T
he School contains or is involved with joint facilities covering a diverse array of state-of-the-art instrumentation,
worth well over $10M. In addition, we have extensive collaborations with major synchrotron radiation and
neutron sources, allowing access to the some of most sophisticated and expensive instrumentation in the World,
on a project specific basis. Further information on facilities and researchers in the School can be found on the Internet
(http://www.chem.usyd.edu.au/).
AAS Spectrophotometry - Varian Spectra AA-20 including graphite furnace; Varian Spectra AA-800; Varian AA220;
Flame photometers for alkali metal analysis.
Annual Research Report
109
Photon Correlation Spectrometer, Malvern HPPS system, Malvern ZetaSizer, Particle Size Distribution Analyser (PLPSDA),Dilatometers, Capillary Hydrodynamic Fractionator (CHDF), Ultracentrifuge, Ozonolyzer, Avestin EmulsiFlex,
Autoclave, IKA Ultra Turrax T25 &T45, Schlenk Line, Dialysis and Ultrafilteration, Thermomixer, Ultrasonicators,
Ovens, Optical Microscopes, Conductivity and pH Meters, Brookfield Viscometer, Karl Fischer Titer, Raman Probe,
VMA-Getzmann Dispermat, KSV Sigma 70 surface Tensiometer, SensaDyne QC3000 Surface Tensiometer, a wide range
of polymerization reactors (including computer controlled ones).
Laser Techniques - Nd:YAG lasers (1064 nm, 532 nm, 355 nm, 266 nm, up to 100 Hz repetition rate); Excimer
lasers (157 nm, 193 nm, 248 nm, 308 nm, up to 50 Hz rep rate), Dye lasers (tunable from ~215 - 800 nm, repetition
rate determined by pump laser above); Optical Parametric Oscillator (20 Hz signal 440nm - 710 nm, idler 710 - 1800
nm); iCCD Spectrograph (3 gratings in turret); Scanning monochromators (1 x high resolution, several lower resolution
instruments); Fluorescence detection; Time-of-Flight Mass-Spectrometry ion detection Magnetic Measurements Including access to a SQUID.
Catalysis Laboratory - Range of small scale catalytic reactors with on line sampling GC.
Mass Spectrometry - 4 instruments including: Polaris-Q (CI/EI)GC-MS with autosampler; Micromass TofSpec2E
(MALDI-TOF); LCQ (Electrospray) and a LCQ Deca (Electrospray)with a HPLC system. There is also access to a QSTAR
XL hybrid LC/MS/MS (in School of Molecular and Microbial Biosciences for high resolution measurements on proteins,
DNA fragments, transition metal and organometallic species).
CD Spectroscopy - Modern JASCO CD spectropolarimeters.
Mixing and Grinding - Retsch MM 200 mixer mill and Retsch PM 100 high-energy planetary ball mill.
Computational Chemistry and Molecular Modelling - High performance computing facilities include access to the
Australian Centre for Advanced Computing and Communications (AC3) and the Australian Partnership for Advanced
Computing (APAC), with a wide range of software packages available (e.g., Gaussian, Materials Studio, Spartan,
Turbomole).
New Equipment for 2005/2006 obtained through ARC LIEF grant (LE0560680) include:- Renishaw Raman
inVia Microprobe with five excitation lines including: 488, 514, 633, 785, 830 nm. The instrument has line mapping
capability which allows 20 times faster data acquisition. The Raman is coupled to a Quanta FEI SEM (EMU unit)
via a Structural Chemical Analyser (SCA) which allows the user to collect SEM images and Raman (514/785 nm) data
from the same area of a sample which is located within the SEM chamber. There is also limited photoluminescent and
cathodoluminescent capabilities; FTIR Spectrometer with a high throughput screening module (Bruker Tensor 27/HTSXT) an automated system which analyses samples placed onto a 96 well infrared transmissive microtitre plate, primarily
used for chacterisation of micro-organisms, but other applications include: analysis of soils and biological fluids.
Calorimeters - Capabilities for titrations of solution reactions.
Crystal Growth - Optical floating-zone image furnace manufactured by Crystal Systems Inc. Four-mirror design, top
temperature of 2200 OC, vacuum and pressure (controlled mixture of 3 gases) capabilities.
Electroacoustics - AcoustoSizer-II for analysis of sizes and charges of colloidal particles and ZetaProbe for zeta potential
measurements.
Electrochemistry - A range of electrochemical techniques, including: microelectrode, rapid scanning, and digital
simulation techniques for polarography and voltammetry; bulk electrolysis and electrochemical synthesis (including
BAS100B/W and PAR Potentiostat Model 273A instruments); spectroelectrochemical techniques (Electronic, EPR,
FTIR, Raman, SERS, XAS); selective electrodes and oxygen sensors.
Electronic Absorption and Emission Spectroscopy - Various Cary instruments, including a Cary 5E system with
UV/Vis and NIR optical fibre and diffuse reflectance capabilities; Hewlett-Packard Diode Array spectrometer; Emission
spectrometers.
Electron Microscopy - Many researchers have access and experience with the advanced instrumentation in the Electron
Microscopy Unit of the University of Sydney.
EPR Spectroscopy - 2 x Bruker EMX, and a Bruker Elexsys E 500 (updated to-state-of-the-art in 2002/2003), X-band,
Q-band, L-band, ENDOR, fast scan, liquid He cryostat in a joint facility with UNSW.
Gas Sorption - Hiden Isochema IGA-002: gravimetric measurement of the adsorption isotherms for gases and liquid
vapours, equipped for measurements up to 10 atm and at high temperature. Quantachrome Autosorb-1 (shared instrument
located at Chemical Engineering): volumetric measurement of gas adsorption isotherms at 77 K.
High Pressure Equipment - Capable of solution phase synthesis of 2 x 5 mL samples at up to 8,000 atm and
100°C.
Key Center for Polymer Colloids - Multidimensional HPLC for polymers, multiple detection size exclusion
chromatography (SEC, refractometer, UV, light scattering, Ubbelohde Glass Capillary Viscometer, Membrane Osmometry,
NMR Spectroscopy - Bruker 600 MHz, 2 x 400 MHz, 1 x 300 MHz, 1 x 200 MHz spectrometers, plus modern data
manipulation and plotting stations.
Potentiometric Equipment - For accurate determinations of metal-complex stability constants.
Scanning Probe Microscopy - Pico+ SPM (shared with EMU) for use in Atomic Force Microscopy, Conducting Atomic
Force Microscopy, Single-Molecule Condctivity, and Scannelling-Tunnelling Microscopy.
Separations - Large range of equipment including GC’s, HPLCs, EPLC, Dionex, gel electrophoresis, etc.
Stopped-Flow Spectrometers - Applied Photophysics SMV-17, UV/Vis, CD and emission detection, global analysis
software; Hi-Tech Scientific SF-61, UV/Vis and emission detection.
Surface Analysis Facility (shared with UNSW) - Large range of surface techniques, XPS, Auger spectroscopy, PIXE
etc.
Surface Characterisation - Atomic force microscopy, neutron reflectometry, small-angle x-ray and neutron
scattering.
Synthesis - Diverse range of specialist equipment and laboratories for inorganic, organic, organometallic and polymer
chemistry.
Thermogravimetric Analysis - TGA and modulated DSC; intelligent gravimetric analyser.
Two-Photon Spectroscopy - Microprobe fluorescence imaging of biological samples (joint with EMU).
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School of Chemistry
Ultracentrifuge - Is used to separate polymers from supernatant in a polymer colloid, so that the polymer properties
can be examined.
Vibrational Spectroscopy - Dispersive Raman spectrometer (Jobin-Yvon U1000, Ar+ ion and Kr+ lasers); FT-Raman
spectrometer (Bruker RFS100) with 90° and 180° sampling. The FT-Raman is coupled via fibre optic probe to a
microscope with 7x7 mm mapping resolution; Renishaw Raman Systems 2000 spectrometer equipped with a 3-axis
motorised stage with ±1 mm repeatability. The instrument is capable of point spectroscopy, 2-D Raman imaging and
3-D Raman mapping with 1-5 mm spatial resolution. The Renishaw Raman can use any of the following excitation lines:
488, 514, 532, 567, 647, 752 nm; access to UV Renishaw Raman at Macquarie University with microprobe which has
325, 406 and 442 nm excitation lines; FTIR Spectrometer (Bruker IFS66v) with DRIFT, ATR (single bounce diamond),
grazing angle and photoacoustic accessories. The instrument is also equipped with a microscope with an MCT detector
and has NIR, MIR and FIR capabilities.
X-ray Absorption Spectroscopy - Access to various synchrotron radiation sources for XANES and XAFS analysis,
microprobe and stopped-flow techniques on a project specific basis.
X-ray and Neutron Powder Diffraction - Benchtop and synchrotron X-ray instruments and access to ANSTO and
overseas neutron sources on a project-specific basis; high temperature (1600 °C) capabilities.
X-ray, Single-Crystal Diffraction - Bruker SMART 1000 and an imminent installation of a Bruker-Nonius APEX
II FR591 high flux and sensitivity system. Oxford Cryosystems cryostats for data collections between 230 deg C and
–250 deg C. Microscopes for crystal and micro-crystal examination and manipulation. Access to diffraction facilities
at synchrotrons such as the ChemMatCARS facility at the Advanced Photon Source and the European Synchrotron
Radiation Facility.
Research
Publications
112
School of Chemistry
Book Chapters
1.
2.
3.
Bilic, A, Reimers, JR, Hush, NS. Functionalization of semiconductor surfaces by organic layers: Concerted
cycloaddition versus stepwise free-radical reaction mechanisms. Properties of Single Organic Molecules on Crystal
Surfaces, 1, Imperial College Press, ISBN: 1-86094-628-3, 1-430, 2006.
Larsen, J, Brüggemann, B, Polívka, T, Sly, J, Crossley, MJ, Sundström, V and Åkesson, E. Energy transfer dynamics
in Zn-porphyrin-appended dendrimers, in Femtochemistry VII: Fundamental ultrafast processes in chemistry,
physics, and biology. Ed. A. Welford Castleman, Jr., Elsevier: Amsterdam, ISBN: 978-0-444-52821-6, 113-116,
2006.
Maschmeyer, T and Van De Water, LG. An overview of zeolite, zeotype and mesoporous solids chemistry: Design,
Synthesis and Catalytic Properties. Catalysts for Fine Chemical Synthesis, 4, John Wiley & Sons Ltd, ISBN: 0471-49054-7, 1-38, 2006.
Annual Research Report
113
Journal Publications
1.
Abdullah, A, Huq, F, Chowdhury, A, Tayyem, H, Beale, P and Fisher, K. Studies on the synthesis characterization
binding with DNA and activities of two cis-planaramineplatinum(II) complexes of the form: cis-PtL(NH3)Cl2
where L = 3-hydroxypyridine and 2,3-diaminopyridine. BMC Chemical Biology, 6, 1-9, 2006.
2.
Alderden, RA, Hall, MD and Hambley, TW. The discovery and development of cisplatin. Journal of Chemical
Education, 83, 728-734, 2006.
3.
Alderden, RA, Mellor, HR, Modok, S, Hambley, TW and Callaghan, R. Cytotoxic efficacy of an anthraquinone
linked platinum anticancer drug. Biochemical Pharmacology, 71, 1136-1145, 2006.
4.
Allen, CR, Richard, PL, Ward, AJ, van de Water, LGA, Masters, AF and Maschmeyer, T. Facile synthesis of ionic
liquids possessing chiral carboxylates. Tetrahedron Letters, 47, 7367-7370, 2006.
5.
Allwood, AC, Walter, MR and Marshall, CP. Raman spectroscopy reveals thermal palaeoenvironments of c.3.5
billion-year-old organic matter. Vibrational Spectroscopy, 41, 190-197, 2006.
6.
Allwood, AC, Walter, MR, Kamber, BS, Marshall, CP and Burch, IW. Stromatolite reef from the Early Archaean
era of Australia. Nature, 441, 714-718, 2006.
7.
Amoore, JJM, Kepert, CJ, Cashion, JD, Moubaraki, B, Neville, SM and Murray, KS. Structural and magnetic
resolution of a two-step full spin-crossover transition in a dinuclear iron(II) pyridyl-bridged compound.
Chemistry – A European Journal, 12, 8220-8227, 2006.
8.
Amoroso, S, Agon, VV, Starke-Peterkovic, T, McLeod, MD, Apell, H-J, Sebban, P and Clarke, RJ. Photochemical
behavior and Na+,K+-ATPase sensitivity of voltage-sensitive styrylpyridinium fluorescent membrane probes.
Photochemistry and Photobiology, 82, 495-502, 2006.
9.
Anand, R, Hamdy, MS, Gkourgkoulas, P, Maschmeyer, Th, Jansen, JC and Hanefeld, U. Liquid phase oxidation
of cyclohexane over transition metal incorporated amorphous 3D-mesoporous silicates M-TUD-1 (M = Ti, Fe, Co,
and Cr). Catalysis Today, 117, 279-283, 2006.
10. Andrews, LE, Bonin, AM, Fransson, LE, Gillson, A-ME and Glover, SA. The role of steric effects in the direct
mutagenicity of N-acyloxy-N-alkoxyamides. Mutation Research-Genetic Toxicology and Environmental Mutagenesis,
605, 51-62, 2006.
11. Antonioli, B, Bray, DJ, Clegg, JK, Gloe, K, Gloe, K, Kataeva, O, Lindoy, LF, McMurtrie, JC, Steel, PJ, Sumby, CJ
and Wenzel, M. Silver(I) complexation of linked 2,2´-dipyridylamine derivatives. Synthetic, solvent extraction,
membrane transport and x-ray structural studies. Dalton Transactions, 4783-4794, 2006.
12. Antonioli, B, Clegg, JK, Bray, DJ, Gloe, K, Gloe, K, Heßke, H and Lindoy, LF. An unprecedented bridging
[Ag2(NO3)6]4– anion as a component of aninfinite silver(I) molecular ladder incorporating a dinuclear cationic
silver complex of a bis-dipyridylamine ligand. Cryst.Eng.Comm., 8, 748-750, 2006.
13. Armstrong, RS, Foran, GJ, Hough, WA, D’Alessandro, DM, Lay, PA and Crossley, MJ. Spectroelectrochemical
evidence for communication within a laterally-bridged dimanganese(III) bis-porphyrin. Dalton Transactions,
4805-4813, 2006.
14. Arora, M, Kennedy, BJ, Elhlou, S, Pearson, NJ, Walker, DM, Bayl, P and Chan, SWY. Spatial distribution of lead
in human primary teeth as a biomarker of pre- and neonatal lead exposure. Science of the Total Environment, 371,
55-62, 2006.
15. Assaad, T, Mavel, S, Parsons, SM, Kruse, S, Galineau, L, Allouchi, H, Kassiou, M, Chalon, S, Guilloteau, D and
Emond, P. Synthesis and in vitro evaluation of N-substituted aza-trozamicol analogs as vesicular acetylcholine
transporter ligands. Bioorganic & Medicinal Chemistry Letters, 16, 2654-2657, 2006.
16. Atefi, F, McMurtrie, JC, Turner, P, Duriska, M and Arnold, DP. meso-porphyrinylphosphine oxides:
Mono- and bidentate ligands for supramolecular chemistry and the crystal structures of monomeric
{[10,20-diphenylporphyrinatonickel(II)-5,15-diyl]-bis-[P(O)Ph2]
and
polymeric
self-coordinated
{[10,20-diphenylporphyrinatozinc(II)-5,15-diyl]-bis-[P(O)Ph2]}. Inorganic Chemistry, 45, 6479-6489, 2006.
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17. Attard, P, Pettersson, T and Rutland, MW. Thermal calibration of photodiode sensitivity for atomic force
microscopy. Review of Scientific Instruments, 77, 116110, 2006.
18. Attard, P. Non-periodic boundary conditions for molecular simulations of condensed matter. Molecular Physics,
104, 1951-1960, 2006.
19. Attard, P. Statistical mechanical theory for steady state systems. IV. Transition probability and simulation
algorithm demonstrated for heat flow. Journal of Chemical Physics, 124, 024109, 2006.
20. Attard, P. Statistical mechanical theory for steady state systems. V. Nonequilibrium probability density. Journal
of Chemical Physics, 124, 224103, 2006.
21. Attard, P. Statistical mechanical theory for steady state systems. VI. Variational principles. Journal of Chemical
Physics, 125, 214502, 2006.
22. Attard, P. Theory for non-equilibrium statistical mechanics. Physical Chemistry Chemical Physics, 8, 3585-3611,
2006.
23. Barlow, CK, Moran, D, Radom, L, McFadyen, WD and O’Hair, RAJ. Metal-mediated formation of gas-phase
amino acid radical cations. Journal of Physical Chemistry A, 110, 8304-8315, 2006.
24. Bastug, T, Gray-Weale, A, Patra, SM and Kuyucak, S. Role of protein flexibility in ion permeation: A case study
in gramicidin A. Biophysical Journal, 90, 2285-2296, 2006.
25. Battle, AR, Choi, R, Hibbs, DE and Hambley, TW. Platinum(IV) analogues of AMD473 (cis-[PtCl2(NH3)(2picoline)]): Preparative, structural, and electrochemical studies. Inorganic Chemistry, 45, 6371-6322, 2006.
26. Beattie, JK, Hunter, RJ and Zhang, H. Electroacoustic detection of the onset of depletion flocculation of latex
dispersions by hydroxyethyl cellulose. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 275, 83-86,
2006.
27. Beattie, JK. The intrinsic charge on hydrophobic microfluidic substrates. Lab on a Chip, 6, 1409-1411, 2006.
28. Beves, JE, Chapman, BE, Kuchel, PW, Lindoy, LF, McMurtrie, McPartlin, M, Thordarson, P and Wei, G. New
discrete metallocycles incorporating palladium(II) and platinum(II) corners and dipyridyldibenzotetraaza[14]annulene side units. Dalton Transactions, 744-750, 2006.
29. Bhuiyan, MDH, Try, AC, Klepetko, J and Turner, P. Diethyl 4,10-dibromo-5,11-methano-6H,12H-dibenzo
[b,f][1,5]diazocine-2,8-dicarboxylate. Acta Crystallographica Section E-Structure Reports Online, E62, 04887-o4888,
2006.
30. Bilic, A, Reimers, JR, Hush, NS, Hoft, RC and Ford, MJ. Adsorption of benzene on copper, silver, and gold
surfaces. Journal of Chemical Theory and Computation, 2, 1093-1105, 2006.
31. Bilic, A, Reimers, JR and Hush, NS. Functionalization of semiconductor surfaces by organic layers: Concerted
cycloaddition versus stepwise free-radical reaction mechanisms. Properties of Single Organic Molecules on Crystal
Surfaces, 333-360, 2006.
Annual Research Report
115
37. Bourgeois, CJ, Garratt, SA, Hughes, RP, Laritchev, RB, Smith, JM, Ward, AJ, Zhang, D, DiPasquale, AG,
Zhakarov, LN and Rheingold, AL. Synthesis and structural characterization of perfluoroalkyl(fluoro)iridium(III)
and perfluoroalkyl(methyl)iridium(III) compounds. Organometallics, 25 (14), 3474-3480, 2006.
38. Brodie, CR, Turner, P, Wheate, NJ and Aldrich-Wright, JR. (4,7-dimethyl-1,10-phenanthroline (ethylenediamine)
platinum(II) dichloride tris(deuterium oxide) solvate. Acta Crystallographica Section E-Structure Reports Online, E62,
m3137-m3139, 2006.
39. Cagnin, A, Kassiou, M, Meikle, SR and Banati, RB. In vivo evidence for microglial activation in neurodegenerative
dementia. ACTA Neurologica Scandinavica, 114, 107-114, 2006.
40. Cai, Z-L, Crossley, MJ, Reimers, JR, Kobayashi, R and Amos, RD. Density functional theory for charge transfer:
The nature of the N-bands of porphyrins and chlorophylls revealed through CAM-B3LYP, CASPT2, and SAC-CI
calculations. Journal of Physical Chemistry B, 110, 15624-15632, 2006.
41. Campbell, KS, Foster, AJ, Dillon, DT and Harding, MM. Genotoxicity and transmission electron microscopy
studies of molybdocene dichloride. Journal of Inorganic Biochemistry, 100, 1194-1198, 2006.
42. Canfield, P, Dahlbom, MG, Hush, NS and Reimers, JR. Density-functional geometry optimization of the
150 000-atom photosystem-I trimer. Journal of Chemical Physics, 124, 24301, 2006.
43. Castignolles, P, Gaborieau, M, Hilder, EF, Sprong, E, Ferguson, CJ and Gilbert, RG. High-resolution separation
of oligo(acrylic acid) by capillary zone electrophoresis. Macromolecular Rapid Communications, 27, 42-46, 2006.
44. Castignolles, P, Nikitin, AN, Couvreur, L, Mouraret, G, Charleux, B and Varion, J-P. Pulsed laser polymerization
of alkyl acrylates: Potential effects of the oxygen presence and high laser power. Macromolecular Chemistry and
Physics, 207, 81-89, 2006.
45. Chan, B and Radom, L. Design of effective zeolite catalysts for the complete hydrogenation of CO2. Journal of the
American Chemical Society, 128, 5322-5323, 2006.
46. Chang, JC, Gurr, GM, Fletcher, MJ and Gilbert, RG. Structure–property and structure–function relations of
leafhopper (Kahaono montana) silk. Australian Journal of Chemistry, 59, 579-585, 2006.
47. Chapman, KW, Chupas, PJ and Kepert, CJ. Compositional dependence of negative thermal expansion in the
Prussian blue analogues MIIPtIV(CN)6 (M = Mn, Fe, Co, Ni, Cu, Zn, Cd). Journal of the American Chemical Society,
128, 7009-7014, 2006.
48. Chapman, KW, Hagen, M, Kepert, CJ and Manuel, P. Low energy phonons in the NTE compounds Zn(CN)2 and
ZnPt(CN)6. Physica B, 385-386, 60-62, 2006.
49. Chartres, JD, Davies, MS, Lindoy, LF, Meehan, GV and Wei, G. Macrocyclic ligand design: The interaction of
selected transition and post-transition metal ions with a 14-membered N2S2-donor macrocycle. Inorganic Chemistry
Communications, 9, 751-754, 2006.
50. Chartres, JD, Lindoy, LF and Meehan, GV. New heterotopic, linked macrocyclic systems derived from selectively
protected macrocycles. Tetrahedron, 62, 4173-4187, 2006.
32. Bishop, MM, Coles, SJ, Lindoy, LF and Parkin, A. A systematic study of ligand intermolecular interactions in
crystals of copper(II) complexes of bidentate guanidino derivatives. Inorganica Chimica Acta, 359, 3565-3580,
2006.
51. Cheah, M, Saines, PJ and Kennedy, BJ. The Jahn–Teller distortion and cation ordering in the perovskite
Sr2MnSbO6. Journal of Solid State Chemistry, 179, 1775-1781, 2006.
33. Biswas, M, Batten, SR, Jensen, P and Mitra, S. Retention of (4,4) connectivity in the absence of pp interactions
in a cadmium tris-dicyanamide compound. Australian Journal of Chemistry, 59 (2), 115-117, 2006.
52. Cheah, MCL, Kennedy, BJ, Withers, RL, Yonemura, M and Kamiyama, T. Synthesis, structures and phase
transitions in the double perovskites Sr2-xCaxCrNbO6. Journal of Solid State Chemistry, 179, 2487-2494, 2006.
34. Blom, A and Warr, GG. Structure and composition of cationic–nonionic surfactant mixed adsorbed layers on
mica. Langmuir, 22, 6787-6795, 2006.
53. Cheng, H, Huq, F, Beale, P and Fisher, K. Synthesis, characterisation, activities, cell uptake and DNA binding
of a trinuclear complex: [{trans-PtC1(NH3)}2m-{trans-Pd(NH3) (2-hydroxypyridine)-(H2N(CH2)6NH2)2]C14.
European Journal of Medicinal Chemistry, 41, 896-903, 2006.
35. Blom, A, Warr, GG and Wanless, EJ. Growth of double-chained cationic surfactant films on mica. Australian
Journal of Chemistry, 59, 381-385, 2006.
36. Bonnitcha, PD, Hall, MD, Underwood, CK, Foran, GJ, Zhang, M, Beale, PJ and Hambley, TW. XANES
investigation of the Co oxidation state in solution and in cancer cells treated with Co(III) complexes. Journal of
Inorganic Biochemistry, 100, 963-971, 2006.
54. Cifuentes, MP, Powell, CE, Morrall, JP, McDonagh, AM, Lucas, NT, Humphrey, MG, Samoc, M, Houbrechts, S,
Asselberghs, I, Clays, K, Persoons, A and Isoshima, T. Electrochemical, spectroelectrochemical, and molecular
quadratic and cubic nonlinear optical properties of alkynylruthenium dendrimers. J. Am. Chem. Soc., 128, 1081910832, 2006.
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Annual Research Report
117
55. Clegg, JK, Gloe, K, Hayter, MJ, Kataeva, O, Lindoy, LF, Moubaraki, B, McMurtire, JC, Murray, KS and Schilter,
D. New discrete and polymeric supramolecular architectures derived from dinuclear (bis-b-diketonato) copper(II)
metallocycles. Dalton Transactions, 3977-3984, 2006.
74. Effendy, Junk, PC, Kepert, CJ, Louis, LM, Morien, TC, Skelton, BW and White, AH. The structural systematics
of protonation of some important nitrogen-base ligands. III - Some (univalent) anion salts of some hindered
unidentate nitrogen bases. Zeitschrift Fur Anorganische Und Allgemeine Chemie, 632, 1312-1325, 2006.
56. Clegg, JK, Hayter, MJ, Jolliffe, KA and Lindoy, LF. Tetraaquabis(pyridine-kN)cobalt(II) diacetate. Acta
Crystallographica Section E-Structure Reports Online, E62, m873-m874, 2006.
75. El-Fayyoumy, S, Mansour, W and Todd, MH. Solid phase synthesis of praziquantel. Tetrahedron Letters, 47, 12871290, 2006.
57. Clegg, JK, Lindoy, LF, McMurtrie, JC and Schilter, D. Extended three-dimensional supramolecular architectures
derived from trinuclear (bis-b-diketonato)copper(II) metallocycles. Dalton Transactions, 3114-3121, 2006.
76. Enders, M and Baker, RW. Synthesis of aryl- and heteroaryl-substituted cyclopentadienes and indenes and their
use in transition metal chemistry. Current Organic Chemistry, 10, 937-953, 2006.
58. Clegg, JK. Di- and tri-nuclear copper(II) metallocycles: Building blocks for supramolecular chemistry. Australian
Journal of Chemistry, 59, 660-660, 2006.
77. Failes, TW and Hambley, TW. Models of hypoxia activated prodrugs: Co(III) complexes of hydroxamic acids.
Dalton Transactions, 1895-1901, 2006.
59. Codd, R, Lay, PA, Tsibakhashvili, NY, Kalabegishvili, TL, Murusidze, IG and Holman, H-Y. Chromium(V)
complexes generated in Arthrobacter oxydans by simulation analysis of EPR spectra. Journal of Inorganic Biochemistry,
100, 1827-1833, 2006.
78. Fainerman-Melnikova, M, Clegg, JK and Codd, RS. Aqua[bis(2-pyridylmethyl)amine][chelidonato(1.5–)]copper(II) chelidonate(0.5–) monohydrate. Acta Crystallographica Section E-Structure Reports Online, E62,
m3582-m3584, 2006.
60. Corral, I, Mó, O, Yànez, M, Salpin, J-Y, Tortajada, J, Moran, D and Radom, L. An experimental and theoretical
investigation of gas-phase reactions of Ca2+ with glycine. Chemistry – A European Journal, 12, 6787-6796, 2006.
79. Faroughi, M, Try, AC and Turner, P. 2,4,8,10-tetrabromo-6H,12H-5,11-methano-dibenzo[b,f][1,5]diazocine.
Acta Crystallographica Section E-Structure Reports Online, E62, o3893-3894, 2006.
61. Costa, LAS, Hambley, TW, Rocha, WR, de Almeida, WB and Dos Santos, HF. Kinetics and structural aspects
of the cisplatin interactions with guanine: A quantum mechanical description. International Journal of Quantum
Chemistry, 106, 2129-2144, 2006.
80. Faroughi, M, Try, AC and Turner, P. 2,8-dibromo-6H,12H-5,11-methanodibenzo[b,f][1,5]diazocine. Acta
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179. Petravic, J and Harrowell, P. Erratum: Linear response theory for thermal conductivity and viscosity in terms of
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180. Pickering, IJ, Gumaelius, L, Harris, HH, Pring, RC, Hirsch, G, Banks, JA, Salt, DE and George, GN. Localizing
the biochemical transformations of arsenate in a hyperaccumulating fern. Environmental Science & Technology, 40,
5010-5014, 2006.
181. Pittaya, T, Photchana, P, Yupa, P and Taylor, WC. Chemical constituents of the roots of Piper Sarmentosum.
Chemical & Pharmaceutical Bulletin, 54, 149-151, 2006.
182. Pittaya, T, Photchana, P, Yupa, P and Taylor, WC. Chromones from the branches of Harrisonda perforata. Chemical
& Pharmaceutical Bulletin, 54, 44-47, 2006.
183. Prescott, SW, Ballard, MJ, Rizzardo, E and Gilbert, RG. Rate optimization in controlled radical emulsion
polymerization using RAFT. Macromolecular Theory and Simulations, 15, 70-86, 2006.
184. Pretsch, T, Chapman, KW, Halder, GJ and Kepert, CJ. Dehydration of the nanoporous coordination framework
ErIII[CoIII(CN)6]·4(H2O): Single crystal to single crystal transformation and negative thermal expansion in
ErIII[CoIII(CN)6]. Chemical Communications, 1857-1859, 2006.
185. Ratinac, KR, Gilbert, RG, Ye, L, Jones, AS and Ringer, SP. The effects of processing and organoclay properties on
the structure of poly(methyl methacrylate)–clay nanocomposites. Polymer, 47, 6337-6361, 2006.
186. Reilly, NJ, Cupitt, GC, Kable, SH and Schmidt, TW. An experimental and theoretical investigation of the
dispersed fluorescence spectroscopy of HC4S. Journal of Chemical Physics, 124, 194310, 2006.
187. Reilly, NJ, Schmidt, TW and Kable, SH. Two-dimensional fluorescence (excitation/emission) spectroscopy as a
probe of complex chemical environments. Journal of Physical Chemistry A, 110, 12355-12359, 2006.
188. Reimers, JR, Ulstrup, J, Meyer Thomas, J and Solomon, GC. The molecules and methods of chemical biochemical,
and nanoscale electron transfer – Part 2 in honour of Noel S. Hush on his 80th birthday. Chemical Physics, 324, 1-2,
2006.
191. Saines, PJ, Elcombe, MM and Kennedy, BJ. Lanthanide distribution in some doped alkaline earth aluminates and
gallates. Journal of Solid State Chemistry, 179, 613-622, 2006.
192. Saines, PJ, Elcome, MM and Kennedy, BJ. Structural studies of oxygen deficient lanthanide containing double
perovskites. Physica B, 385-386, 187-189, 2006.
193. Sandala, GM, Smith, DM and Radom, L. In search of radical intermediates in the reactions catalyzed by lysine 2,3aminomutase and lysine 5,6-aminomutase. Journal of the American Chemical Society, 128, 16004-16005, 2006.
194. Sandala, GM, Smith, DM, Coote, ML, Golding, BT and Radom, L. Insights into the hydrogen-abstraction reactions
of diol dehydratase: Relevance to the catalytic mechanism and suicide inactivation. Journal of the American Chemical
Society, 128, 3433-3444, 2006.
195. Sandala, GM. Suicide inactivation in adenosylcobalamin-dependent enzymes. Australian Journal of Chemistry, 59,
289-289, 2006.
196. Save, M, Guillaneuf, Y and Gilbert, RG. Controlled radical polymerization in aqueous dispersed media. Australian
Journal of Chemistry, 59, 693-711, 2006.
197. Sciortino, NF and Kepert, CJ. 3-methyl-1-(3-methylpyridinium-4-yl)pyridinium dichloride monohydrate. Acta
Crystallographica Section E-Structure Reports Online, 62, o997-o998, 2006.
198. Sharp, RG, Reilly, NJ, Kable, SH and Schmidt, TW. Sequence structure emission in the red rectangle bands.
Astrophysical Journal, 639, 194-203, 2006.
199. Shi, L, Jing, H, Ren, G, Levina, A and Lay, PA. Studies on the mechanism of Cr-induced DNA damage in glucose
and its derivative. Weisheng Yanjiu, 35 (3), 348-351, 2006.
200. Simons, C, Hanefeld, U, Arends, IWCE, Maschmeyer, T and Sheldon, RA. A one-pot enantioselective chemoenzymatic synthesis of amino acids in water. Advanced Synthesis & Catalysis, 348, 471-475, 2006.
201. Simons, C, Hanefeld, U, Arends, IWCE, Maschmeyer, T and Sheldon, RA. Comparison of supports for the
electrostatic immobilisation of asymmetric homogeneous catalysts. Journal of Catalysis, 239, 212-219, 2006.
202. Simons, C, Hanefeld, U, Arends, IWCE, Maschmeyer, T and Sheldon, RA. Towards catalytic cascade reactions:
Asymmetric synthesis using combined chemo-enzymatic catalysts. Topics in Catalysis, 40, 35-44, 2006.
203. Soapi, KM and Hutton, CA. Preparation of b-nitroalanine using the Easton three-component coupling method.
Amino Acids, 31, 337-339, 2006.
204. Solomon, GC, Gagliardi, A, Pecchia, A, Frauenheim, T, Di Carlo, A, Reimers, JR and Hush, NS. Molecular
origins of conduction channels observed in shot-noise measurements. Nano Letters, 6, 2431-2437, 2006.
205. Solomon, GC, Gagliardi, A, Pecchia, A, Frauenheim, T, Di Carlo, A, Reimers, JR and Hush, NS. Understanding
the inelastic electron-tunneling spectra of alkanedithiols on gold. Journal of Chemical Physics, 124, 094704,
2006.
206. Solomon, GC, Gagliardi, A, Pecchis, A, Frauenheim, T, Di Carlo, A, Reimers, JR and Hush, NS. The symmetry
of single-molecule conduction. Journal of Chemical Physics, 125, 184702, 2006.
207. Somphon, W, Ting, V, Liu, Y, Withers, RL, Zhou, Q and Kennedy, BJ. Local crystal chemistry, structured diffuse
scattering and the dielectric properties of (Bi1-xYx)2(MIIINbV)O7 (M=Fe3+, In3+) Bi-pyrochlores. Journal of Solid State
Chemistry, 179, 2495-2505, 2006.
208. Southwood, TJ, Curry, MC and Hutton, CA. Factors affecting the efficiency and stereoselectivity of a-amino acid
synthesis by the Petasis reaction. Tetrahedron, 62, 236-242, 2006.
209. Sprong, E, Leswin, JSK, Lamb, DJ, Ferguson, CJ, Hawkett, BS, Pham, BTT, Nguyen, D, Such, CH, Serelis, AK
and Gilbert, RG. Molecular watchmaking: ab initio emulsion polymerization by RAFT-controlled self-assembly.
Macromolecular Symposia, 231, 84-93, 2006.
124
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125
210. Squires, C, Baxter, CW, Campbell, J, Lindoy, LF, McNab, H, Parkin, A, Parsons, S, Tasker, PA, Wei, G and
White, DJ. Design of base metal extractants. Part 1. Inter-ligand hydrogen bonding in the assembly of pseudomacrocyclic bis(aminosulfonamidato)M(II) complexes. Dalton Transactions, 2026-2034, 2006.
229. Usher, AJ, Lucas, NT, Dalton, GT, Randles, MD, Viau, L, Humphrey, MG, Petrie, S, Stranger, R, Willis, AC
and Rae, AD. Mixed-metal cluster chemistry. 29. Core expansion and ligand-driven metal exchange at group 6iridium clusters. Inorg. Chem., 45, 10859-10872, 2006.
211. Starke-Peterkovic, T, Turner, N, Vitha, MF, Waller, MP, Hibbs, DE and Clarke, RJ. Cholesterol effect on the
dipole potential of lipid membranes. Biophysical Journal, 90, 4060-4070, 2006.
230. van Berkel, KY, Russell, GT and Gilbert, RG. The dissociation rate coefficient of persulfate in emulsion
polymerization systems. Polymer, 47, 4667-4675, 2006.
212. Stiernstedt, J, Rutland, MW and Attard, P. A novel technique for the in situ calibration and measurement of
friction with the atomic force microscope. Review of Scientific Instruments, 76, 83710, 2006.
231. van de Water, LGA, Bezemer, GL, Bergwerff, JA, Versluijs-Helder, M, Weckhuysen, BM and de Jong, KP.
Studying the preparation process of alumina-supported cobalt Fischer-Tropsch catalysts by spatially resolved UVV is microspectroscopy. J. Catal., 242 (2), 287-298, 2006.
213. Stootman, FH, Fisher, DM, Rodger, A and Aldrich-Wright, JR. Improved curve fitting procedures to determine
equilibrium binding constants. The Analyst, 131, 1145-1151, 2006.
214. Taechowisan, T, Wanbanjob, A, Tuntiwachwuttikul, P and Taylor, WC. Identification of Streptomyces sp Tc022, an
endophyte in Alpinia galanga, and the isolation of actinomycin D. Annals of Microbiology, 56, 113-117, 2006.
215. Tamanini, E, Watkinson, M and Todd, MH. Improved synthesis of the valuable peptidomimetic intermediate
3-azido-4-hydroxy cyclopentanoic acid. Tetrahedron: Asymmetry, 17, 2235-2239, 2006.
216. Thickett, SC and Gilbert, RG. Mechanism of radical entry in electrosterically stabilized emulsion polymerization
systems. Macromolecules, 39, 6495-6504, 2006.
217. Thickett, SC and Gilbert, RG. Rate-controlling events for radical exit in electrosterically stabilized emulsion
polymerization systems. Macromolecules, 39, 2081-2091, 2006.
218. Thomas, BS, Marks, NA and Harrowell, P. Inversion of defect interactions due to ordering in Sr1-3x/2LaxTiO3
perovskites: An atomistic simulation study. Physical Review B, 74, 214109, 2006.
219. Thomassen, PJ, Foekema, J, Lluch, RJ, Thordarson, P, Elemans, JAAW, Nolte, RJM and Rowan, AE. Selfassembly studies of allosteric photosynthetic antenna model systems. New Journal of Chemistry, 30, 148-155,
2006.
220. Thominiaux, C, Bruin, B, Bramoulle, Y, Hinnen, F, Demphel, S, Bottlaender, M, Besret, L, Kassiou, M and
Dolle, F. Radiosynthesis of (E)-N-(2-[11C]methoxybenzyl)-3-phenyl-acrylamidine, a novel subnanomolar NR2B
subtype-selective NMDA receptor ligand. Appl. Rad. Isotop., 64, 348-354, 2006.
221. Thominiaux, C, Dollé, F, James, ML, Bramoullé, Y, Boutin, H, Besret, L, Grégoire, MC, Valette, H, Bottlaender,
M, Tavitian, B, Hantraye, P and Kassiou, M. Improved synthesis of the peripheral benzodiazepine receptor ligand
[11C]DPA-713 using [11C]methyl triflate. Appl. Rad. Isotop., 64, 570-573, 2006.
222. Thompson, K, Crittenden, DL, Kable, SH and Jordan, MJ. A classical trajectory study of the photodissociation of
T1 acetaldehyde: The transition from impulsive to statistical dynamics. Journal of Chemical Physics, 124, 044302,
2006.
223. Thordarson, P, Atkin, R, Kalle, WHJ, Warr, GG and Braet, F. Developments in using scanning probe microscopy
to study molecules on surfaces – from thin films and single-molecule conductivity to drug-living cell interactions.
Australian Journal of Chemistry, 59, 359-375, 2006.
224. Thordarson, P, Le Droumaguet, B and Velonia, K. Well-defined protein-polymer conjugates – synthesis and
potential applications. Applied Microbiology and Biotechnology, 73, 243-254, 2006.
225. Todd, MH, Motevalli, M, El-Fayyoumy, S and Richards, C. (R)-2-ferrocenyl-4-hydroxymethyl-4,5dihydro-1,3oxazole. Acta Crystallographica Section E-Structure Reports Online, E62, m719-m720, 2006.
226. Tonge, MP, Calitz, FM and Sanderson, RD. ESR detection of propagating radical species during RAFT-mediated
polymerization. Macromolecular Chemistry and Physics, 207, 1852-1860, 2006.
227. Troy, TP and Schmidt, TW. A theoretical treatment of the absorption spectra of all-benzenoid hydrocarbons.
Monthly Notices of the Royal Astronomical Society, 371, L41-L44, 2006.
228. Truong, L, Allbutt, H, Kassiou, M and Henderson, JM. Developing a preclinical model of Parkinson’s disease: A
study of behaviour in rats with graded 6-OHDA lesions. Behav. Brain Res. 169, 1-9.
232. Vasilescu, IM, Bray, DJ, Clegg, JK, Lindoy, LF, Meehan, GV and Wei, G. Rational ligand design for metal ion
recognition. Synthesis of a N-benzylated N2S3-donor macrocycle for enhanced silver(I) discrimination. Dalton
Transactions, (43), 5115-5117, 2006.
233. Vercouillie, J, Mavel, S, Galineau, L, Ragusa, T, Innis, R, Kassiou, M, Chalon, S, Dollé, F, Besnard, J-C, Guilloteau,
D and Emond, P. Synthesis and in vitro evaluation of novel diphenylsulfide derivatives as serotonin transporter
ligands. Bioorg. Med.Chem. Lett., 16, 1297-1300, 2006.
234. Waern, JB, Turner, P and Harding, P. Synthesis and hydrolysis of thiol derivatives of molybdocene dichloride
incorporating electron-withdrawing substituents. Organometallics, 25, 3417-3421, 2006.
235. Ward, AJ, Burger, M, Aquino, C, Clegg, JK, Turner, P, Masters, AF and Maschmeyer, T. Bis(2,2´,2˝nitrilotriethanol)cobalt(II) bis(acetate). Acta Crystallographica Section E-Structure Reports Online, E62, m2429m2431, 2006.
236. Ward, RM, Gao, Q, de Bruyn, H, Gilbert, RG and Fitzgerald, MA. Improved methods for the structural analysis
of the amylose-rich fraction from rice flour. Biomacromolecules, 7, 866-876, 2006.
237. Webb, JA and James, JM. Karst evolution of the Nullarbor Plain, Australia. Geological Society of America, Special
Paper, 404, 65-78, 2006.
238. Wee, S, Mortimer, A, Moran, D, Wright, A, Barlow, CK, O’Hair, RAJ, Radom, L and Easton, CJ. Gas-phase
regiocontrolled generation of charged amino acid and peptide radicals. Chemical Communications, 4233-4235,
2006.
239. Whitby, CP, Djerdjev, AM, Beattie, JK and Warr, GG. Nanoparticle adsorption and stabilisation of surfactantfree emulsions. Journal of Colloid and Interface Science, 301, 342-345, 2006.
240. Whitten, A, Turner, P, Klooster, WT, Piltz, RO and Spackman, MA. Reassessment of large dipole moment
enhancements in crystals: A detailed experimental and theoretical charge density analysis of 2-methyl-4nitroaniline. Journal of Physical Chemistry A, 110, 8763-8776, 2006.
241. Wichmann, K, Antonioli, B, Söhnel, T, Wenzel, M, Gloe, K, Gloe, K, Price, JR, Lindoy, LF, Blake, AJ and
Schröder, M. Polyamine-based anion receptors: Extraction and structural studies. Coordination Chemistry Reviews,
250, 2987-3003, 2006.
242. Widmer-Cooper, A and Harrowell, P. Free volume cannot explain the spatial heterogeneity of Debye–Waller
factors in a glass-forming binary alloy. Journal of Non-crystalline Solids, 352, 5098-5102, 2006.
243. Widmer-Cooper, A and Harrowell, P. Predicting the long-time dynamic heterogeneity in a supercooled liquid on
the basis of short-time heterogeneities. Physical Review Letters, 96, 185701, 2006.
244. Willis, AC, O’Connor, PD, Taylor, WC and Mander, LN. The absolute stereochemistry of the Galbulimima
alkaloids. Australian Journal of Chemistry, 59, 629-632, 2006.
245. Winkelman, GB, Dwyer, C, Marsh, C, Hudson, TS, Nguyen-Manh, D, Doblinger, M and Cockayne, DJH. The
crystal/glass interface in doped Si3N4. Materials Science & Engineering, A: Structural Materials: Properties, Microstructure
and Processing, A422 (1-2), 77-84, 2006.
246. Wittick, LM, Jones, LF, Jensen, P, Moubaraki, B, Spiccia, L, Berry, KJ and Murray, KS. New mixed-valence
MnII2MnIII2 clusters exhibiting an unprecedented MnII/III oxidation state distribution in their magnetically coupled
cores. Dalton Transactions, (12), 1534-1543, 2006.
126
School of Chemistry
Annual Research Report
127
247. Witting, PK, Harris, HH, Rayner, BS, Aitken, JB, Dillon, CT, Stocker, R, Lai, B, Cai, Z and Lay, PA. The
endothelium-derived hyperpolarizing factor H2O2, promotes metal-ion efflux in aortic endothelial cells: Elemental
mapping by a hard x-ray microprobe. Biochemistry, 45, 12500-12509, 2006.
Conference Publications
248. Wood, GPF, Easton, CJ, Rauk, A, Davies, MJ and Radom, L. Effect of side chains on competing pathways for
b-scission reactions of peptide-backbone alkoxyl radicals. Journal of Physical Chemistry A, 110, 10316-10323,
2006.
Refereed
249. Wood, GPF, Radom, L, Petersson, GA, Barnes, EC, Frisch, MJ and Montgomery (Jr), JA. A restricted-open-shell
complete-basis-set model chemistry. Journal of Chemical Physics, 125, 94106, 2006.
~
~
250. Yin, H-M and Kable, SH. Rotational analysis of the HCO B(2A´ ) – X(2A´ )311 and 312 bands. Journal of Molecular
Spectroscopy, 237, 163-173, 2006.
1.
Brooker, L, Goebel, C, Kazlauskas, R, Trout, G and George, AV. Confirmation of Triamcinolone Acetonide Use
by LC-MS-MS. Recent Advances in Doping Analysis (14). Proceedings of the Manfred Donike Workshop, 24th Cologne
Workshop on Dope Analysis, 4th to 9th June 2006, p463-466, Koln: Sportverlag Strauss. Ed: W. Schanzer, H. Geyer,
A. Gotzmann, U. Mareck. ISBN: 978-3-939390-14-5.
251. Yin, HM, Kable, SH, Zhang, X and Bowman, JM. Signatures of H2CO photodissociation from two electronic
states. Science, 311, 1443-1446, 2006.
2.
Cawley, A, Kazlauskas, R, Trou, G, Tjoa, J, Huynh, T and George, AV. GC-C-IRMS Analysis of Endogenous
Reference Compounds. “Recent Advances in Doping Analysis (14)”. Proceedings of the Manfred Donike Workshop,
24th Cologne Workshop on Dope Analysis, 4th to 9th June 2006, p267-276, Koln: Sportverlag Strauss. Ed: W. Schanzer,
H. Geyer, A. Gotzmann, U. Mareck. ISBN: 978-3-939390-14-5.
3.
Fernandez, JR and Harrowell, P. What stabilizes the intermediate structure of an amorphous alloy? AIP Conference
Proceedings, Flow Dynamics, 832, 3-10, 2006.
4.
Marshall, CP. Special issue - A collection of papers presented at 6th Australian Conference on Vibrational Spectroscopy
(ACOVS 6) - Sydney, Australia - 28-30 September, 2005 - Preface. Vibrational Spectroscopy, 41, 143-143, 2006.
5.
Noren, L, Christensen, J, Lidin, S, Schmid, S and Withers, RL. The Sn1-xSb1+x, x ~ 0.5, Solid Solution: The
Relationship Between a and b. 30th Annual Condensed Matter and Materials Meeting, 7-10 February, 2006, Wagga
Wagga, Australia. Australian Institute of Physics, ISBN: 1-920791-09-4, 1-3, 2006.
256. Zhou, Q, Kennedy, BJ and Elcombe, MM. Synthesis and structural studies of cation-substituted Aurivillius
phases ASrBi2Nb2TiO12. Journal of Solid State Chemistry, 179, 3744-3750, 2006.
6.
257. Zhu, H, Zheng, Z, Gao, X, Huang, Y, Yan, Z, Zou, J, Yin, H, Zou, Q, Kable, SH, Zhao, J, Xi, Y, Martens, WN
and Frost, RL. Structural evolution in a hydrothermal reaction between Nb2O5 and NaOH solution: From Nb2O5
grains to microporous Na2Nb2O6 · 2/3H2O fibers and NaNbO3 cubes. Journal of the American Chemical Society, 128,
2373-2384, 2006.
Pecchia, A, Gagliardi, A, Solomon, G, Di Carlo, A, Frauenheim, Th and Reimers, JR. Incoherent tunneling and
heat dissipation in molecular bridges. Progress in Nonequilibrium Green’s Functions III, August 22-25, 2005. Journal
of Physics: Conference Series. Institute of Physics Publishing, 35, 349-356, 2006.
7.
Read, JR, Buntine, MA, Crisp, GT, Barrie, SC, George, AV, Kable, SH, Bucat, RB and Jamie, IM. The ACELL
project: Student participation, professional development, and improving laboratory learning. Symposium Proceedings:
Assessment in Science and Learning, September 28, 2006, The University of Sydney, Australia, 113-119, 2006.
258. Ziolkowski, EJ, Turner, P and Rendina, LM. Mono- and di-nuclear platinum(II) complexes containing O- and
N-bonded acetamide. Inorganic Chemistry Communications, 9, 53-56, 2006.
8.
Schmid, SA, Elcombe, M and Rhode, M. Defect perovskites in the SrO-ZrO2Nb2O5 system. 30th Annual Condensed
Matter and Materials Meeting, 7-10 February, 2006, Wagga Wagga, Australia. Australian Institute of Physics, ISBN:
1-920791-09-4, 1-3, 2006.
9.
Yeung, A, George, A, Schmid, S and King, M. Testing the personalisation hypothesis in pre-laboratory e-learning
environments. Symposium Proceedings: Assessment in Science and Learning, September 28, 2006, The University of Sydney,
Australia, 146-152, 2006.
252. Yuen, AKL, Jolliffe, KA and Hutton, CA. Preparation of the central tryptophan moiety of the celogentin/moroidin
family of anti-mitotic cyclic peptides. Australian Journal of Chemistry, 59, 819-826, 2006.
253. Zhou, Q and Kennedy, BJ. The nature of the orthorhombic to tetragonal phase transition in Sr1-xCaxMnO3. Journal
of Solid State Chemistry, 179, 3568-3574, 2006.
254. Zhou, Q and Kennedy, BJ. Thermal expansion and structure of orthorhombic CaMnO3. Journal of Physics and
Chemistry of Solids, 67, 1595-1598, 2006.
255. Zhou, Q, Kennedy, BJ and Elcombe, MM. Neutron powder diffraction studies of Ca2-xSrxCoWO6 double
perovskites. Physica B, 385-386, 190-192, 2006.
10. Youl, DJ, Read, JR, George, AV and Schmid, S. Bridging courses: Good learning environments for engaging
students? Engaging Students, 12-14 July, Gold Coast, QLD, Australia. Published by Queensland University of
Technology. ISBN: 0-646-46313-6, 1-11, 2006.
128
School of Chemistry
129
Annual Research Report
Patents
1.
Max Crossley, Pall Thordarson, Neil Hunter, Benjamin Yap, and Charles Andrew Collyer, Porphyrin Linked
Metronidazole for Treatment of Gum Disease Caused by Porphyromonas Gingivalis. PCT Int. Appl.
W02006005137, A1 20060119; CAN 144:128797; AN 2006:54402 85 pp. 19th January 2006. International
Classification: (IPC1-7): C07D403/14
2.
Bis-pyridinium compounds. K. Jolliffe, A. Widmer, Australian Provisional Patent, Application no. 2006902367,
The University of Sydney.
3.
C.J. Kepert, M.E.R. Green; Indicator, Australian Provisional Patent, Application No. 2006904033, the University
of Sydney (2006).
4.
Lay, Peter; Hambley, Trevor; Kennedy, Brendan; Morgan, Ying. Preparation of copper indomethacin complexes
having antiinflammatory activity. PCT Int. Appl. (2006), 80pp. WO 2006099684
5.
Lay, Peter; Hambley, Trevor; Kennedy, Brendan; Morgan, Ying; Kaur, Ravinder; Davies, Neal. Preparation of
transition metal acemetacin complexes with antiinflammatory activity. PCT Int. Appl. (2006), 69pp. WO
2006099677
6.
Lay, Peter; Hambley, Trevor; Kennedy, Brenden; Davies, Neal. Method for the prophylaxis or treatment of carcinomas
using metal complexes of antiinflammatory drugs. PCT Int. Appl. (2006), 132pp. WO 2006099685
7.
Lay, Peter; Methods and compositions for the prophylaxis or treatment of cancers of the skin, PCT/IB2006/002423,
01/09/06
8.
Lay, Peter; Hambley, Trevor, Methods for prophylaxis or treatment of cardiovascular inflammation, Provisional
patent applications, Aus 2006901557, 27/03/06; USA, 60/830,203, 11/07/06
9.
Lay, Peter; Hambley, Trevor, Methods for prophylaxis or treatment, Provisional patent applications, Aus 2006901583,
28/03/06; USA, 11/07/06
10. Lay, Peter, Hambley, Trevor, Metal complexes having anti-inflammatory activity, Provisional patent applications,
Aus 2006905170, 19/09/06; Aus 2006905267, 22/09/06; Aus 2006905377, 28/09/06.
11. Lay, Peter, Hambley, Trevor, Prophylaxis and treatment of cancer. Provisional patent application, Aus 2006905259,
22/09/06
12. Lay, Peter, Hambley, Trevor, Combination Therapy for the Treatment of Cancer. Provisional patent application,
Aus 2006905260, 22/09/06.
13. Lay, Peter, Hambley, Trevor, Metal complexes having anti-inflammatory activity II, Provisional patent applications,
Aus 2006905265, 22/09/06; Aus 2006905378, 28/09/06
14. Lay, Peter, Hambley, Trevor, Skin treatment and wound repair. Provisional patent application, Aus 2006905266,
22/09/06.
15. Maschmeyer, T., Fois, A., Masters, A.F., COmpartmentlaised Nanoreactors, Provisional Application US Patent
Office: Filed on 25 August 2006, United States of America Patent Application No. 60/840009.
16. Shan, Z., Jansen, J. C., Yeh, C. Y., Angevine, P. J., Maschmeyer, T. & Hamdy, M. S., Mesoporous metal oxide-based
supports and catalysts for petroleum refining and conversion of organic compounds, 2005-198564 2006052234,
((USA).), 34 pp , Cont -in-part of U S Ser No 313,720 2006.
17. Vesiculated Polymer Particles, Australian Provisional Patent number 12844010, October 2006.
2005
Total
Book Chapters
Journal Publications
Conference Papers
Patents
5
224
18
7
2006
Total
Book Chapters
Journal Publications
Conference Papers
Patents
3
258
10
17
Research
Fellowships
& Grants
132
School of Chemistry
Fellowships
Annual Research Report
133
ARC Grants
Discovery Projects
Dr Rob Atkin
ARC Australian Postdoctoral Fellowship
Professor Jeffrey Reimers
ARC Professorial Fellowship
Associate Professor Phil Attard
ARC Australian Professorial Fellowship
Dr Pall Thordarson
ARC Australian Research Fellowship
Dr Gregory Giles
University of Sydney Postdoctoral Fellowship
Dr Catherine Whitby
Gritton Postdoctoral Fellowship
Dr Angus Gray-Weale
ARC Australian Postdoctoral Fellowship
Dr Hugh Harris
ASRP Postdoctoral Fellowship
Dr Toby Hudson
University Postdoctoral Research Fellowship
Dr Kate Jolliffe
ARC Queen Elizabeth II Fellowship
Dr Meredith Jordan
ARC Australian Research Fellowship
Professor Cameron Kepert
ARC Federation Fellowship
Professor Peter Lay
ARC Australian Professorial Fellowship
Dr Nigel Lucas
ARC Australian Postdoctoral Fellowship
Dr Craig Marshall
ARC Australian Postdoctoral Fellowship
Professor Thomas Maschmeyer
ARC Federation Fellowship
Dr Damian Moran
Sesqui Postdoctoral Fellowship
Dr Klaas Nauta
ARC Australian Research Fellowship
Professor Leo Radom
ARC Australian Professorial Fellowship
Nanotribology and nanorehometry: A fundamental study of the dynamic interactions of particles and surfaces at the
molecular level
Attard, P – $160,934
The interface of oil-in-water emulsions
Beattie, JK, Warr, GG – $95,827
Anti-cancer natural products: Total synthesis and biological evaluation of lasonolide A and analogues
Coster, MJ – $114,444
Design and development of HIV-1 integrase inhibitors based on a natural product lead
Coster, MJ – $55,232
Molecular electronics: From electron transfer through photosynthesis towards functional nano devices
Crossley, MJ, Reimers, JR, Hush, NS – $301,103
Organometallic transformations of organic molecules
Field, LD – $90,198
Reactions of coordinated dinitrogen
Field, LD, Messerle, BA – $103,931
Formation and stability of polymerically stabilized colloids
Gilbert, RG – $99,641
Molecular archaeology: New knowledge from molecular weight distributions of synthetic and natural polymers
Gilbert, RG – $197,686
Disorder and dynamics in superionic conductors
Gray-Weale, A – $75,907
Probing and developing hypoxia-selective anti-cancer agents
Hambley, TW – $85,179
Functionalised MMP inhibitors as radiodiagnostic, radiotherapeutic, and radiation-sensitising agents for metastatic
cancer
Hambley, TW, Kassiou, M – $93,748
Antifreeze proteins and glycoproteins
Harding, MM, Haymet, ADJ – $8,992
Synthesis and applications of antifreeze proteins and glycoproteins
Harding, MM – $140,000
The stability of glass-forming alloys: simulation studies
Harrowell, PR – $74,532
134
School of Chemistry
135
Annual Research Report
Backbone modified cyclic peptides: Scaffolds for supramolecular chemistry
Jolliffe, KA – $11,152
Elucidating the mode of action of nicotinic receptor ligands
McLeod, MD – $96,805
Cross-linked Tyrosine Residues in Peptides and Proteins
Jolliffe, KA, Hutton, CA – $1,597
Superfluid helium nanodroplets: A unique matrix for molecular spectroscopy
Nauta, K – $130,698
Self-assembly of nanoscale molecular capsules
Jolliffe, KA, Lindoy, LF – $135,252
Free radicals in chemistry and biology: A computational quantum chemistry investigation
Radom, L – $91,425
Predicting environmental effects on structure and reactivity
Jordan, MJT – $62,424
Molecular electronics principles and applications
Reimers, JR – $232,947
The first chemically accurate tools in theoretical materials research
Jordan, MJT – $105,818
Platinum-carborane complexes as new agents for boron neutron capture therapy
Rendina, LM – $93,636
Understanding phase transitions through precise structural studies
Kennedy, BJ, Siegbert, SA – $77,474
DNA nanoshuttles: A new class of DNA-binding molecules
Rendina, LM, Harding, MM – $128,964
Polynuclear spin-crossover molecular switches: Host-guest chemistry magnetism and memory
Kepert, CJ – $96,237
Laser spectroscopy of molecular electronic components
Schmidt, T – $152,850
Molecular framework materials: Nanoporosity and anomalous thermal expansion
Kepert, CJ – $150,812
Optical spectroscopy of extraterrestrial molecules
Schmidt, T – $136,546
The chemistry and biochemistry of chromium: Cancer and nutrition
Lay, PA – $144,976
Light-activated bioconjugates for application in synthesis and biosensors
Thordarson, P – $242,788
Nanoprobe and microprobe structural and spectroscopic studies in biomedical research
Lay, PA, Harris, HH, Stampfl, AP – $127,375
Surfactant self-assembly in ionic liquids
Warr, GG, Atkin, R – $97, 755
Metal directed assembly of new supramolecular systems
Lindoy, LF, Meehan, GV – $86,900
Platinum-group metal oxides with modulated crystal structures: Flexible frameworks designed for geometrically
frustrated magnetism
Ling, Dr CD – $81,520
Metallographitic discs as new materials
Lucas, N – $125,328
Organic geochemistry of the McArthur River hydrothermal deposit
Marshall, CP – $94,760
From nanostructured catalysts to process innovation
Maschmeyer, T – $156,060
Molecular recognition in chiral ionic liquids
Maschmeyer, T – $163,040
Improved catalysts for the liquid phase hydrocarbon oxidation
Masters, A, Beattie, JK, Maschmeyer, T – $85,179
Synthesis of the pyrrolo[21-c][14]benzodiazepines: potent DNA binders
McLeod, MD – $117,122
TOTAL: $4,924,794
ARC Linkage Projects
Synthesis and evaluation of anti-microbial porphyrin adducts for the targeted inhibition of Porphyromonas gingivalis
Crossley, MJ, Collyer, C – $73,714
Development of a molecular flash memory for long-term extremely high-capacity unpowered data storage
Crossley, MJ, Reimers, JR, Hush, NS, Thordarson, P – $322,513
Novel barrier products: Synthesis design using controlled radical polymerization in dispersed systems
Gilbert, RG – $3,189
Rubbery nanoparticles for improved plastics additives and adhesives through novel low-temperature polymerization
Gilbert, RG – $48,082
Nanoparticles with designed morphology for surface-coating applications
Hawkett, BS, Warr, GG, Gilbert, RG – $322,524
Metal-based anti-inflammatory drugs with high efficacy and low side-effects
Lay, PA, Hambley, TW, Pearce S, Dillon, C – $106,506
136
School of Chemistry
Supercritical highly-integrated and modular, continuous solid-catalysed biodiesel production from plant and animal
feedstocks
Maschmeyer, T, Haynes, BS – $78,972
Inception of a practical biomimetic flexible photovoltaic device
Reimers, JR, Crossley, MJ, Hush, NS – $252,355
137
Annual Research Report
ARC Linkage International Grants
Polynuclear spin-crossover molecular switches: Host-guest chemistry, magnetism and memory
Kepert, CJ – $7,133
Development of a test bed for molecular memory and molecular photovoltaic devices
Reimers, JR – $10,000
Bubble stabilization and density control in self-supporting explosive emulsions
Warr, GG, Hawkett, BS, Tanner, RI, Gore, J – $134,067
TOTAL: $1,341,922
Ditopic receptors for the co-operative binding of cations and anions
Lindoy, LF – $9,157
Chemistry of the archaean ocean and its impact on Earth’s early atmosphere and ecosystems
Rey, PF, Philippot, P, Dutkiewicz, A, Marshall, CP, Van Kranendonk – $133,670
ARC Linkage - Infrastructure Equipment and Facilities (LIEF)
Structure of polymer surfactant lubricant layers
Warr, GG, Richetti, P – $24,279
LIEF grants are multi-institutional, often involving a large number of researchers. In 2006, members
of the School were involved in the following successful LIEF grants:Combinatorial deposition and characterisation facility for new alloy thin film materials
Bilek, MM, Valanoor, N, McKenzie, Dr, O’Connor, J, Green, MA, Lay, PA, Ekins-Daukes, NJ, King, BV, James, BW,
Conibeer, GJ, Kable, SH, Schmidt, T, Ostrikov, K, Hoffman, MJ, Riley, DP, Ferry, M – $1,200,000
Access for Australian researchers to advanced neutron beam techniques
Kennedy, BJ and AINSE – $240,000
TOTAL: $184,239
ARC Special Research Initiative
Scientific instruments as ICT components in building a GrEMLIN for e-research
Kepert, CJ, Turner, P, Zomaya, A – $62,424
e-Research infrastructure for the molecular and materials structure sciences
Kepert, CJ and University of Queensland – $1,000,000
Floating-zone crystal growth facility
Ling, CD, Kennedy, BJ, Schmid, SA, Robinson, R, Curfs, C, Welberry, TR, Withers, RL, Stampfl, AP
– $210,000
Elemental and structural analysis facility comprising a FTICR mass spectrometer and a CHNS analyser
Maschmeyer, T, Lay, PA, Kable, SH, Karuso, PH, Gore, DB, Downard, KM, McLeod, MD, Jolliffe, KA, Johnston,
GA, Hanrahan, JR, Fisher, KJ – $730,000
TOTAL: $62,424
ARC Research Network
Molecular and materials structure network
Kepert, CJ (plus 100 other participants) – $300,000
The rapid kinetics research facility – an integrated system for rapid kinetic studies of materials using synchrotron
radiation
Maschmeyer, T and The University of Newcastle – $195,000
TOTAL: $300,000
ARC Centres of Excellence
Nanostructure deposition facility
Reimers, JR and The University of Newcastle – $180,240
Facility for structural analysis of bio-molecular complexes and self assembly
Trewhella, J, Curmi, PM, Mabbutt, BC, Warr, GG, Stokes, HW, Cavicchioli, R – $950,000
TOTAL: $4,705,240
Free radical chemistry and biotechnology
Radom, L – $392,873
TOTAL: $392,873
138
School of Chemistry
139
Annual Research Report
Australian Nuclear Science and Technology
Organization (ANSTO)
ARC Fellowships
Dr Rob Atkin
ARC Australian Postdoctoral Fellowship
Associate Professor Phil Attard
ARC Australian Professorial Fellowship
Dr Angus Gray-Weale
ARC Australian Postdoctoral Fellowship
Access to Major Research Facilities Program
Dr Kate Jolliffe
ARC Queen Elizabeth II Fellowship
Structure of discrete and bicontinuous room-temperature ionic liquid microemulsions
Microemulsion structure in some new protic ionic liquid
Atkin, R – $10,327
Dr Meredith Jordan
ARC Australian Research Fellowship
Phase transitions in two double perovskites - K2SnCl6 and K2ReCl6 - Neutron Science Laboratory (KENS), Japan, 21
April 2004
Kennedy, BJ – $12,711
Professor Cameron Kepert
ARC Federation Fellowship
Isotropic negative thermal expansion in a molecular framework - ISIS facility UK February 2003, 3 days
Kepert, CJ – $16,403
Professor Peter Lay
ARC Australian Professorial Fellowship
Neutron powder diffraction studies of oxygen vacancy ordering in misfit-layered cobaltates
Ling, C – $5,953
Dr Nigel Lucas
ARC Australian Postdoctoral Fellowship
An XAFS study of non-heme iron oxidase mimics
Rutledge, PJ – $3,891
Dr Craig Marshall
ARC Australian Postdoctoral Fellowship
Experiments at ISIS, UK - September 2003
Warr, GG – $11,377
Professor Thomas Maschmeyer
ARC Federation Fellowship
TOTAL: $60,662
Dr Klaas Nauta
ARC Australian Research Fellowship
Professor Leo Radom
ARC Australian Professorial Fellowship
Australian Synchrotron Research Program
Professor Jeffrey Reimers
ARC Professorial Fellowship
Negative thermal expansion in coordination framework materials
Kepert, CJ, Halder, Dr Greg – $9,900
Dr Pall Thordarson
ARC Australian Research Fellowship
Investigations into the rate of biotransformation of inorganic chemotherapeutics - ANBF
Hambley, TW – $15,936
TOTAL: $1,801,740
ARC TOTAL: $13,713,232
Biotransformations of chemopreventative selenium compounds in bulk cell cultures - ANBF
Harris, HH – $20,036
Structures and phase transitions in metal oxides and halides - ANBF
Kennedy, BJ – $22,943
XAFS studies of bioinorganic systems - ANBF and NSRRC
Lay, PA – $49,162
140
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Annual Research Report
Other External Competitive Grants
Travel under the Australian Synchrotron Research Program
Ling, CD – $7,363
Ceramic materials with modulated structures - ANBF, Japan, 18-19 November 2003
Schmid, SA – $594
Australian Antarctic Science Grant
Molecular characterisation of cold-adapted metallo-oxtransferases from the dimethylsulfoxide reductase family expressed
by Antarctic bacteria (Genus: Shewanella)
Codd, R – $9,245
Fellowships
Dr Hugh Harris
ASRP Postdoctoral Fellowship
International Joint Research Grants
TOTAL: $162,579
Australian Institute of Nuclear Science
and Engineering (AINSE)
Scholarships and Awards
New strategies for developing ultrathin nanostructured polymer films
Warr, GG, Gilbert, RG – $33,805
Australian Academy of Technological Sciences and Engineering/
DEST
Sydney-SIOC new chemical technologies workshop, Shanghai, China
Todd, MH – $32,000
FAST, DEST/French Embassy
Self-assembly of diblock copolymers
Blom, A – $6,660
Light induced electronic switching in nanoporous materials and supramolecular clusters
Kepert, CJ – $16,500
Structure of Bi double perovskites
Kennedy, BJ – $20,400
TOTAL: $91,550
Negative thermal expansion in molecular framework materials
Kepert, CJ – $7,525
Optimising magnetic frustration: search for a ‘quantum spin-liquid’ state in a variable crystal structure
Ling, CD – $44,200
Geometrically frustrated magnetism in bismuth platinum-group oxides
Ling, CD – $13,000
Structural studies of ionic conductive defect perovskites
Saines, P, Kennedy, BJ – $13,000
Structure of polymerised surfactant films on quartz
Warr, GG – $27,415
Ceramic materials with modulated structures
Schmid, SA – $32,300
TOTAL: $164,500
142
School of Chemistry
University of Sydney Grants
143
Annual Research Report
Fellowships
Dr Gregory Giles
University of Sydney Postdoctoral Fellowship
Research and Development Scheme
New antibacterial agents effective against methicillin-resistant Staphylococcus Aureus (MRSA)
Coster, MJ – $21,000
Misfit-layered cobaltates: Structurally flexible ceramic oxides with tuneable magnetic and electronic properties
Ling, CD – $29,000
Dr Toby Hudson
University Postdoctoral Research Fellowship
Dr Damian Moran
Sesqui Postdoctoral Fellowship
Dr Catherine Whitby
Gritton Postdoctoral Fellowship
New catalysts for hydrocarbon oxidation
Rutledge, PJ – $21,000
A new chemical route to an important antiparasitic pharmaceutical
Todd, MH – $24,000
TOTAL: $786,892
NH&MRC Grants
Project Grant
Fungal phospholipases: A novel target for drug discovery
Jolliffe, KA – $191,950
Equipment Grant
New strategies for developing ultrathin nanostructured polymer films
Lay, PA – $65,500
Industrial Research Partnerships
Codd, R – (Herman Slade Foundation)
Crossley, MJ, Reimers, JR, Hush, NS, Thordarson, P – (Research Contract)
Gilbert, RG – (BASF)
Gilbert, RG – (Research Contract)
Gilbert, RG, Hawkett, BS – (Ansell Shah Alam Sdn Bhd)
Cancer Research Fund Grants
Synthesis and biological evaluation of new anti-mitotic anti-cancer compounds based on a highly cytotoxic natural
product
Coster, MJ – $49,737
Tumour specific boronated peptides as a new class of agents for boron neutron capture therapy
Rendina, LM, Jolliffe, KA – $49,885
A new class of DNA-cleaving artificial enzymes
Todd, MH– $49,888
Harrowell, PR – (AOARD-US Air Force)
Hawkett, BS – (Sirtext Medical Ltd)
Hawkett, BS – (Kerr-McGee Chemical)
Hawkett, BS, Warr, GG, Gilbert, RG – (Research Contract)
Kepert, CJ – (UCOM Ten)
Kepert, CJ – (DEST)
Lay, PA, Hambley, TW – (Medical Therapies Ltd)
Lay, PA, Hambley, TW, Pearce, S, Dillon, C – (Nature Vet Pty Ltd)
Maschmeyer, T – (CSIRO Flagship Collaboration Research Fund)
Ridley, D, Stamford, NP – (Silverbrook Research Pty Ltd)
Stamford, NP – (NSW Department of Primary Industries (through Yanco Agricultural Institute))
Stamford, NP – (Ultraceuticals Pty Ltd)
Bridging Support Grants
Redox enzymes from Antarctic organisms
Codd, R – $26,300
Turner, P – (Grangenet)
Vonwiller, S – (Research Contract)
TOTAL: $ 1,810,448
144
School of Chemistry
Bequests
145
Annual Research Report
The Cornforth Foundation for Chemistry
Bae, Ms Carol
Bellas, Dr Thomas
Cannon, Dr Jack
Ridley, Dr Anne
Agnes Campbell Bequest
Bruce Veness Chandler Bequest
Professor Archibald Liversidge Bequest
Scholfield Bequest
RJW Le Fèvre Bequest
GG Blake Radio Research Bequest
Janet Elspeth Crawford Bequest
Charles E Fawsitt Bequest
Edna Maude Goulston Bequest
Arthur Hollis Memorial Prize
George Harris Scholarship
CH Wilson Prize
Dr Joan R Clark Research Scholarship
John A Lamberton Research Scholarship
Surface Coating Association of Australia Scholarship
The Gritton Scholarships
The Hush Trust
Lim, Associate Professor Kieran
TOTAL: $4,525
TOTAL: $589,359
Other Donations
The School of Chemistry would like to thank the following people for their generous donations during 2006:-
The School of Chemistry Alumni Fund
Broadhurst, Associate Professor Norman
Petfield, Mr Gregory
The Foundation for Inorganic Chemistry
Alpha Chemicals Pty Ltd
Barlow, Dr Thomas
Freeman, Emeritus Professor Hans
Geyer, Mr Robert
Huq, Dr Fazlul
Lay, Professor Peter
Lindoy, Emeritus Professor Len
Nell & Herman Slade Trust
Savage, Mr Thomas
Total Income for 2006
$17,383,747
146
School of Chemistry
Awards,
Scholarships
& Prizes
148
School of Chemistry
Annual Research Report
149
Awards to Staff
Ms Katie Cergol, PhD Student
Jim O’Donnell Travel Award from the RACI.
Dr Mark Coster
RACI Organic Division Lectureship for Recently Appointed Staff.
Mr Malcolm Green, PhD Student
Shared the Grand Prize in the University of Sydney Innovation Challenge competition for his business plan on the
applications of nanotubular clays. Malcolm’s was judged the equal top from more than 400 entries received across the
entire University. The prize, amounting to $20,000, is to be directed towards the commercialisation of his research.
Dr Deanna D’Alessandro
Cornforth Medal of the RACI for the most outstanding PhD thesis submitted in any branch of chemistry, chemical
science or chemical technology.
Dr Brian Hawkett
Citation by the RACI Polymer Division at the 28th Australasian Polymer Symposium in Rotorua. This award recognises
Brian’s scientific achievement in the study of emulsion polymerization and for services to the Polymer Division.
Dr Kate Jolliffe
RACI’s Biota Award for her work on Inhibitors of Fungal Phospholipase B: Novel Antifungal Agents. The Medal is
awarded to the chemist judged to be responsible for the best drug design and development paper published, patent
taken out, or commerical-in-confidence report in the previous calendar year concerning small molecules (less than 1,000
Da) as potential therapeutic agents.
Professor Cameron Kepert
Inaugural Alan Sargeson Award. This award has allowed Cameron to visit and talk at chemistry departments around
the country during 2006.
Emeritus Professor Len Lindoy
Mercator Guest Professorship at the Technical University Dresden for a period of five months.
Professor Leo Radom
Fukui Medal. The senior medal of the Asian Pacific Association of Theoretical and Computation Chemists.
Awards to Students
Ms Kaitlin Beare, PhD Student
Best poster presentation at the RACI Drug Design Conference. This is a high profile conference attended by leading
academic and industrial medicinal chemistry groups within Australia.
Mr David Bray, PhD Student
C.G. and R.J.W. Le Fèvre Postgraduate Student Lectures Award. These lectures were established in 1985 following a gift
of $2 000 from Emeritus Professor R.J.W. Le Fèvre and are awarded on the recommendation of the Sydney University
Chemical Society.
Mr Lance Brooker, PhD Student
The Chromatography Prize. This prize was presented at the 14th Annual RACI R&D Topics Conference, 5th to 8th
December 2006 at Wollongong University.
Mr Peter Brotherhood, PhD Student
C.G. and R.J.W. Le Fèvre Postgraduate Student Lectures Award. These lectures were established in 1985 following a gift
of $2 000 from Emeritus Professor R.J.W. Le Fèvre and are awarded on the recommendation of the Sydney University
Chemical Society.
Ms Annie Nguyen, Honours Students
NSW RACI Analytical Chemistry Award
Mr Joshua Peterson, PhD Student
Best Oral Presentation at the RACI NSW Organic Chemistry Group One Day Symposium at the RSC, ANU on the
27th November, 2006.
Mr Nima Sayyadi, PhD Student
Best Poster Presentation at the RACI NSW Organic Chemistry Group One Day Symposium at the RSC, ANU on the
27th November, 2006.
Ms Natasha Sciortino, PhD Student
Ludo Crystallography Scholarship by the International Centre for Diffraction Data (ICDD). Only six of these are awarded
each year.
Mr Stuart Thickett, PhD Student
1. C.G. and R.J.W. Le Fèvre Postgraduate Student Lectures Award. These lectures were established in 1985 following
a gift of $2 000 from Emeritus Professor R.J.W. Le Fèvre and are awarded on the recommendation of the Sydney
University Chemical Society.
2. NSW Student RACI Polymer Prize.
Mr Shane Wilkinson, PhD Student
Best oral presentation at the RACI Drug Design Conference. This is a high profile conference attended by leading
academic and industrial medicinal chemistry groups within Australia.
Ms Alexandra Yeung, PhD Student
Jim O’Donnell Travel Award from the RACI.
150
School of Chemistry
Student Prizes and Scholarships
T
he School of Chemistry awards over $85 000 in Prizes and Scholarships each year to the best of its students. The
following students were awarded prizes or scholarships in 2007 based on their academic achievements in 2006.
Scholarships are awarded subject to the students satisfying conditions required for each of the individual scholarships.
Agnes Campbell Prize
Postgraduates
Samuel Banister
Kaitlin Beare
David Bray
Peter Brotherhood
Katie Cergol
Jack Clegg
Joshua Fischer
Hendra Gunosewoyo
Jill Halliday
Tony Khoury
Rebecca Lesic
Daniel Obando Gutierrez
Joshua Peterson
Shiva Prasad
Nima Sayyadi
David Schilter
Erin Sheridan (Ziolkowski)
Grace Simpkins
Maxine Sintic
Danial Stocks
Cody Szczepina
James Webb
Shane Wilkinson
Tomasz Wyczesany
Benjamin Yap
Agnes Campbell Prize
Honours
Hong Yue Ching
James Cochrane
John Nguyen Doan
Alessandro Fois
Adam Hambly
Joseph Ioppolo
Wing Yan Leung
Iman Moussa
Adam Piggott
Katie Tong
Shane Wilkinson
Philip Young
Arthur Hollis Memorial Prize
Nithin Iyer
Australian-USA Foundation Prize
Kathryn Gall
Charles E. Fawsitt Prize
Amelia Parker
Joan R Clark Research Scholarship
Jarrod Amoore
Cindy Aquino
Jack Clegg
Jeannette McAlpine
Mark Roberston
Natasha Sciortino
Benjamin Yap
Chemistry Alumni Scholarship
Jill Halliday
Levey Scholarship 2
Yu Heng Lau
Edna Maude Goulston Prize in
Organic Chemistry (shared)
Rhiannon Stewart
Shane Wilkinson
Levey Scholarship 3
David Llewellyn
C.H. Wilson Prize
Adam Pigott
Frank E. Dixon Scholarship
George Zhong
G.S. Caird Scholarship (3 awards)
Patricia Donovan
Jenna Joester
Jessica Veliscek Carolan
G e o rg e H a r r i s S c h o l a r s h i p
(shared)
Rebecca Lesic
Jeannette McAlpine
Joshua Peterson
Hush Prize
Oliver Thorn-Seshold
Inglis Hudson Scholarship
(3 awards)
William Early
Michael Lee
Belinda Lu
Iredale Prize
Cameron Weber
Janet Elspeth Crawford Prize in
Chemistry
Natsuho Yamamoto
R.J.W. Le Fèvre – DAASN RAO
Prize
Jenna Joester
R.J.W. Le Fèvre Research Travelling
Scholarship
Erin Sheridan
Slade Prize
Alexandra Manos-Turvey
Surface Coating Association of
Australia Scholarship
Stuart Thickett
Walter Burfitt Scholarship No.1
Oliver Thorn-Seshold
2006
Staff and
Students
152
Academic Staff
Head of School
HAMBLEY, Prof Trevor
Deputy Head of School
WARR, Prof Greg
School of Chemistry
Annual Research Report
MASCHMEYER, Prof Thomas
MASTERS, A/Prof Tony
McLEOD, Dr Mal
RENDINA, Dr Lou
RUTLEDGE, Dr Peter
SCHMID, Dr Siggi
SCHMIDT, Dr Timothy
TODD, Dr Mat
WARR, Prof Greg
Head of Research
KENNEDY, A/Prof Brendan
Head of Teaching
BAKER, Dr Rob
1st Year Coordinator
SCHMID, Dr Siggi
2nd Year Coordinator
CLARKE, Dr Ron
3rd Year Coordinator
BAKER, Dr Rob
Honours
RENDINA, Dr Lou (Director)
SCHMIDT, Dr Timothy (Coordinator)
Postgraduate Studies
KENNEDY, A/Prof Brendan (Director)
COSTER, Dr Mark (Coordinator)
BAKER, Dr Rob
BEATTIE, A/Prof James
CLARKE, Dr Ron
CODD, Dr Rachel
COSTER, Dr Mark
CROSSLEY, Prof Max
GEORGE, Dr Adrian
GILBERT, Prof Bob
HAMBLEY, Prof Trevor
HARROWELL, Prof Peter
HUNGERFORD, Dr Natasha
JORDAN, Dr Meredith
KABLE, A/Prof Scott
KASSIOU, A/Prof Michael
KENNEDY, A/Prof Brendan
KEPERT, Prof Cameron
LACEY, Dr Tony
LAY, Prof Peter
LINDOY, E/Prof Len
LING, Dr Christopher
Academic - Research Staff
ATKIN, Dr Rob
YUEN, Mr Alex
ATTARD, A/Prof. Phil
BLAKE, Dr Iain
BOBILLIER, Ms Sophie
BONIN, Dr Antonio
CAI, Dr Zheng-Li
CASTIGNOLLES, Dr Patrice
CHOW, Dr Hoi Shan
D’ALESSANDRO, Dr Deanna
DE BRUYN, Dr Hank
DJERDJEV, Dr Alex
DONG, Dr Ying
FANG, Dr Hongjuan
FIRKIN, Dr Kate
FISHER, Dr Dianne
GABORIEAU, Dr Marianne
GALLAGHER, Dr Sean
GANEVA, Dr Desislava
GRAY-WEALE, Dr Angus
HALDER, Mr Greg
HARRIS, Dr Hugh
HAWKETT, Dr Brian
HUDSON, Dr Toby
ISSA, Dr Fatiah
JAIN, Dr Nirmesh
JOLLIFFE, Dr Kate
LARSEN, Dr Allan
LEVINA, Dr Aviva
LUCAS, Dr Nigel
MACQUART, Dr Rene
MAHIDASHT, Dr Reza
MANGE, Dr Siyabonga
MARSHALL, Dr Craig
McDONALD, Dr James
McDONOUGH, Dr Matthew
MORAN, Dr Damian
MULCAHY, Dr Clodagh
NAUTA, Dr Klaas
NGUYEN, Dr Duc
153
154
PERRY, Dr Alexis
PETERSON, Dr Vanessa
PETHERICK, Dr Janice
PETRAVIC, Dr Janka
PHAM, Dr T T Binh
RADOM, Prof Leo
REIMERS, Prof Jeff
REYNOLDS, Dr Aaron
RICH, Dr Anne
SACCAVINI, Dr Catherine
SINTIC, Dr Paul
SOUTHON, Dr Peter
SPRONG, Dr Ewan
STAMFORD, Dr Patrick
TAYLOR, Dr Mark
THOMPSON, Dr Keiran
THORDARSON, Dr Pall
VAN DE WATER, Dr Leon
WANG, Dr Yanjun
WANG, Dr Yun
WARD, Dr Antony
WHITBY, Dr Catherine
ZHOU, Dr Qingdi
ZHOU, Dr XIANGTING
ZONDANOS, Ms Hollie
Honorary Staff
ARMSTRONG, A/Prof Bob
ARONEY, Dr Manuel
BACSKAY, Dr George
BARNES, Dr Craig
CHIA, Dr Peter
ECKERT, Dr Jim
FAILES, Dr Tim
FIELDER, Dr Simon
FREEMAN, Prof Hans
GUO, Mr Chris
HALL, Mr Matt
HIDI, Mr Peter
HUNTER, A/Prof Bob
HUSH, Prof Noel
JAMES, Dr Julia
MACKIE, A/Prof John
PINHEY, Prof John
RADFORD, Dr Don
SANGSTER, Mr David
STERNHELL, Prof Sev
TAYLOR, Prof Wal
WEDER, Dr Jane
WEI, Dr Gang
WILLIAMS, Dr Alan
School of Chemistry
Annual Research Report
Administrative & Finance Staff
HURST, Dr Jeanette
LAZER, Dr Warren
MATTERSON, Ms Pat
MOERMAN, Ms Rachel
PATSALIDES, Ms Sophie
PENWRIGHT, Mr Philip
PERERA, Mrs Shanthi
SANTOSA, Ms Trisanti
SUTJIADI, Ms Stella
THOMPSON, Ms Gemma
WOODS, Ms Anne
WOODS, Ms Kate
WU, Ms Lisa
Technical & Professional Staff
ARMSTRONG, Mr Jeff
BARASOAIN, Mr Fernando
CARTER, Dr Elizabeth
CHEE, Dr Clinton
DELLIT, Mr Bruce
DUCKWORTH, Mr John
FISHER, Dr Keith
GARSKE, Mr Arthur
GATFIELD, Mr Cliff
GOPAL, Mr Hitendra
IONN, Mr Howard
JENSEN, Dr Paul
KAEGI, Mr Marcel
KENT, Mr John
LA, Mr Tuan
LOGGE, Mr Bernie
LUCK , Dr Ian
OPRYSA, Mrs Anna
PICKER, Dr Kelvin
PISCICELLI, Mr Carlo
POPIOLKIEWICZ, Mr Jarek
SAINSBURY, Mr James
TURNER, Dr Peter
TURNER, Mr Mike
WHANG, Mr Barry
155
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School of Chemistry
Research Assistants
ALI, Mr Mohamed
TEO, Ms Chih-Lynne
Honours Students
AIVAZIAN, Ms Karina
BAIN, Mr James
BARISIC, Ms Ivanka
CHING, Mr Vincent
CLEMENTS, Mr Richard
COCHRANE, Mr James
DOAN, Mr John
DONA, Mr Anthony
DUYKER, Mr Samuel
EJJE, Ms Najwa
FOIS, Mr Alessandro
GWEE, Ms Yee Yen
HAMBLY, Mr Adam
HERNANDEZ AMEZQUITA, Mr Javier
IOPPOLO, Mr Joseph
KAN, Ms Casina
KHAN, Mr Arfhan
KOKIBAC, Mr Simon-Peter*
KONKOLEWICZ, Mr Dominik
LAU, Mr Vincent
LEUNG, Ms Wing Yan
LOKE, Mr Ping
MCKENZIE, Mr Scott
MERRICK, Mr Jeffrey
MORRIS, Mr Christopher
MOUSSA, Ms Iman Ahmed
NGUYEN, Mr Truclam
NGUYEN, Ms Annie
PEATE, Mr Jonathan
PHILLIPS Mr Anthony
PIGOTT, Mr Adam
STEWART Ms Rhinnon
TING, Mr Jimmy
TONG, Ms Katie
TROY, Mr Tyler Patrick
WILKINSON, Mr Shane
WONG, Ms Shwomun
YAMAMOTO, Ms Natsuho
YOUNG, Mr Philip
ZHANG, Ms Jenny
* Mr Simon-Peter Kokibac tragically died on the 25 April, 2006. A memorial plaque has been erected in the Chemistry
Courtyard in remembrance of Simon-Peter.
Annual Research Report
Postgraduate Students
AMOORE, Mr Jarred
AQUINO, Ms Cindy
ARAOS, Mr Miguel
AUNGSUPRAVATE Ms Ornsiri
BANISTER, Mr Sam
BEARE, Ms Kaitlin
BEVITT, Mr Joseph
BLOM, Ms Annabelle
BONNITCHA, Mr Paul
BRAY, Mr David
BROOKER, Mr Lance
BROTHERHOOD, Mr Peter
BUTLER, Mr Stephen
CAFE, Mr Peter
CANFIELD, Mr Peter
CARTER, Ms Melody
CAWLEY, Mr Adam
CERGOL, Ms Katie
CHANG, Mr Jung Chi
CHAPMAN, Ms Karena
CHATJAROENPORN, Ms Khwanrat
CHIN, Mr Yiing
CLEGG, Mr Jack
CROSSLEY, Ms Ellen
CUEVAS, Ms Rosa
EDWARDS-DAVIS, Mr David
FISCHER, Mr Josh
GIBSON, Mr Bligh
GONG, Ms Xiao Juan
GREEN, Mr Malcolm
GUEST, Ms Ruth
GUNOSEWOYO, Mr Hendra
HALLIDAY, Ms Jill
HAQUE, Mr Enamul
HOSSEINI NEJAS, Ms Elham
HUGHES, Mr Peter
IREMONGER, Mr Simon
IVANIC, Miss Sandra
KAUR, Mrs Ravinder
KAY, Ms Danielle
KAZA, Mrs Arati
KHOURY, Mr Tony
KOKKIN, Mr Damian
LESIC, Ms Rebecca
LESWIN, Mr Joost
McALPINE, Ms Jeannette
MENON, Mrs Ambili
MILLER, Mr Daniel
MITCHELL, Mr Christopher
MULYANI, Ms Irma
NEW, Ms Elizabeth
OBANDO GUTIERREZ, Mr Daniel
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O’CONNOR, Mr Sean
PAKCHUNG, Ms Amalie
PETERSON, Mr Josh
PRASAD, Mr Shiva
PU, Mr Fan
READ, Mr Justin
RICHMOND, Mr Craig
REILLY, Mr Neil
ROBERTON, Mr Mark
ROWLING, Mr Steven
SAINES, Mr Paul
SALOUROS, Ms Helen
SAYYADI, Mr Nima
SCHILTER, Mr David
SCHULTZ, Ms Tennille
SCHUSTER-WOODHOUSE, Ms Allira
SCIORTINO, Ms Natasha
SEABROOK, Mr Shane
SENGUPTA, Mr Devashish
SHARMA, Mr Neeraj
SHARMA, Mrs Vikashni Vandana
SHASHA, Ms Adelle
SIMPKINS, Ms Grace
SIMPSON, Ms Pip
SINTIC, Ms Maxine
SOLOMON, Ms Gemma
STADTMUELLER, Ms Lisa
STOCKS, Mr Danial
SYNA, Mr Ritnesh
SZCZEPINA, Mr Cody
TAM, Mr Koman
TAYLOR, Mr James
THICKETT, Mr Stuart
THOROGOOD, Mr Gordan J
TOPP, Ms Kathryn
TRONOFF, Mr Ashley
WARD, Ms Rachelle M
WEBB, Mr James
WHAN, Ms Renee
WIDMER-COOPER, Mr Asaph
WILLOUGHBY, Mr Douglas
WOOD, Mr Geoffrey
WYCZESANY, Mr Tomasz
YAP, Mr Benjamin
YEUNG, Ms Alexandra
YOUSSEF, Mr Ali
ZHANG, Mr Hui
ZIOLKOWSKI, Ms Erin
School of Chemistry
Annual Research Report
Visitors
BARTHOLOMäUS, Mr Ruben
CHAN, Dr Bun
CONSTABLE, Professor Ed
EL-FAYYOUMY, Ms Shaimaa
GHEIBI, Mr Nematollah
GRAHAM, Dr David
MEEJOO, Dr Siwaporn
MULLINS, Dr Joe
ORVIG, Professor Chris
SANDALA, Mr Greg
SEURING, Mr Jan
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School of Chemistry
2006
Chemistry
Graduates
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School of Chemistry
Annual Research Report
Graduates of 2006
Mr Joseph Anthony Ioppolo
Boronated Phosphonium Salts as a New Class of Agents for Boron Neutron Capture Therapy
Supervisor: Dr Louis Rendina
Bachelor of Science (Honours)
Ms Casina Wing Sze Kan
Metabolism of Chemopreventative Selenium Nutritional Supplements In Vitro
Supervisor: Dr Hugh Harris
The following students had their degrees awarded in 2006:Ms Karina Aivazian
Oxygen Non-Stoichiometry and Cation-Doping in Thermoelectric Misfit-Layered Cobaltates
Supervisor: Dr Christopher Ling
Mr James Hay Bain
Investigating Mutant ß-glycosidases: Synthesis and Analysis of Drug Metabolites
Supervisor: Dr Malcolm McLeod
Ms Ivanka Terezia Barisic
Defect Perovskites and Lithium Intercalation
Supervisor: Dr Siegbert Schmid
Mr Hong Yue Vincent Ching
Novel DNA Metallointercalators for Boron Neutron Capture Therapy
Supervisor: Dr Louis Rendina
Mr Richard James Clements
Semi-Empirical Nucleation Theory in Binary Eutectic Alloys
Supervisor: Professor Peter Harrowell
Mr James Robert Cochrane
Towards the Synthesis of an Antifungal Cyclic Peptide
Supervisor: Dr Katrina Jolliffe
Mr John Nguyen Phuc Doan
Modified MMP Inhibitors as Potential Radiodiagnostic Agents for Metastatic Cancer
Supervisors: Professor Trevor Hambley and Associate Professor Michael Kassiou
Mr Anthony Dona
Relating Diffusion and Dissolution Properties of Starch with its Digestability
Supervisor: Professor Robert Gilbert
Mr Samuel Duyker
Lanthanoid Hexacyanometalates: Negative Thermal Expansion and Hydration Characteristics
Supervisor: Professor Cameron Kepert
Ms Najwa Ejje
A Novel Application of Immobilized Metal Affinity Chromatography (IMAC) for Siderophore Purification
Supervisor: Dr Rachel Codd
Ms Yee Yen Gwee
Investigations of the Anti-Metastatic Properties of NAMI-A and its Biotransformations in Blood
Supervisor: Professor Peter Lay
Mr Adam Christopher Hambly
Porphyrin-Appended Dendrimers: Synthesis, Structure and Function
Supervisor: Professor Maxwell Crossley
Mr Arfhan Khan
The Synthesis and Magnetism of Transition Metal Borates
Supervisor: Dr Christopher Ling
Mr Dominik Lech Konkolewicz
A Model for Starch and Other Hyperbranched Polymers
Supervisors: Dr Angus Gray-Weale and Professor Robert Gilbert
Mr Vincent Wing-Hei Lau
Towards Hydrogen Generation by the Photocatalytic Splitting of Water
Supervisors: Professor Thomas Maschmeyer and Associate Professor Anthony Masters
Ms Wing Yan Leung
Asymmetric Catalytic Synthesis of Praziquantel
Supervisor: Dr Matthew Todd
Mr Ping Loke
Synthesis of the C17-C25 Fragment of (-)-Lasonolide A
Supervisor: Dr Mark Coster
Mr Scott Dylan McKenzie
Aurivillius Phases as a Framework for Multiferroic Materials
Supervisors: Dr Christopher Ling and Associate Professor Brendan Kennedy
Mr Jeffrey Merrick
An Evaluation of Harmonic Vibrational Frequency Scale Factors
Supervisors: Professor Leo Radom and Dr Damian Moran
Mr Christopher William Morris
Extraterrestrial Metastable Species: Towards a Better Understanding of the Interstellar Environment
Supervisor: Dr Timothy Schmidt
Ms Iman Ahmed Moussa
Novel Sigam Selective Ligands: Synthesis and Resolution of Trishomocubanes
Supervisors: Associate Professor Michael Kassiou and Dr Mark Coster
Ms Annie Nguyen
Speciation of Chromium and Vanadium Dietary Supplements In Vitro
Supervisor: Professor Peter Lay
Mr Truclam Nguyen
TACA as a Biological Template for the GABAc Receptor
Supervisor: Dr Meredith Jordan
Mr Jonathan Andrew Peate
Towards a Better Characterisation of Starch
Supervisor: Professor Robert Gilbert
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Mr Anthony Edward Phillips
Tunable Thermal Expansion in Cyanide-Bridged Frameworks with Single-Network Diamond Topology
Supervisor: Professor Cameron Kepert
Mr Adam James Pigott
Synthetic Studies Towards the F-Ring/Side-Chain of Spongistatin 1
Supervisor: Dr Mark Coster
Ms Rhiannon Troye Stewart
Microsclerodermin C: Methodologies Towards the Hydroxypyrrolidinone Fragment
Supervisor: Dr Mal McLeod
Mr Thirugnanasambanthar Thirukkumaran
Asymmetric Synthesis with Dihydroisoquinolines
Supervisor: Dr Matthew Todd
Mr Sai Chung Jimmy Ting
A Structural Study of B-Cation Substituted Lanthanum Rhodates
Supervisor: Associate Professor Brendan Kennedy
Ms Katie Wing Ki Tong
Self-Assembled Gels From Small Organic Molecules
Supervisor: Dr Pall Thordarson
Ms Shwo Mun Wong
New Iron-Based Reagents for the Dihydroxylation of Alkenes
Supervisor: Dr Peter Rutledge
Ms Natsuho Yamamoto
Fluorescent Hydroxamic Acids as Models of Cytotoxins in Hypoxia-Selective Cobalt Prodrugs
Supervisor: Professor Trevor Hambley
Mr Philip Young
Cyclic Peptide Molecular Scaffolds: Synthesis and Anion Binding
Supervisor: Dr Katrina Jolliffe
Ms Jenny Zhang
Lysosomal Localisation of Platinum(II)-Anthraquinone Complexes
Supervisor: Professor Trevor Hambley
Mr Christopher James Charles Watts
Interpreting Size-Exclusion Data for Hyper-Branched Polymers: A glimpse at Starch
Supervisors: Dr Angus Gray-Weale and Professor Robert Gilbert
Mr Shane Michael Wilkinson
Glucuronylsynthase: A Novel “Designer Enzyme” to Catalyse Glucuronylation
Supervisor: Dr Malcolm McLeod
School of Chemistry
Annual Research Report
Master of Science
The following students had their degrees awarded in 2006:Mr Ahmad Faiz Abdul Latip
Nanoporous Lanthanoid–Oxalate Framework Materials: Characterisation and Host-Guest Properties
Supervisor: Professor Cameron Kepert
Associate Supervisor: Associate Professor Brendan Kennedy
Mr Mark Absalom
Porphyrin-Appended and Dendrimers for Use in Photonics and Catalysis
Supervisor: Professor Maxwell Crossley
Associate Supervisor: Dr Robert Baker
Doctor of Philosophy
The following students had their degrees awarded in 2006:Dr Rebecca Alderden
The Distribution of Platinum Complexes in Biological Systems
Supervisor: Professor Trevor Hambley
Associate Supervisor: Professor Margaret Harding
Dr Joseph Bevitt
Functionalised Nanoporous Molecular Materials
Supervisor: Professor Cameron Kepert
Associate Supervisor: Professor Jeffrey Reimers
Dr Malcolm Green
Characterisation, Modification and Loading of Nanotubular Clays for Controlled Release Technologies
Supervisor: Professor Cameron Kepert
Associate Supervisor: Dr Hui Zhu
Dr Tony Khoury
Multiple Connector Building Blocks for Use in Novel Porphyrin Assemblies
Supervisor: Professor Maxwell Crossley
Associate Supervisor: Professor Jeffrey Reimers
Dr Nicholas Lambropoulos
Design of a Directed Self-Assembled Molecular N-Bit Shift-Register Memory Device
Supervisor: Professor Jeffrey Reimers
Associate Supervisors: Dr George Bacskay and Professor Maxwell Crossley
Dr Ignace Louis
The Total Synthesis of the Cytotoxic Marine Macrolide (-)-Dactylolide
Supervisor: Dr Malcolm McLeod
Associate Supervisor: Dr Craig Hutton
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School of Chemistry
Dr Emily Shuter
Studies Toward the Synthesis of the Microsclerodermin Natural Products
Supervisor: Dr Malcolm McLeod
Associate Supervisor: Dr Mark Coster
Dr Appadurai Thiyakesan
Nanoporous Molecular Framework Materials of Mixed-Donor Ligands with Lanthanoids and Transition Metals
Supervisor: Professor Cameron Kepert
Associate Supervisor: Emeritus Professor Leonard Lindoy
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Annual Research Report
Honours & Postgraduates 2006
Below are some of our Chemistry Honours and Postgraduate students.
Honours Students
Dr Jenny Waern
The Biological Chemistry of the Antitumor Agent Molybdocene Dichloride
Supervisor: Professor Margaret Harding
Dr Asaph Nathan Widmer-Cooper
Structure and Dynamics in Two-Dimensional Glass-Forming Alloys
Supervisor: Professor Peter Harrowell
Associate Supervisor: Dr George Bacskay
Dr Geoffrey Wood
Radical-Mediated Protein Oxidation
Supervisor: Professor Leo Radom
Associate Supervisor: Dr George Bacskay
Dr Alexander Yuen
Synthetic Studies Towards Stephanotic Acid
Supervisor: Dr Katrina Jolliffe
Associate Supervisor: Dr Craig Hutton
Postgraduate Students
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School of Chemistry