TABLE OF CONTENTS
Introduction and Welcome 2 Research Facilities 2 Research Strengths 2 Teaching and Higher Degree Programs 4 Recent Research Highlights 6 Our People 9 Research Interests 11 Dr Jennifer L Beck 11 Dr Stephen Blanksby 13 Professor John B Bremner 15 Dr Carolyn T Dillon 17 Professor Nick Dixon 19 Professor David Griffith 21 Dr Mark in het Panhuis 23 Dr Dianne Jolley 25 Professor Leon Kane-Maguire 27 Associate Professor Paul Keller 29 Dr Wilford Lie 31 Dr Garry Mockler 33 Dr Glennys O’Brien 34 Professor William Price 35 Professor Stephen Pyne 38 Dr Stephen Ralph 40 Professor Margaret M Sheil 42 Dr Danielle Skropeta 43 Professor Gordon G Wallace 45 Associate Professor Stephen Wilson 47 Major Equipment 49 Research Funding 52 Current Successful Grants 53 2004-2005 Publications Data 59
Chemistry Department Research Booklet Updated February 2007 Page 1
INTRODUCTION AND WELCOME
Welcome to the Department of Chemistry at the University of Wollongong, NSW. Our Department is currently one of the larger Chemistry based Departments in Australia with a national and international reputation for excellence in teaching and research. There is a close nexus between our research and teaching programs where much of our undergraduate program is informed by our research.
The Department has particular internationally recognized research strengths in biomolecular science and medicinal chemistry, materials chemistry and environmental chemistry. The Department has around 55 Academic staff, including research only personnel and approximately 50 PhD students. In addition, there is about 20 staff engaged in research support positions, giving over 120 staff members dedicated to research projects and outcomes.
The Chemistry Department at UoW has been consistently successful over a number of years in attracting funding for its work from both competitive Government sources such as the Australian Research Council (ARC), National Health and Medical Research Council (NHMRC) and other agencies and from Industrial sources, through collaborative linkages and direct contract research. More details of research funding are given later in this publication but we give here a list illustrating the range of collaborative partners we are currently involved with: AMRAD, ANSTO, AstraZeneca, Avexa, BHP Billiton, BlueScope Steel, Cochlear, CSIRO, CRC Cochlear Implants, CRC SmartPrint, CRC IMST, CRC Polymers, Defence Science and Technology Organisation (DSTO), Department of Primary Industry, Glaxo, Johnson and Johnson Research Pty Ltd and Rio Tinto.
Research Facilities
The Department has modern equipment and facilities for research and teaching.
Particularly important are state-of-the-art facilities in mass spectrometry (including high resolution electrospray, LC/ion trap/MS, LC/MS, GC/MS and MALDI), NMR spectroscopy (300 MHz, 2 x 500 MHz and access to both an 800 MHZ Brucker Spectrometer at ANU and a 600 MHz at UNSW), an electrochemical surface mapping facility, FTIR spectroscopy, various CD UV-vis spectrometers and an extensive range of other analytical equipment. The Department also has strong capabilities in computer-aided molecular modelling.
Research Strengths
The Department has active research programs in both pure and applied chemistry. These programs are concentrated into four partly overlapping areas: • Bio-organic/Medicinal Chemistry • Structural Determination of Biomolecules and Protein Biochemistry • Environmental Chemistry • Intelligent Polymers and Electromaterials Science
An integral and interconnecting component of each of four major programs is the exploitation of the Department’s analytical /instrumental expertise and equipment.
Chemistry Department Research Booklet Updated February 2007 Page 2 Centre for Medicinal Chemistry and Pharmacology
The Centre for Medicinal Chemistry and Pharmacology (CMCP) was established in November 2006 and forms part of the Illawarra Health and Medical Research Institute. There are 8 academic staff, more than 9 post-doctoral fellows and 27 post-graduate students endeavouring to enhance the understanding of the molecular origins of disease and undertake modern drug design, leading to the development of new pharmaceuticals. The three major disease states currently being targeted by the CMCP are: anti-infectives, encompassing antibacterial agents, including multi-drug resistant strains, anti-viral agents (e.g. HIV, Dengue fever, hepatitis C, anti-fungals) and anti-malarial agents; anti-cancer agents, incorporating both drug design and development as well as formulation and clinical aspects; and cardio-vascular disease, including fundamental research associated with phospholipids and diet as well as the development of new small molecule therapeutics. Our research has attracted approximately $4.5 million (2004-2006) and expanding collaborations with hospitals, pharmaceutical companies and other research organisations (e.g. The Centre for Medical Bioscience at UoW) enables continued opportunities to progress our understanding of disease states.
Biological Chemistry and biochemistry
The physical sciences (chemistry, physics, mathematics) are the foundations for understanding biological processes. The Chemistry Department has several research groups involved in projects that include: (i) elucidating fundamental processes in biology such as the mechanism of replication of the bacterial genome, (ii) investigating unusual DNA structures that are present under different conditions in cells, (iii) developing new methods for clinical analysis of plasma proteins that may be important in diagnosis of disease, (iv) understanding changes in lipid composition of various tissues as result of aging and disease, and (v) measuring oestrogen mimics in waste water. These research areas directly involve seven academic staff in Chemistry in addition to numerous higher degree students and collaborators in the Science faculty and at other institutions. Some of the staff are members of the University’s Centre for Medical Bioscience. Other staff members within Chemistry in the Centre for Medicinal Chemistry and Pharmacology (see above) have interests in discovering new drugs that inhibit biological processes. For example, there are projects investigating the interactions of anticancer ruthenium- and arsenic- based chemotherapeutic agents with cellular proteins and DNA.
Environmental Chemistry
This diverse research area involves 7 academic staff and over 12 other research personnel throughout the faculty of Science. The research covers aspects of air, water, sediment and soil chemistry. Current water based projects include the fate and speciation of metal contaminants in marine ecosystems, the identification of biological indicators of aquatic contamination and toxicity. Atmospheric projects include the measurement of greenhouse gas emission rates and their isotopic signature from various sources (such as agriculture), the measurement of changes in atmospheric composition on both a regional and global scale, and quantification of solar radiation as a tool in understanding atmospheric processes.
Intelligent Polymer Research Institute
The Intelligent Polymer Research Institute (IPRI) is one of seven institutes at the University of Wollongong. The Institute comprises of approximately 38 personnel (full-time research staff and students) and is located in purpose built laboratories on the University of Wollongong campus and is soon to move to new world class facilities at UoW’s Innovation campus located also in Wollongong close to the commercial centre. IPRI is recognised internationally as a pioneer in Intelligent Polymer Research. The research looks at the ability of Inherently Conducting Polymers (ICPs) or carbon nanotubes to act as the sensing and actuating elements within Intelligent material systems. Realisation of the true potential of these systems now depends on their integration into other material structures with desirable mechanical properties and the development of new electrolyte systems based on room temperature ionic liquids. The Institute has strategic links and alliances with other research institutions in the USA, Japan, Korea, Italy, Ireland and the United Kingdom.
Chemistry Department Research Booklet Updated February 2007 Page 3
The Intelligent Polymer Research Institute is also the leading partner and main administrative centre for the ARC Centre of Excellence for Electromaterials Science. The Centre was formally opened in February 2006 and is a collaborative partnership between IPRI, Monash University, The Bionic Ear Institute, and St Vincents Health in Melbourne. The work program of the Centre of Excellence expands on research conducted under the previous ARC Centre for Nanostructured Electromaterials. The main aim of the centre is still to explore the science of nanomaterials having an electron or charge transfer functionality: to prepare such nanomaterials, study and develop theories for their behaviour, and exploit these new behaviours in useful applications. An ethical dimension is also included to monitor the impact of such developments on the community as a whole.
IPRI will continue to explore the science of nanomaterials having an electron or charge transfer functionality: to prepare such nanomaterials, study and develop theories for their behaviour, and exploit these new behaviours for applications in membrane technology, asymmetric synthesis, chromatography, sensors, biomaterials, advanced coatings, actuators and solid state devices.
Teaching and Higher Degree Programs
The Department offers a number of undergraduate and postgraduate courses in Chemistry, Medicinal Chemistry and Nanotechnology.
Undergraduate Degrees
It has a highly successful four year speciality degree in Medicinal Chemistry (B. Med. Chem.) and a new Bachelor of Nanotechnology degree, both of which give students understanding of the research method and experience of leading edge research from an early stage. In addition there are three year Bachelor of Science (B.Sc.) programs offering majors in Chemistry, Medicinal Chemistry or Nanotechnology.
Postgraduate Courses
In addition to the PhD program, the Department offers a choice of Master’s Programs in both Chemistry and Medicinal Chemistry, which can be taken as Coursework Masters or as Research Masters degrees. The Research Master degrees are a 72 credit point program and provide for an additional one-year full time research project (48 credit points) on completion of the coursework component (24 credit points).
• Master of Science • Master of Science (Medicinal Chemistry) • Master of Science by Research • Master of Science by Research (Medicinal Chemistry)
For complete information on undergraduate and postgraduate courses at the University of Wollongong, including brochures and application forms, visit http://www.uow.edu.au/prospective/
Chemistry Department Research Booklet Updated February 2007 Page 4
The pages of the brochure contain details of the research carried out within the Department. If you would like further information please contact the research group concerned directly (details given for each group). Alternatively, if you require more information of a general nature, please contact me at the email address below.
Best wishes
William Price Head, Department of Chemistry Email: [email protected]
Chemistry Department Research Booklet Updated February 2007 Page 5
RECENT RESEARCH HIGHLIGHTS
These news excerpts were taken from the University of Wollongong Webpage (URL: http://media.uow.edu.au/news/latest.html)
ARC Minister announces first Wollongong Federation Fellow May 11, 2006 A University of Wollongong (UOW) scientist, whose research efforts promise to revolutionise medical science, was today (11 May) honoured with UOW’s first-ever Australian Research Council (ARC) Federation Fellowship to develop a nanobionics research base. Federal Education, Science and Training Minister, the Hon. Julie Bishop, at a ceremony in Canberra announced the awarding of the fellowship which carries over $1.5 million in funding over the next five years from the ARC to Professor Gordon Wallace. UOW will provide matching funding for new staff and infrastructure. Professor Wallace is Director of the ARC Centre of Excellence for Electromaterials which was officially opened earlier this year.
Nanobionics is the merging of biology and electronics using recent advances in nanotechnology. [Nanotechnology is simply the building of devices that are 1-100 nanometre in size – one nanometre is a billionth of a metre, so nano-scale devices are composed of just a handful of atoms/molecules]. With previous research achievements in the use of organic conductors to assist in communication across the biology-electronics interface in the body, Professor Wallace’s future research efforts promise to revolutionise medical science and dramatically improve the quality of life for many individuals by creating new bionic materials. Established under the Australian Government’s 2001 innovation action plan, Backing Australia’s Ability, the ARC’s Federation Fellowships are highly prestigious awards designed to develop and retain Australian skills. Federation Fellowships provide opportunities for outstanding Australian researchers to return to, or remain in, key positions in Australia. Up to 25 Federation Fellowships with a standard tenure of five years are available each year. Professor Wallace plans to use the Fellowship to further develop his research team and introduce new and multi- skilled researchers to the University of Wollongong. His research, within the framework of the ARC Centre of Excellence in Electromaterials Science, already builds on a world-class expertise and infrastructure which is looking at endothelial cell growth (cells that make up the inside of blood vessels) and nerve cell regeneration. This work involves collaborations with Professor Graeme Clark (Bionic Ear inventor), Associate Professor Rob Kapsa at St Vincent’s Hospital (Melbourne), Professor Rick Kaner at UCLA (USA), Professor Suzi Jervis at Trinity College (Dublin), Professor Doug MacFarlane (Monash University), Professor Maria Forsyth (Monash University), Professor Alan Bond (Monash University), Professor Geoff Spinks (UOW), Professor Mark Wilson (UOW) and Professor Philippe Poulin (Centre National de la Recherche Scientifique, France).
$100,000 donation for anti-cancer drug project Feb 23, 2006 The Illawarra Cancer Carers group presented a donation of $100,000 to the University of Wollongong for promising research into an anti-cancer drug project. The money will provide a major boost to the research into the new anti-cancer drug formulation project headed by Professor John Bremner, Department of Chemistry and Institute for Biomolecular Science, University of Wollongong and Professor Philip Clingan, Honorary Clinical Professor, Graduate Medical School at the University of Wollongong and Director, Illawarra Cancer Care Centre; together with colleagues Associate Professor Marie Ranson, Dr Tamantha Stutchbury, Dr Julie Locke and Ms Laurel Morrissey.
Chemistry Department Research Booklet Updated February 2007 Page 6 The new formulation of drug components has shown considerable promise against cancer cells and is now being tested in animals.After the animal experiments, Professor Bremner and Professor Clingan hope to further develop this drug combination for use in humans. If successful, the drug combination should greatly ease painful side effects on drug administration and be more effective in the treatment of certain cancers such as colo-rectal cancer. The current animal experiments have been assisted by the provision of a dedicated Illawarra Cancer Carers President, Mr Rex Saunders (centre), presents the donation mouse housing facility made possible by the Illawarra Cancer Carers' previous support. cheque to the UOW research team including The new donation will provide a much-needed boost for the continuing testing (left to right) Dr Tamantha Stutchbury, Professor Philip Clingan, Professor John experiments. Bremner and Dr Julie Locke
The President of the Illawarra Cancer Carers group, Rex Saunders, said that with the improved methods of detection of cancer, the treatment itself should now be a priority. "We are all affected when a friend or family member is diagnosed with cancer. Our group decided to donate to this research at the University of Wollongong again because we feel strongly about the need to improve the treatment of cancer," he said. Professor Clingan told those attending the donation ceremony at Wollongong Hospital that it was very difficult obtaining research funding so the UOW team was very grateful for the trust placed in them by the Illawarra Cancer Carers. "We have a talented team and I can assure everybody that the money will be used wisely to pursue new anti-cancer drugs," Professor Clingan said. Professor Bremner said he was overwhelmed by the fund-raising efforts achieved by the Illawarra Cancer Carers and he vowed that the funding would be put to good use.
ARC $12m ARC Centre of Excellence to play revolutionary role Feb 16, 2006
The world is on the verge of a revolution in electromaterials science and Wollongong will be playing a significant role, the audience heard at today's (February 16) official opening of the Australian Research Council (ARC) Centre of Excellence for Electromaterials Science based at the University of Wollongong. Centre Director, Professor Gordon Wallace, predicted that the next five years would herald an array of exciting developments in the fields of electromaterials science and nano (ultra minute) technology particularly following discoveries such as plastics (under certain conditions) can conduct electricity. Professor Wallace said the ARC would play a pivotal role in creating the electromaterials required for such areas as a new generation of bionic ear, artificial muscles, nerve repairs and, in collaboration with Monash University, developing the bio-batteries and the bio-fuel cells to drive them. The Centre promises to tackle some of the biggest challenges facing society such as enhancing human health, renewable energy and sustainable industries. "On just an everyday basis, people will see the 'revolution' in changes from the types of mobile phones they carry to the computer screens on their desks," Professor Wallace said. Professor Wallace said the breakthroughs in electromaterials science were being achieved through a "unique team of researchers combining their individual talents" along with a recognition from the ARC and various commercial collaborators who shared his centre's vision. The official opening was performed by the Chief Executive Officer of the ARC, Professor Peter Hoj, who stressed how competitive it was to receive funding from the ARC -- in the case of Professor Wallace's application 11 centres were funded from 97 applications. Professor Hoj said funding did not automatically go to the larger universities pointing out that if regional universities can show they can tackle ground-breaking research in a The Chief Executive Officer of the ARC, Professor Peter Hoj, unveils a collaborative fashion major funding is achievable. plaque to officially open the new ARC Centre of Excellence for Electromaterials Science at the University of Wollongong
Chemistry Department Research Booklet Updated February 2007 Page 7
UOW's Deputy Vice-Chancellor, Research (representing the Vice-Chancellor), Professor Margaret Sheil, described it as a tremendous day for UOW and its partners and a clear acknowledgment of the world-class research being undertaken. "It's a clear example of how we, as a university, are reaping the benefits of not trying to be excellent in everything in research but to concentrate our resources in our areas of strength such as electromaterials science," Professor Sheil said. The NSW Minister for Regional Development, Mr David Campbell, who is also a member of the University Council, said he was always pleased to visit UOW as the University had a vibrancy about it that was contagious. He said that vibrancy was clearly on show at today's official opening and he was proud of the fact that the NSW Department of State and Regional Development was one of the centre's sponsors.
The Centre draws its core expertise from its partners: the Intelligent Polymer Research Institute (UOW), the ARC, the NSW Department of State and Regional Development, Monash University, the Bionic Ear Institute, and St Vincent's Health. The Centre has already attracted 21 visiting scientists from eight different countries since the Federal Government announced plans for its introduction in 2005. This combination, with the input of other distinguished collaborators, brings together some of the foremost researchers in chemistry, materials science, physics, biology and mathematics in Australia. Participants at the official opening of the ARC Centre of Excellence for The Centre will carry out collaborative research with four different Co-operative Electromaterials Science are (from left): Professor Doug MacFarlane (Monash Research Centres -- CRC Polymers, CRC Smart Print, CRC Intelligent University), Centre Director, Professor Manufacturing and CRC Cochlear Implant and Hearing. Gordon Wallace (UOW); UOW's Deputy Vice-Chancellor, Research (representing the Vice-Chancellor), Professor Margaret Sheil; Professor Wallace said his area already had established links with industry and ARC's CEO, Professor Peter Hoj; Professor attending today's opening were representatives from Cochlear, Quantum Maria Forsyth (Monash University); and Professor Graeme Clark (Bionics Program Technology, Schefenacker Vision Systems, Aqua Diagnostics, CAP-XX, Leader) Australian Surgical Design, BlueScope Steel and Boston Scientific (from the USA).
Coinciding with the opening, the new ARC Centre is hosting the first international symposium on electromaterials science held at UOW (see http://media.uow.edu.au/releases/2006/0215b.html) involving researchers from the world's leading scientific institutions including Germany, Italy, France, USA, Canada, The Netherlands, Ireland, Australia and New Zealand. The inventor of the bionic ear, Professor Graeme Clark, is among scientists attending the conference. The symposium, to be held from 15 to 17 February, will provide a forum for the discussion of recent advances in this research area, particularly the role and impact of nanostructure -- structures that are minute or micrometer- sized. Introduction of the world's strongest artificial muscles, the announcement of a patent involving a new sensor that will have special environmental implications and the latest wearable solar cells and fibre batteries on clothing are among highlights at the first international symposium on electromaterials science.
Chemistry Department Research Booklet Updated February 2007 Page 8
OUR PEOPLE
Head of Department William E Price, BSc, PhD (London), DIC, MRSC, FRACI
Professor of Chemistry John B Bremner, BSc (WA), PhD (ANU), Dip Chem Pharm (Edin), FRACI, FRSC Nicholas E Dixon, BSc, PhD (Q'ld), MRACI David Griffith, BSc, PhD (Monash), FRACI Leon Kane-Maguire, BSc PhD (Q'ld), FRACI Stephen G Pyne, BSc (Adel), PhD (ANU), FRACI Margaret M Sheil, BSc, PhD (UNSW), MRACI
Professorial Fellow Associate Professors Gordon G Wallace, BSc, PhD (Deakin), FRACI, DSc, FTSE Stephen Wilson, (Monash) BSc, PhD (ANU), MRACI Paul Keller, BSc, PhD (UNSW) Stephen Ralph, BSc, PhD (Q'ld), MRACI
Senior Lecturers Lecturers Garry M Mockler, BSc, PhD (UNSW), MRACI Carolyn Dillon, BSc. PhD (Syd) Jenny Beck, BSc, PhD (Q'ld) Wilford Lie, BSc, PhD Stephen Blanksby, B.Sc. PhD (Adel) Glennys O'Brien, BSc, PhD (Auckland) Dianne Jolley, BAppl.Sci., PhD (Canb) Danielle Skropeta, BSc, PhD (ANU) Marc in het Panhuis, MSc(Twente), PhD(TCD)
Research Fellows Celine Kelso, MSc, PhD(Woll) Syed Ashraf BSc, PhD (Woll) Julie Locke, BSc, PhD Toni Campbell BSc, PhD (Woll) Carol Lynam BSc, PhD (Ireland) Jun Chen, BSc (China), PhD (Woll) Andrew Minett BSc, PhD (Woll) David Harman BSc, PhD Violeta Misoska BSc, PhD (Woll) Peter Innis, PhD (UTS) Simon Moulton, Btech, BSc, PhD (Woll) Nicholas Jones, BSc, MSc (U. Waikato), PhD (U. Denver) Clare Murphy, BSc, PhD Byung Chul Kim, DipChemEng, BSc, MSc, PhD (Woll) MinYan Tang BSc (China), PhD (Woll) Cindy Henriques, B.Biotech(Adv)Woll) Chee On Too, BSc, PhD (London) Guergana Guerova Alison Ung, BSc, PhD (UNSW) Michael Kelso, B.Med.Chem(Hons1), PhD Caiyun Wang, BSc, PhD Rao Yepuri, BSc, PhD (Woll)
Chemistry Department Research Booklet Updated February 2007 Page 9 Laboratory Manager John Korth, BSc, (UNSW), MSc, PhD (Woll)
Mass Spectrometry Facility Manager Larry Hick, BSc (Hons) (Woll)
Technical Officers Simon Bland, BCSc (Woll) – IT Support Sue Butler, BSc (Woll) – Environmental & Analytical Chemistry Sandra Chapman, BSc (Hons) (Woll) - NMR Support Roza Dimeska, BSc (Hons) (Woll) – Organic Chemistry Roger Kanitz, BSc (Woll) – First Year Chemistry Cathy Lancaster, BSc (Woll) – Environmental & Analytical Chemistry Karin Maxwell, BSc (JCU), GradDipEd (Woll) – Biological and Medicinal Chemistry, Web & WebCT Support Peter Pavlik, BSc, MSc (Woll) – Inorganic & Physical Chemistry Peter Sarakiniotis – Electronic Support
The Department is also serviced by the Faculty electronic and mechanical workshops (2 technicians).
Administrative Assistants Phil Smugreski – Intelligent Polymer Research Institute Rebecca Potter - Intelligent Polymer Research Institute Louisa Willdin – Department of Chemistry Carol Weall – Department of Chemistry
Chemistry Department Research Booklet Updated February 2007 Page 10
RESEARCH INTERESTS
Dr Jennifer L. Beck email: [email protected]
Mass Spectrometry of Proteins and DNA
Research in the Beck laboratory is aimed at solving problems in biochemistry using biophysical techniques, in particular mass spectrometry. There are three major areas of research:
(1) Investigations of protein-protein and protein-DNA interactions within the bacterial replisome. The replisome is the dynamic assembly of proteins, DNA and cofactors (metal ions, nucleotides) that functions to replicate the chromosome. Although the components of the Escherichia coli replisome are known, little is known about the order of assembly and contact points between binding partners. Some of these questions can be addressed using mass spectrometry. The projects aim to test the limits of mass spectrometry and (in collaboration with Prof Nick Dixon) to uncover new information about chromosome replication.
(2) Higher order DNA structures: fundamentals and drug targeting. The classical, familiar model of DNA structure elucidated by Watson and Crick is a double-stranded helix made up of chemical units that consist of a sugar phosphate backbone attached to various sequences of purine and pyrimidine bases (the genome sequence). In order for the information stored in the sequence to be read and eventually expressed in the vast range of normal (e.g. metabolism) and abnormal (e.g. growth of cancer cells) life processes, the DNA must interact with many cofactors and proteins that catalyse the chemical reactions that drive these processes. Therefore, proteins with different roles must recognise specific regions of the DNA. This molecular recognition is possible, in part, because some DNA sequences elicit interactions among atoms within the DNA structure that alter its shape from that of the familiar double helix (duplex). Some sequences predispose DNA towards higher order structures such as quadruplexes (four strands) and triplexes (three strands), while some sequences cause significant deviations of the “normal” double helical (B-form) DNA resulting in Z-DNA. Z-DNA differs from B-DNA in a number of ways including that it is a left-handed, rather than a right-handed helix. In this project, mass spectrometry is used as a major tool in conjunction with other techniques such as circular dichroism spectrophotometry, X-ray crystallography and ion mobility mass spectrometry (collaboration with Prof Mike Bowers, UCSB) to understand the interactions between the various DNA structures and potential chemotherapeutic agents.
(3) Development of simple mass spectrometry-based methods for analysis of clinically important plasma proteins. Plasma, the extracellular matrix of the blood, is the most frequently analysed clinical sample. It contains “classical” plasma proteins such as albumin (small molecule transport), transferrin (iron transport), immunoglobulins (antibodies), and blood clotting proteins such as fibrinogen and prothrombin. Additionally, there are other proteins that normally function inside cells but are released into the plasma as a result of cell damage or death. These
Chemistry Department Research Booklet Updated February 2007 Page 11 include proteins that are markers of myocardial infarction such as creatinine kinase or myoglobin. Also important are foreign proteins that derive from infectious or parasitic organisms. To 2002, there were 289 proteins that had been detected in plasma, of which 117 are clinical analytes. The most abundant of these proteins, albumin, is 1010 times more abundant than the least abundant, interleukin 6 (indicator of inflammation or infection).1 Detection of medium-low abundance proteins therefore requires efficient, rapid removal of abundant proteins that may interfere with analyses. In this project the research to be carried out will result in development of simple, relatively low-cost techniques for fractionating plasma proteins of diagnostic importance, and analysing the fractions containing subsets of proteins within the dynamic range of modern electrospray ionisation mass spectrometers.
Selected publications:
1. Watt, SJ; Oakley, A; Sheil, MM; Beck, JL. Comparison of negative and positive ion electrospray ionization mass spectra of calmodulin and its complex with trifluoperazine Rapid Commun. Mass Spectrom., 19: 2123-2130, 2005
2. Williams, NK; Liepinsh, E; Watt, SJ; Prosselkov, P; Matthews, JM; Attard, P; Beck, JL; Dixon, NE; Otting, G. Stabilization of native protein fold by intein-mediated covalent cyclization. J. Mol. Biol., 346: 1095-1108, 2005
3. Gupta, R; Hamdan, SM; Dixon, NE; Sheil, MM; Beck, JL. Application of electrospray ionization mass spectrometry to study the hydrophobic interaction between the epsilon and theta subunits of DNA polymerase III. Protein Sci., 13: 2878- 2887, 2004
4. Gupta, R; Beck, JL; Ralph, SF; Sheil, MM; Aldrich-Wright, JR. Comparison of the binding stoichiometries of positively charged DNA-binding drugs using positive and negative ion electrospray ionization mass spectrometry. J. Am. Soc. Mass Spectrom., 15: 1382-1391, 2004
5. Beck, JL; Ambahera, S; Yong, SR; Sheil, MM; de Jersey, J; Ralph, SF. Direct observation of covalent adducts with Cys34 of human serum albumin using mass spectrometry. Anal. Biochem., 325: 326-336, 2004
6. Oakley, AJ; Prosselkov, P; Wijffels, G; Beck, JL; Wilce, MCJ; Dixon, NE Flexibility revealed by the 1.85 angstrom crystal structure of the beta sliding-clamp subunit of Escherichia coli DNA polymerase III. Acta Crystallographica D-Biol. Crystallog., 59: 1192-1199 Part 7, 2003
7. Kapur, A; Beck, JL; Brown, SE; Dixon, NE; Sheil, MM. Use of electrospray ionization mass spectrometry to study binding interactions between a replication terminator protein and DNA. Protein Sci., 11: 147-157, 2002
Chemistry Department Research Booklet Updated February 2007 Page 12
Dr Stephen Blanksby email: [email protected]
Mass spectrometry (MS): applications and fundamentals
The mass spectrometry laboratory at UoW has a range of sophisticated instrumentation for the detection and characterization of molecular species based on their mass/charge ratio. These state-of-the-art technologies can be employed for applications as diverse as determining the lipid profile of cellular membranes in biological tissue samples or probing the oxidation products from weathered colorbond® roofing panels! In addition to these analytical applications, the mass spectrometer provides the ideal gas phase “test tube” for probing the structure and reactivity of molecular ions and neutral radicals.
Applications: phospholipid mass spectrometry
My group is currently involved in the rapidly expanding field of lipidomic research. Using modern MS techniques we are able to observe subtle changes in the lipid composition of cell membranes. These changes in the membrane lipid profile can associated with a range of factors including; diet, exercise, illness or age. For example, in collaboration with Dr Todd Mitchell (Biomedical Science), Prof Tony Hulbert (Biological Sciences) and Assoc. Prof. Paul Else (Biomedical Science) we are probing changes in the lipid profile that may be associated with the metabolic syndrome, which includes Type II Diabetes and obesity. Characterizing the changes that occur during these pathologies at the molecular level may provide a better understanding of the underlying mechanisms of such diseases. In a new collaboration with Prof. Roger Truscott (University of Sydney) we are using MS to search for changes in the lipid profile of the human lens that may be associated with the onset of cataract or presbyopia.
In addition to studies of biological samples we are also working toward improved methods for the structural characterization and the quantification of phospholipids by electrospray ionization MS. We have several ongoing projects that aim to provide a better understanding of the underlying mechanisms of phospholipid ionization, fragmentation and oxidation in the mass spectrometer. We have recently developed a new technique for chemically induced fragmentation of lipids using ozone that determines the position of double bonds in lipids.
Applications: keeping colorbond® colourful
In collaboration with Dr Philip Barker at Bluescope Steel Research we are using the complementary technologies of electron spin resonance (ESR), electrospray ionization mass spectrometry (ESI-MS) and a new technique known as desorption electrospray ionization mass spectrometry (DESI-MS) to elucidate oxidation processes that occur within the polymer coating of Bluescope’s flagship sheet steel product, colorbond®. ESR readily identifies free radicals formed by these oxidation processes, while ESI-MS and DESI-MS provide structural information about both radical and non-radical species formed by these processes. These studies are directed towards improving the longevity of colorbond® under the harsh oxidizing conditions encountered on the typical Australian roof!
Fundamentals: perxoyl radicals and peroxide anions in the gas phase The advantage of gas phase studies, using mass spectrometers, over traditional “wet-chemistry” is that the former allow us to understand the fundamental reactivity of ions and molecules without interference from either solvent or counter-ions. Furthermore, some critically important ions and molecules are so reactive that they can only be studied in the isolation of the
Chemistry Department Research Booklet Updated February 2007 Page 13 vacuum inside the mass spectrometer. The results of these fundamental studies contribute to our understanding of complex applied problems in biological, atmospheric, interstellar and combustion chemistries. Selected projects currently under investigation are outlined below.
In collaboration with Dr Shuji Kato (University of Colorado, Boulder) we have identified the reactions of small organic peroxides with anions and radical anions in the gas phase using a specialized mass spectrometer called a flowing afterglow- selected ion flow tube. These investigations demonstrate that anions can decompose peroxides to form hydroxide ions and potentially genotoxic aldehydes and ketones. The results of this experimental investigation are complemented by theoretical studies, carried out using supercomputers, which show that the reaction proceeds by an elimination mechanism (see figure below). Further work is underway using mass spectrometry to investigate the reactions of peroxides with radical anions.
Using the latest in ion-trap mass spectrometry equipment (the ThermoFinnigan LTQ) we are developing a range of methods for producing distonic peroxyl radical anions in the gas phase using electrospray ionization. Distonic anions have a separated charge and radical center and can thus act as “charge tagged radicals” where the charge does not significantly perturb the reactivity of the radical but simply provides us with a convenient handle with which to isolate it in the ion trap mass spectrometer. We are currently investigating methods for reacting our charge tagged peroxyl radicals with a range of neutral substrates in the gas phase. This new methodology will provide unique insight into the chemistry of peroxyl radicals in the gas phase and thus the role of peroxyl radical intermediates in biochemical and atmospheric processes.
Selected Publications
1. Thomas, M. C., Mitchell, T. W., and Blanksby, S. J., "Ozonolysis of phospholipid double bonds during electrospray ionization: A new tool for structure determination" Journal of the American Chemical Society 2006, 128(1), 58-59.
2. Harman, D. G. and Blanksby, S. J., "Trapping of a tert-adamantyl peroxyl radical in the gas phase" Chemical Communications 2006, 8, 859-861.
3. Thomas, M. C.; Mitchell, T. W.; Blanksby, S. J. A Comparison of the Gas Phase Acidities of Phospholipid Headgroups: Experimental and Computational Studies. Journal of the American Society for Mass Spectrometry 2005, 16, 926-939.
4. Mitchell, T. W.; Turner, N.; Else, P. L.; Hulbert, A. J.; Lee, J. S.; Bruce, C. R.; Hawley, J. A.; Blanksby, S. J. Exercise Alters Phospholipid Molecular Species in Rat Skeletal Muscle. Journal of Applied Physiology 2004, 97, 1823-1829.
5. Blanksby, S. J.; Kato, S.; Bierbaum, V. M.; Ellison, G. B. Fragmentations of Deprotonated Alkyl Hydroperoxides (ROO-) Upon Collisional Activation: A Combined Experimental and Computational Study. Aus. J. Chem. 2003, 56, 459-472.
6. Blanksby, S. J.; Ellison, G. B. Bond Dissociation Energies of Organic Molecules. Acc. Chem. Res. 2003, 36, 255-263.
7. Blanksby, S. J.; Ellison, G. B.; Bierbaum, V. M.; Kato, S. Direct Evidence for Base-Mediated Decomposition of Alkyl Hydroperoxides (ROOH) in the Gas Phase. J. Am. Chem. Soc. 2002, 124, 3196-3197.
8. Blanksby, S. J.; McAnoy, A. M.; Dua, S.; Bowie, J. H. Cumulenic and Heterocumulenic Anions: Potential Interstellar Species? Mon. Not. R. Astron. Soc. 2001, 328, 89-100.
9. Blanksby, S. J.; Schroeder, D.; Dua, S.; Bowie, J. H.; Schwarz, H. Conversion of Linear to Rhombic C4 in the Gas Phase: A Joint Experimental and Theoretical Study. J. Am. Chem. Soc. 2000, 122, 7105-7113.
Chemistry Department Research Booklet Updated February 2007 Page 14
Professor John B Bremner email: [email protected]
The research activities are based on the three interacting themes of medicinal chemistry, synthetic heterocyclic chemistry and natural products chemistry. The long term goal is centered on the development of new selective medicinal agents for the treatment of disease.
Medicinal Chemistry
Computer-based molecular design (including new drug design approaches), synthesis and development of new selective medicinal agents including antibacterial, antiviral and antimalarial agents to counteract antimicrobial resistance, anti- cancer agents and new anti-cancer agent formulations, and cardiovascular agents targeting selective modulation of alpha 1 - adrenoceptors .
Selected Publications
1. Samosorn, S., Bremner, J.B., Ball, A., and Lewis, K., ‘Synthesis of Functionalised 2-Aryl-5-nitro-1H-indoles and their Activity as Bacterial NorA Efflux Pump Inhibitors’, Bioorg. Med. Chem., 2006, 14, 857-865.
2. Ball, A.R., Casadei, G., Samosorn, S., Bremner, J.B., Ausubel, F.M., Moy, T.I., and Lewis, K., ‘Conjugating Berberine to a Multidrug Resistance Pump Inhibitor Creates an Effective Antimicrobial’, ACS Chemical Biology, 2006, 1, 594-600.
3. McGinty, S.J., Finch, A., Griffith, R., Graham, R.M., and Bremner, J.B.,’Synthesis and Biological Evaluation of Bicyclic and Tricyclic Substituted Nortropane Derivatives: Discovery of a Novel Selective alpha-1D-Adrenergic Receptor Ligand’, Bioorg. Med. Chem., 2004, 12, 5639-5650.
Synthetic Heterocyclic Chemistry
Development of concise, efficient methodology for the synthesis of heterocyclic systems, particularly in the poorly developed area of medium-sized heterocycles (7- to 11- membered rings) and assessment of their properties; more than forty new ring systems have been made.
Selected Publications
1. Bremner, J.B., and Perkins, D.J., ‘Synthesis of Functionalised Azecine and Azonine Derivatives via an Enolate Assisted Aza Claisen Rearrangement’, Tetrahedron, 2005, 61, 2659-2665.
2. Bremner, J.B., and Sengpracha, W., ‘ An Iodoacetamide-based Free Radical Cyclisation Approach to the 7,12-Dihydro- indolo[3,2-d][1]benzazepin-6(5H)-one(Paullone) System’, Tetrahedron, 2005, 61, 5489-5498.
3. Bremner, J.B. and Sengpracha, W., 'A Free Radical Cyclization Approach to Indolo-benzodiazocine Derivatives',Tetrahedron, 2005, 61, 941-953.
Chemistry Department Research Booklet Updated February 2007 Page 15
Natural Products Chemistry
Discovery of new alkaloids and the use of alkaloids as starting materials in synthesis of new potential bio-active agents. Development of bio-rational and combined chemo- and bio-rational approaches to indentifying natural products from terrestrial or marine sources as novel antibacterial or antimalarial lead compounds and their synthetic analogue development. Natural dyes and the mechanism of dye-textile interactions are also of interest.
Selected Publications
1. Apisantiytakom, S., Kittakoop, P., Manyum, T., Kirtikara, K., Bremner,J.B., and Thebtaranonth, Y., ‘ Novel Biologically Active Bibenzyls from Bauhinia saccocalyx PIERRE’, Chemistry and Biodiversity, 2004, 1, 1694-1701.
2. Chairat, M., Rattanaphani, S., Bremner, J.B., and Rattanaphani, V., ‘An Adsorption and Kinetic Study of Lac dyeing on Silk’, Dyes and Pigments, 2005, 64, 231-241.
3. Berry,Y., Bremner, J.B. ,Davis, A., and Samosorn, S., ‘Isolation and NMR Spectroscopic Clarification of the Alkaloid 1,3,7-Trimethylguanine from the Ascidian Eudistoma maculosum’, Nat. Prod. Res., 2006, 20, 479-483.
Chemistry Department Research Booklet Updated February 2007 Page 16
Dr Carolyn T. Dillon email: [email protected]
Bioinorganic and Medicinal Chemistry
Research interests of the Dillon laboratory include studies of the modes of action of metal and metalloid containing anti- cancer agents for the design and synthesis of more effective drugs. Techniques include: • Microprobe X-ray fluorescence (XRF) mapping of cells and X-ray absorption spectroscopy (XAS) performed at the Advanced Photon Source in Chicago; • XAS performed at the Photon Factory in Tsukuba, Japan; • Mass spectrometry; • Gel electrophoresis assays; • Cell assays; • Electron microscopy; • Spectroscopy.
Arsenic Anti-Cancer Drugs
Recently, the FDA approved the use of arsenic trioxide (Trisenox™) as a potent anti-leukemia drug. Furthermore, at least two other arsenic compounds, tetraarsenic tetrasulfide (As4S4) and 4-(N-(S-glutathionylacetyl)amino)-phenylarsinoxide (GSAO), are undergoing clinical trials as anti-cancer drugs. The current research interests include the investigations of arsenic species for understanding the metabolic events that lead to arsenic-induced anti-cancer activity and the development of future arsenic anti-cancer agents.
Determining the Intracellular Targets of Arsenic Trioxide
The underlying factor that appears to be crucial to the success of arsenic anti-cancer drugs is their multi-faceted mechanisms of toxicity towards cancer cells. While most anti-cancer drugs act by targeting DNA and enzymes involved in DNA synthesis, arsenic has been aptly described as an anti-cancer missile with multiple warheads as it also induces toxicity through interactions with a number of critical enzymes and proteins, including mitochondrial ANT and tubulin. Currently we are investigating the biomolecular interactions of arsenic trioxide and its metabolites with each of these targets to assess their importance in arsenic-induced anti-cancer action. This study involves the use of microprobe-XRF mapping of intracellular arsenic, graphite furnace atomic absorption spectroscopy, mass spectrometry and radiolabelled arsenic assays for assessing arsenic binding interactions.
Investigating the Metabolism of Arsenic Trioxide and Other Potential Arsenic Anti-Cancer Drugs
A recent (2005) publication by Hayakawa proposed a new metabolic pathway for arsenic. This contradicts critical aspects of previously proposed metabolic pathways that have dominated the literature for up to 50 years. Consequently, we are employing mass spectrometry in conjunction with direct XAS probing of arsenic-treated cells to study the arsenic molecules formed intracellularly. The accurate elucidation of the arsenic metabolic pathway is highly relevant for arsenic drug/prodrug design.
Chemistry Department Research Booklet Updated February 2007 Page 17 Design and Synthesis of New Arsenic Anti-Cancer Drugs.
While As complexes are gaining notoriety as anti-cancer drugs, one of the main drawbacks of their use is their toxicity arising from their indiscriminate toxicity in vivo. Importantly, however, subtle differences occur between normal cells and tumour cells. For example, it is well established that the greater bioenergetic requirements of transformed cells over normal cells results in a more rapid uptake of glucose to satisfy the requirements of increased glycolysis. In this project, the logical incorporation of glucose moieties into arsenic compounds is being utilized as a selective targeting strategy for producing arsenic anti-cancer drugs. Similarly, the coordination of arsenic to “tumour-homing peptides”, that are recognised by and incorporated into tumour cells, is also being studied. Ideally, the incorporation of these peptides and glucose ligands into arsenic compounds should improve patient efficacy and at the same time reduce adverse side-effects. Consequently, the synthesis, stabilities, cellular metabolism/reactivities and selectivity of such arsenic compounds in and to tumour cells is being investigated to determine if the “targeting devices” remain bound to the arsenic and furthermore, whether they aid in delivering arsenic to the tumour cells. Techniques include basic inorganic syntheses, purification and characterization (nmr, UV/Vis and mass spectrometry) techniques, and cell culture assays.
Selected Publications
1. Dillon, C. T.; Lay, P. A.; Kennedy, B. J.; Stampfl, A. P. J.; Cai, Z.; Ilinski, P.; Rodrigues, W.; Legnini, D. G., Lai, B. and Maser, J. Hard X-ray microprobe studies of chromium(VI)-treated V79 Chinese hamster lung cells: intracellular mapping of the biotransformation products of a chromium carcinogen. J. Biol. Inorg. Chem. 2002, 7, 640-645.
2. Dillon, C. T.; Hambley, T. W.; Kennedy, B. J.; Lay, P. A.; Zhou, Q.; Davies, N. M.; Biffin, J. R. and Regtop, H. L. Gastrointestinal damage, anti-inflammatory activity and superoxide dismutase activity of copper and zinc complexes of the anti-inflammatory drug, indomethacin. Chem. Res. Toxicol. 2003, 16, 28-37.
3. Levina, A.; Codd, R.; Dillon, C. T.; Lay, P. A. Chromium in biology: nutritional aspects and toxicology. Prog. Inorg. Chem., 2003, 51, Chapter 2, 145-250.
4. Hall, M. D.; Dillon, C. T.; Zhang, M.; Beale, P.; Cai, Z.; Lai, B.; Stampfl, A. P. J.; Hambley, T. W. The Cellular Distribution and Oxidation State of Platinum(II) and Platinum(IV) Antitumour Complexes in Cancer Cells. J. Biol. Inorg. Chem., 2003, 8, 726-732.
5. Dillon, C. T.; Hambley, T. W.; Kennedy, B. J.; Lay, P. A.; Weder, J. E.; Zhou, Q. Copper and zinc complexes as anti- inflammatory drugs. in Metals in Biological Systems, 2004, Volume 41, Chapter 8. Metal ions and their complexes in medication. Sigel, A and Sigel, H. (eds).
6. Waern, J.B.; Dillon, C.T.; Harding, M. M. Organometallic anticancer agents: cellular uptake and cytotoxicity studies on thiol derivatives of the antitumour agent molybdocene dichloride. J Med Chem. 2005, 48, 2093-2099.
Chemistry Department Research Booklet Updated February 2007 Page 18
Professor Nicholas E Dixon email: [email protected]
Some proteins are enzymes that promote chemical reactions; others provide molecular switches that control metabolic and developmental processes through precise interactions with other proteins, nucleic acids and other ligands. The chemistry that governs the specificity and strength of interactions of proteins with substrates, inhibitors, nucleic acids, and other proteins is being explored in two complementary research programs.
Molecular Motors in the Bacterial Replisome
The first program concerns the thirty or so different proteins that collaborate to replicate the DNA of the bacterial chromosome prior to cell division. DNA replication is a very good model system to study protein– protein and protein–nucleic acid interactions because the proteins act together in a giant nucleoprotein assembly called the replisome, to make perfect copies of the chromosome. The replisome comprises three interacting molecular motors, the DNA helicase that separates the two DNA strands, and the two DNA polymerases that simultaneously make copies of them at the replication fork. Interactions among the proteins are dynamic and are often mediated by flexible intrinsically unstructured regions within the protein subunits. Since correct function of the replisome is essential for survival of bacteria, it also represents a good target for developmnt of new animicrobial drugs.
In this program, we use molecular genetics to engineer rich sources of the proteins and to produce mutant derivatives and segments of them, and conventional enzymology, DNA synthesis and protein interaction assays to study protein function. This program is supported by many local, national and international collaborations, in areas as diverse as protein X-ray crystallography, ESR and high-field NMR spectroscopy, mass spectrometry, electron microscopy, computational methods and single-molecule techniques. These are used to further understand the structures of the individual proteins, and to relate their structures to how they work and interact with each other and with DNA in the various processes that occur as the replisome functions.
New Protein Technologies
Our other research program has complementary objectives. A suite of new techniques in protein chemistry is being developed, including methods for in vitro evolution of new protein functions, in vitro synthesis of proteins on a preparative
Chemistry Department Research Booklet Updated February 2007 Page 19 scale, including methods for site-specific incorporation of unnatural amino acids, library methods for precise location of boundaries between distinct folded domains in larger proteins, and stabilisation of small protein domains by end-to-end cyclisation of their polypeptide chains. New methods based on protein mass spectrometry are also being exploited to map protein interaction interfaces in macromolecular complexes. Used together, these techniques are helping to overcome some of the bottlenecks in rapid determination of protein structures and functions, thereby increasing the efficiency of worldwide efforts in structural and functional genomics. They are also being used to study the fundamental chemistry that underpins the relationship between the structure, folding, stability and functions of proteins.
Selected Publications
1. Williams, N.K., Liepinsh, E., Watt, S.J., Prosselkov, P., Matthews, J.M., Attard, P., Beck, J.L., Dixon, N.E. & Otting, G. (2005) Stabilization of native protein fold by intein-mediated covalent cyclization. Journal of Molecular Biology, 346, 1095–1108.
2. Elvin, C.M., Carr, A.G., Huson, M.G., Maxwell, J.M., Pearson, R.D., Vuocolo, T., Liyou, N.E., Wong, D.C.C., Merritt, D.J. & Dixon, N.E. (2005) Synthesis and properties of crosslinked recombinant pro-resilin. Nature, 437, 999–1002.
3. Pintacuda, G., Park, A.Y., Keniry, M.A., Dixon, N.E. & Otting, G. (2006) Lanthanide labeling offers fast NMR approach to 3D structure determinations of protein–protein complexes. Journal of the American Chemical Society, 128, 3696–3702.
4. Beck, J.L., Urathamakul, T., Watt, S.J., Sheil, M.M., Schaeffer, P.M. & Dixon, N.E. (2006) Proteomic dissection of DNA polymerization. Expert Reviews in Proteomics, 3, 197–211.
5. Mulcair, M.D., Schaeffer, P.M., Oakley, A.J., Cross, H.F, Neylon, C., Hill. T.M. & Dixon, N.E. (2006) A molecular mousetrap determines polarity of termination of DNA replication in E. coli. Cell, 125, 1309–1319.
6. Su, X-C., Schaeffer, P.M., Loscha, K.V., Gan, P.H.P., Dixon, N.E. & Otting, G. (2006) Monomeric solution structure of the helicase binding domain of Escherichia coli DnaG primase. FEBS Journal, 273, 4997–5009.
Chemistry Department Research Booklet Updated February 2007 Page 20
Professor David Griffith email: [email protected]
Atmospheric Chemistry and Spectroscopy
See also Dr. Stephen Wilson Research in atmospheric chemistry is concerned with measurements and interpretation of atmospheric trace gas composition and the exchange of trace gases between the atmosphere, biosphere and geosphere. These studies are aimed at a better understanding of the budgets, sources and sinks of trace gases important in atmospheric chemistry, the greenhouse effect, climate change, stratospheric ozone chemistry and ultraviolet radiation. These gases include CO2, CH4, N2O, CO, O3, NH3, NO, NO2, water vapour and many others. Current foci and specific examples include: • exchange of trace gases with soils, animals and agricultural environments • Especially methane from livestock and nitrous oxide from soils • spectroscopic measurement of isotopic composition in trace gases • Using isotopic fractionation to trace the sources and sinks of trace gases – nitrous oxide, methane, carbon dioxide, water vapour • solar spectroscopy for ground-based remote sensing of atmospheric composition • Tracing biomass burning emissions and estimating their atmospheric impacts • Global carbon dioxide measurements and modelling • global satellite-based measurements of carbon dioxide – the Orbiting Carbon Observatory (http://oco.jpl.nasa.gov)
This research involves a strong component of development of novel applications of spectroscopy (especially FTIR spectroscopy) for measurements of atmospheric trace gas composition and fluxes. The main areas of development are: • Long path, low-resolution FTIR spectroscopy for simultaneous high precision analysis of trace gases in air. The technique is being used for example at the Cape Grim clean air monitoring station in Tasmania, at the CSIRO trace gas analysis laboratory (GASLAB), and at the campus in Wollongong to determine concentrations and sources of CO2, CH4, N2O and CO. • A high precision FTIR spectrometer is used together with micrometeorological sampling methods to measure fluxes of greenhouse gases (CO2, CH4, N2O) from the earth’s surface, in particular from agricultural environments and landfills. This work involves extensive collaboration with the CSIRO. • Very high resolution solar FTIR spectroscopy is used for ground-based remote sensing of atmospheric composition. This work is combined with parallel measurements of solar ultraviolet and visible spectra and UV radiation (Dr. Stephen Wilson) to investigate in particular stratospheric ozone and its link with ground level UV radiation. It forms part of the international Network for Detection of Stratospheric Change. Recent and current work is focused on using remote sensing to quantify biomass burning emissions to the atmosphere.
Chemistry Department Research Booklet Updated February 2007 Page 21 • We have pioneered the use of high resolution FTIR spectroscopy as a new technique for isotopic analysis of atmospheric trace gases. There are several applications where the FTIR-based method provides complementary information to that from conventional analysis by mass spectrometry. These include distinguishing isotopically- 15 14 16 14 15 16 13 substituted species of similar mass and structural isomers such as N N O + N N O, or CH4 + CH3D.
Selected Publications
1. Griffith, D. W. T. (2002). FTIR measurements of atmospheric trace gases and their fluxes. Handbook of Vibrational Spectroscopy. J. M. Chalmers and P. R. Griffiths, John Wiley & Sons. 4: 2823-2841.
2. Turatti, F., D.W.T. Griffith, S.R. Wilson, M.B. Esler, T. Rahn, H. Zhang, G. Blake, and M. Wahlen, Positionally dependent 15N fractionation factors in the photolysis of N2O determined by high resolution FTIR spectroscopy, Geophys. Res. Lett., 27 (16), 2489-2492, 2000. 3. Griffith, D.W.T., Toon, G.C., Sen, B., Blavier, J.-F., and Toth, R.A., 2000. Vertical profiles of nitrous oxide isotopomer fractionation measured in the stratosphere. Geophysical Research Letters, 27 (16), 2485-2488. 4. Esler, M.B., D.W.T. Griffith, S.R. Wilson, and L.P. Steele, Precision trace gas analysis by FT-IR spectroscopy, Anal. Chem., 72 (1), 206-215 and 216-221, 2000. 5. Griffith, D.W.T., and B. Galle, Flux measurements of NH3, N2O and CO2 using dual beam FTIR spectroscopy and the flux-gradient technique, Atmos. Environ., 34 (7), 1087-1098, 2000. 6. Leuning, R., S.K. Baker, I.M. Jamie, C.H. Hsu, L. Klein, O.T. Denmead, and D.W.T. Griffith, Methane emission from free ranging sheep: a comparison of two measurement methods, Atmos. Environ., 33 (9), 1357-1365, 1999. 7. Griffith, D.W.T., N.B. Jones, and W.A. Matthews, Interhemispheric ratio and annual cycle of carbonyl sulfide (OCS) total column from ground based solar FTIR spectra, J. Geophys. Res., 103 (D7), 8447-8454, 1998. 8. Griffith, D.W.T., Synthetic calibration and quantitative analysis of gas phase infrared spectra, Applied Spectroscopy, 50 (1), 59-70, 1996.
Chemistry Department Research Booklet Updated February 2007 Page 22
Dr Marc in het Panhuis email: [email protected]
Multi-functional and Intelligent Materials based on surfactants, polymers and carbon nanotubes
Intelligent or smart materials are under active investigation for their potential applications in health monitoring, space exploration, civil engineering, automotive, aerospace, textiles and the battlefield of the future. An intelligent material is defined as a material capable of recognising appropriate environmental stimuli, processing the information arising from the stimuli and responding to it in an appropriate manner and time frame. Intelligent materials differentiate themselves from conventional materials by their dynamic character, which allows them to respond autonomously to changing environmental conditions.
Combining polymers with carbon nanotubes could offer the enticing prospect of materials with enhanced functionality compared to polymers. Of particular interest are conducting electroactive polymers (CEP) such as the polyanilines, polypyrroles and polythiophenes which have been recognised as suitable building blocks for intelligent materials applications as they can be engineered to recognise stimuli, are conductive and can actuate. However the properties of CEP are lower compared to the conductivity and current carrying capacity of most metals, mechanical properties of Kevlar and actuation stress of skeletal muscle. Hence there is room for improvement in the properties of electroactive polymers. This could be achieved by combination of these polymers with materials whose properties are superior to those of the polymers. Carbon nanotubes are an ideal candidate for such materials.
Carbon nanotubes have attracted enormous attention due to their phenomenal properties. For example, the mechanical and electrical properties of carbon nanotubes are several orders of magnitude higher compared to CEP such as the polyanilines. However, one of the main disadvantages of carbon nanotubes is their process-ability, i.e. they are not easily dispersed in most solvents due to their hydrophobic nature. This issue can be overcome by incorporating carbon nanotubes into a polymer material. This can result in composite materials with enhanced functionality.
My research focuses on synthesis, characterisation and applications of composite materials with enhanced properties. The composite materials are fabricated using surface active molecules and polymers. Fabrication methods for composite materials include (but are not limited to) functionalisation, intercalation and in-situ polymerisation. A solution based approach is used to process these materials for application. Currently we are studying applications ranging from conducting textiles to optically active films and flexible transparent films for sensors.
Optical active and conducting composite materials
An interesting aspect of polyaniline is its ability to become optically active through the addition of chiral dopants such as camphorsulfonic acid (CSA). The optical activity is thought to arise from adoption of either a one-handed helical conformation or a helical packing of polymer chains. In-situ polymerisation of aniline in the presence of multi-walled carbon nanotubes and chiral agents provides a route to optically active and electrically conducting composite materials. It is thought that chiral materials can be used as chiral films or membranes in the production of enantiomerically pure compounds.
Chemistry Department Research Booklet Updated February 2007 Page 23
Carbon nanotube networks
Carbon nanotubes (CNT) possess many unique electronic and mechanical properties that make them highly versatile and of great interest to researchers from a wide range of scientific disciplines. One of the key challenges is processing or engineering CNT for potential applications such as electronic components or coatings. The routes available to engineering single-walled carbon nanotubes (SWNT) into networks with electrical and mechanical properties involve (but are not limited to) direct growth (onto a substrate) and solution based processing.
Selective Publications
1. M. in het Panhuis, ‘Carbon nanotubes: enhancing the polymer building blocks for intelligent materials’, Journal of Materials Chemistry 16, 3598-3605 (2006).
2. M. in het Panhuis, R. Sainz, P.C. Innis, L.A.P. Kane-Maguire, A.M. Benito, T.M. Martínez, S.E. Moulton, G.G. Wallace, and W.K. Maser, ‘An optically active polymer carbon nanotube composite’, Journal of Physical Chemistry B 109, 22725-22729 (2005).
3. M. in het Panhuis, S. Gowrisanker, D.J. Vanesko, C.A. Mire, H. Jia, H. Xie, R.H. Baughman, I.H. Musselman, B.E. Gnade, G.R. Dieckmann and R.K. Draper, ‘Nanotube network transistors from peptide-wrapped single-walled carbon nanotubes’, Small 1, 820-823 (2005).
4. R. Gupta, R.E. Smallcup and M. in het Panhuis, ‘Reversible transport characteristics of multi-walled carbon nanotubes in free space’, Nanotechnology 16, 1707-1711 (2005).
5. G. Chambers, C. Carroll, G.F. Farrell, A.B. Dalton, M. McNamara, E. Cummins, M. in het Panhuis, and H.J. Byrne, ‘Characterisation of the interaction between γ-cyclodextrin and single wall carbon nanotubes’, Nano Letters 3, 843-846 (2003)
6. M. in het Panhuis, 'Vaccine delivery with carbon nanotubes', Chemistry and Biology 10, 897-898 (2003).
7. M. in het Panhuis, R.W. Munn, P.L.A. Popelier, J.N. Coleman, B. Foley, and W.J. Blau, ‘Distributed response analysis of conductive behaviour in single molecules’, Proceedings of National Academy of Sciences USA 99, 6514 – 6517 (2002).
8. F. Frehill, J.G. Vos, S. Benrezzak, A. Koos, Z. Konya, M. Rüther, W.J. Blau, A. Fonseca, J.B. Nagy, L.P. Biro, A.I. Minett and M. in het Panhuis, ‘Interconnecting carbon nanotubes with an inorganic metal complex’, Journal of the American Chemical Society 124, 13694-13695 (2002).
9. R. Sainz, W.R. Small, N.A. Young, C. Valles, A.M. Benito, W.K. Maser, and M. in het Panhuis, ‘Synthesis and characterization of optically active polyaniline carbon nanotube composites’, Macromolecules 39, (2006), 7324-7332.
Chemistry Department Research Booklet Updated February 2007 Page 24
Dr Dianne Jolley email: [email protected]
The behaviour of elements in key ecosystems (e.g., estuaries, wetlands, mangroves, soils) is a major issue in environmental research. Modern environmental research is adopting a holistic approach using a combination of information (e.g., biological indicators, sediment quality, speciation and modelling) to get a better understanding of the processes controlling the behaviour of critical elements. This often involves the analysis of complex mixtures of materials for a range of chemical species. Recent developments in instrumental technology will enable scientists to develop a greater understanding of trace elements in animals, plants, water, sediment, and gaseous environments (e.g., using isotopic signatures). Most previous studies have examined only compositional aspects of these systems, with limited attempts being made to determine the pathways of the elements through the systems. Information on trace element pathways will expand our understanding of element behaviour under differing conditions, including their bioavailability. As we gain a greater understanding of these pathways, scientists are in a better position to explain past environmental changes and to predict the environmental impacts of current human activities. Trace metals in particular are very interesting, as they may be essential or non-essential. Essential trace metals play a critical role in many biological systems, as they are required in minute amounts in order to sustain good health. For example, they are essential in the function of key enzymes in the stabilisation of proteins in nucleic acids, in energy conversion and transport, and in a variety of drug treatments (metallo- based anticancer agents, radiopharmaceuticals). In marine systems, some metals are structurally incorporated into animals, e.g., Zn in the jaws of nereid polychaetes (marine worms), Cu in the blood of molluscs and crustacea. Non-essential trace metals such as cadmium, mercury and lead have little known metabolic function. In addition, some trace metals are found in amino acids that actively incorporated into functioning proteins by specific tRNA molecules. These proteins are called metallo-proteins, and are important in the function of a variety of biological projects and organisms. The uptake of trace elements (e.g., Se) may also be used as a marker of environmental pollution. Studies of trace metal uptake in marine organisms require determination of the elements associated with different classes of proteins within the organism (e.g., proteins that will protect the organism from oxidative stress). All trace elements, both essential and non-essential may be toxic in excessive amounts.
My research interests lie between the fields of Analytical and Environmental Chemistry. Specifically I have interest in:
• The development of new methods to investigate the uptake, metabolism and storage of metal species in aquatic biological systems (including diffusive gradients in thin films – DGT); • The development/optimisation of techniques to determine the biologically available portion of toxic compounds in marine ecosystems; • The investigation of chemically induced physiological changes in organisms; • Environmental toxicology in aquatic systems (marine micro-algae); • Determining the fate of chemicals both within the biotic and abiotic environment; • The characterisation of seleno-compounds in marine tissues.
Chemistry Department Research Booklet Updated February 2007 Page 25
Specific topics of current interest include:
• Toxicity of trace metals to marine organisms (in collaboration with CSIRO Energy Technology) • Development of new methods to isolate and quantify different metal species in biological and abiotic samples (currently diffusive gradients in thin films (DGT) for anionic contaminants) • The uptake, metabolism and storage of trace metals in marine organisms • Trace metal pathways (incl. Se, As) in coastal and estuarine systems
Selected Publications
1. Simpson, S. L, Burston, V. L., Jolley, D. F., and Chau, K. 2006 Application of surrogate methods for assessing the bioavailability and bioaccumulation of PAHs in sediments to sediment ingesting organisms. Chemosphere 65 (11), 2401-2410
2. Levy J.L., Stauber J.L., Adams M.S., Kirby J.K., Maher W.A., Jolley D.F. 2005 Toxicity, biotransformation and mode of action of arsenic in two freshwater microalgae (Chlorella sp. and Monoraphidium arcuatum). Environmental Toxicology and Chemistry. 24 (10), 207-216.
3. Jolley, D.F., Maher, W. and Kyd, J. 2004 Selenium accumulation in the Sydney Cockle Anadara trapezia. Environmental Pollution. 132, 203-212.
4. Simpson, S. L., Angel, B. M., Jolley, D.F. 2004 Metal equilibration and bioavailability in laboratory-contaminated (spiked) sediments used for the development whole-sediment toxicity tests. Chemosphere 54(5), 597-609.
5. Simpson, S., Pryor, I., Mewburn, B.; Batley, G.; Jolley, D.F. 2002. Considerations for Capping Metal-Contaminated Sediments in Dynamic Estuarine Environments. Environmental Science and Technology, 36, 3772-3778.
6. Jolley, D.F.; Maher, W. and Cullen, P. 1998. Rapid method for isolating and quantifying orthophosphate and polyphosphates: Application to sewage samples. Water Research, 32: 711-716.
Chemistry Department Research Booklet Updated February 2007 Page 26
Professor Leon Kane-Maguire email: [email protected]
Preparation of Enantiomerically Pure Drugs Using Chiral Conducting Polymers
The majority of drugs (eg. amines) contain chiral centres, and thus exist in two mirror image enantiomeric forms. These enantiomers frequently have very different biological effects, leading in some cases to serious medical problems where they have been administered as the racemic mixture of the two enantiomers. There is therefore an urgent need to develop methods for either (a) the asymmetric synthesis of drugs in only the one (desired) enantiomeric form, or (b) the efficient separation of the two enantiomeric forms of the drug. We are exploring a novel and promising approach for the preparation of enantiomerically pure drugs, namely the use of chiral electrically conducting polymers In collaboration with Professor Gordon Wallace in the Intelligent Polymer Research Institute, we have reported the first synthesis of optically active polyaniline, a polymer that possesses the unusual feature of being both electrically conducting and chiral. These polymers can be readily made with either a right–or a left-handed helical chain.
We have also recently shown that these chiral polyanilines have considerable potential as: (a) chiral electrodes for the electrochemical asymmetric synthesis of drugs (b) chiral membranes for the separation of chiral species.
These applications are now being actively explored. Particularly attractive would be their use as chiral electrodes in electrochemical asymmetric synthesis. This little explored approach could have major advantages over conventional chemical asymmetric syntheses, such as no requirement for expensive chiral auxiliaries and the reduced number of by- products.
Photo-Initiated Redox Reactions of Polyanilines This project will exploit out recent discovery that the irradiation of conducting polyanilines with visible light (330-500 nm) generates photo-excited states of these polymers that are remarkably effective oxidising and reducing agents. With Australian Research Council funding, we are exploring their use for a wide range of novel photo-initiated redox reactions that do not occur in the absence of light. Exciting potential for these remarkable processes include; (i) Photochemically – driven asymmetric synthesis of drugs (a previously untouched area); (ii) Light – initiated polymer synthesis, including the production of conducting polymer patterns on fabrics, for use in Smart Clothes; (iii) Development of reversible light switches (i.e. Materials that rapidly change colour, electrical conductivity, and other properties upon exposure to light.
Chemistry Department Research Booklet Updated February 2007 Page 27 Selected Publications
1. E V Strounina, L A P Kane-Maguire and G G Wallace, “Optically Active Sulfonated Polyanilines”, Synthetic Metals, 106 , 129-137 (1999).
2. Patent: L A P Kane-Maguire, A G MacDiarmid, I Di Norris, G G Wallace and W Zheng, "Chiral Polyanilins and the Synthesis Thereof", US Patent No. 6,090,985, issued July 18, 2000.
3. I. D. Norris, L. A.P Kane-Maguire and G. G. Wallace, “Electrochemical Synthesis and Chiroptical Properties of Optically Active Poly ( o- methoxyaniline)”, Macromolecules, 33, 3237-3243 (2000)
4. L. A. P Kane-Maguire and G. G. Wallace, “Communicating with the Building Blocks of Life”, Synthetic Metals, 119, 39-42 (2001)
5. G. G. Wallace and L. A. P Kane-Maguire, “Manipulating and Monitoring Biomolecular Interactions with Conducting Electroactive Polymers”, Advanced Materials, 14, 953-960 (2002)
Chemistry Department Research Booklet Updated February 2007 Page 28
A/Professor Paul A Keller e-mail: [email protected]
Bioorganic and Medicinal Chemistry
The design and synthesis of new agents for therapeutic use. Techniques include: • organic synthesis, including methodology development, with an emphasis on the asymmetric synthesis of sterically hindered systems, spiro compounds, and new fullerenyl derivatives. • Computer-aided molecular modeling, with the design of new targets and methodology development investigating flexible protein systems.
Chiral Ligand Design for the Stereoselective Synthesis of Sterically Hindered Systems
We have recently reviewed5 the available stereoselective methods for atroposelective biaryl formation. Despite the numerous well-developed strategies, we identified no general method that was potentially applicable to the synthesis of all atropomeric biaryls in a direct fashion. The proposed best strategy was the use of palladium-based couplings (e.g. Suzuki reactions) in the presence of chiral catalysts, generated from palladium and chiral ligands. There are currently no chiral ligand design programs which address this problem. We are currently investigating a De Novo design program to address this problem, using synthetic and computational techniques.
Drug Design and Development
New Anti-HIV The recent emergence of resistance to the latest generation of HIV therapeutics highlights the continual urgent need for new drugs in the fight against AIDS. We are investigating a new, broad-based class of anti-viral agents through design and the advanced chemical synthesis. Our target is the non-nucleoside inhibitor binding pocket of the HIV-1 reverse transcriptase and HIV-1 integrase enzymes, and the approaches include novel structure and ligand based computer-aided molecular modeling studies to direct our designs.
The Fight for Life – Targeting the Prevention of Premature Birth Premature birth remains the greatest cause of death in babies in the Western world and a major consumer of health dollars. Corticotropin releasing hormone (CRH) has been implicated in the N onset of labour in pregnancy and the “fight or flight” response, in addition to a large number of physiological disorders. Antagonists of CRH have been shown to delay the onset of labour in N N N animal studies, however current available antagonists are unsuitable for therapeutic use. Our N Cl program involves the generation and development of new design principles through the construction of pharmacophores and novel molecular scaffolds. This project has a team of medicinal chemists (Depts. of Chemistry, Universities of Wollongong and Newcastle) aiming
Cl
Chemistry Department Research Booklet Updated February 2007 Page 29 towards developing these more effective, placental permeable therapeutics.
New Synthetic Fullerene Chemistry
Since its discovery, [60]-fullerene and its homologues have shown promise for exciting new developments and applications in medicinal chemistry and material science. However, an enhanced understanding of HH fulleryl chemistry and reactivity is vital for the accurate prediction of chemical outcomes Ho O and its application to such uses. The aims of this project are to: N • Develop new methods for the stereoselective and regioselective functionalisation of O Ph H the fullerene surface to give optically active, multifunctionalised fullerenes, 91 O H 17 • Develop spectroscopic methods (particularly advanced NMR techniques) to determine O the precise site of remote functionalisation in C60 derivatives, 16 O • Undertake mechanistic and computational studies to understand and predict the O Me regiochemistry, reactivity and chemistry of C60 systems, and
• Utilize this chemistry in the construction of simple nanomachines, using C60 fullerenes as templates, emulating biological processes.
The Development of Computer-Aided Molecular Modeling Techniques
With the increasing use of computer modeling in chemical research comes the increasing need for the development of new methods for a wider variety of uses. One of the current major problems is the lack of techniques available for the investigation of movement and flexibility in large molecules. We have a research program investigating flexibility in large proteins using an array of different techniques including docking, pharmacophores development, structure-based analysis, database searching and program writing.
Selected Publications
1. Keller, P. A.; Bowman, M.; Dang, K. H.; Leach, S. P.; Smith, R.; McClusky, A.; Pharmacophore Development for Corticotrophin Releasing Hormone: New Insights into Inhibitor Activity, J. Med Chem. 1999, 42, 13, 2351-2357. 2. Bremner, J. B.; Coates, J. A.; Coghlan, D. R.; David, D. M.; Keller, P. A.; Pyne, S. G.; The Synthesis of A Novel Binaphthyl-Based Cyclic Peptoid with Anti-Bacterial Activity, N. J. Chem. 2002, 26,1549-1552. 3. Burley, G. A.; Keller, P. A.; Pyne, S. G.; Ball, G. E.; The Synthesis and Characterisation of Mono- and Bis- methano[60]fulleryl Amino Acid Derivatives and their Reductive Ring-Opening Retro-Bingel Reactions J. Org. Chem., 2002, 67, 8316-8330. 4. Griffith, R.; Luu, T. T. T.; Garner, J.; Keller, P. A. Combining Structure-Based Drug Design and Pharmacophores. J. Mol. Graph. 2005, 23, 439-446. 5. Bringmann, G.; Price Mortimer, A. J.; Keller, P. A.; Garner, J.; Gresser, M. J.; Breuning, M. Modern Concepts for the Atropselective Synthesis of Axially Chiral Biaryls. Angew. Chem. 2005, 44, 5384-5427.
Chemistry Department Research Booklet Updated February 2007 Page 30
Dr Wilford Lie email: [email protected]
Nuclear magnetic resonance spectroscopy
Nuclear magnetic resonance spectroscopy (NMR) has been widely used as one of the most powerful instrumental techniques available for molecular structure and molecular dynamic research. It relies on magnetic properties possessed by many species of nuclei. An NMR signals arises from a nuclear property called spin, which is a quantum phenomenon whenever an external magnetic field is present. A model of it imagines a spin being a dipole spinning with its axis sweeping on a conical surface like a dying top. All nuclear spins are quantised at equilibrium; many of them have only two spinning directions, either up or down, notably those of 1H, 13C, 15N, 19F and 31P. A spinning nuclear as well as the nuclei and other moving charges surrounding the nuclear generate a local magnetic field. The result is a change in the spinning frequency of the nuclear itself, called the chemical shift, which allows us to distinctively identify it from NMR spectra. Furthermore, nuclear spins can be manipulated by different sequences of pulses to produce different types of NMR spectra in different dimensions, giving us useful structural information of different aspects, including the connection and the distances between neighbouring nuclei, etc.
Particular areas of research interest are:
Bio-molecular NMR
The applications of multi-dimensional NMR spectroscopy have been developed rapidly since 2D NMR spectroscopy was proposed [Jeener 1971] and materialised [Ernst 1974, 1975, 1976]. With its fascinating potential to study the molecular information and the ease of applications using the commercially available high-resolution NMR spectrometers, NMR spectroscopy has become one of the most rapidly developed and widely used tools in molecular research. This is marked by an upsurge of multi-dimensional NMR experimental methods, resulting in thousands of NMR-related papers being published in the last 30 years. Many of the published evidences have unequivocally proved that the NMR spectroscopy is a powerful tool for investigating 3D molecular structure of proteins in solution, which in many cases is a complimentary to the X-ray crystallography. Research on protein folding, protein stability, as well as interactions between protein-chemical, protein-protein, protein-DNA and protein-RNA has also been conducted using NMR spectroscopy. These applications have opened a new era to reason some important properties of bio-molecules at 3D molecular level, such as biological functions of bio-molecules, disease mechanism, and drug designs.
Chemistry Department Research Booklet Updated February 2007 Page 31 NMR in medical applications
The applications of NMR spectroscopy in medicine have been widely seen as MRI, the magnetic resonance imaging. However, at the molecular level, little has been achieved in routine applications of the NMR spectroscopy in solution, although it is potentially attractive. For example, the detection of phospholipids using 31P NMR has shown significant achievement recently in biological applications, which is one of the many areas we can expect to achieve excellent results in our lab.
Selected Publications
1. Phytochemical studies on Stemona plants: isolation of new tuberostemonine and stemofoline alkaloids. Sastraruji, Thanapat; Jatisatienr, Araya; Issakul, Kritchaya; Pyne, Stephen G.; Ung, Alison T.; Lie, Wilford; Williams, Morwenna C. Natural Product Communications (2006), 1(10), 813-818.
2. Confirmation of the structure of oxystemokerrin by single crystal X-ray structural analysis and a proposed biosynthesis.Mungkornasawakul, Pitchaya; Matthews, Hayden; Ung, Alison T.; Pyne, Stephen G.; Jatisatienr, Araya; Lie, Wilford; Skelton, Brian W.; White, Allan H. ACGC Chemical Research Communications (2005), 1930-33.
3. Caerin 4.1, an antibiotic peptide from the Australian tree frog, Litoria caerulea. The NMR-derived solution structure.Chia, Brian C. S.; Carver, John A.; Lindner, Robyn A.; Bowie, John H.; Wong, Herbert; Lie, Wilford. Australian Journal of Chemistry (2000), 53(4), 257-265.
Chemistry Department Research Booklet Updated February 2007 Page 32
Dr Garry Mockler email: [email protected]
Model Compounds of Copper Proteins
The structures and properties of model compounds of copper proteins are studied in order to better understand the functions, structures and properties of these metalloproteins which occur in biological systems. Galactose oxidase, which contains a type 1b copper atom, oxidizes a number of primary alcohols including galactose to the corresponding aldehydes. Model compounds of galactose oxidase are being synthesized and characterised and their reactions with sugars and alcohols are being investigated.
Selected Publications
1. R J Butcher, G Diven, G Erickson, J Jasinski, G M Mockler, R Y Pozdniakov, E Sinn, Inorg. Chim. Acta., 239, 107-116 (1995)
2. Ray J, Butcher, Garry Mockler, Owen McKern, Acta Cryst, E59, m20– m22 (2003)
3. Ray J. Butcher, Garry Mockler, Owen McKern, Acta Cryst. E59, m61-m63 (2003)
Chemistry Department Research Booklet Updated February 2007 Page 33
Dr Glennys O’Brien email: [email protected]
Research interests combine analytical and environmental chemistry with respect to water quality, in particular the behaviour of trace metals, both essential and toxic.
Trace metals in sediment systems
Because of the variable chemistry of complex formation / absorption / adsorption / redox / insolubility of metal species, the behaviour of metals in the aquatic environment is complex. Metals are most often associated with the solid phase either as suspended matter or deposited material. This behaviour is also dependent on chemical and physical conditions within the sediment system and in the overlying water. The bioavailability of toxic metals is a function of this chemical behaviour.
Particular interests
• The influence of the chemistry of sediment pore water on sediment trace metals behaviour, - identifying metal species, transport, cycling. • The chemical behaviour of metals in relation to the macrocomponents – organic carbon, nitrogen and sulfur. • The use of surface analysis - spectroscopic techniques to investigate the binding of metals to different mineral phases, especially the pyritic phases.
Water quality issues
The Illawarra Coast and Southern Highlands has been subjected to the normal run of historical development – development of farming, urbanisation, mining, and at Port Kembla in particular, heavy industry. All these activities have had and continue to have major impacts on the quality of various parts of the local physical environment. Particular interests: • The investigation of surface water quality in various catchments. • Stream sediment metals loadings within stream / drainage catchments. • Trace metal loadings and behaviour in the local streams and harbour systems.
Selected Publications
1 Jolley, D., O’Brien G. and Morrison J. 2003. Evolution of Chemical Contaminant and Toxicology Studies, Pt 1- An Overview. S. Pac. J. Nat. Sci., 21, 1-5.
2 O’Brien G., Jolley, D. and Morrison J. 2003. Evolution of Chemical Contaminant and Toxicology Studies, Pt 2 – case studies of Selenium and Arsenic. S. Pac. J. Nat. Sci., 21, 6-14.
3 Muhammad D., O’Brien G., Price W. and Chenhall B. 2005. Fractionation of sedimentary arsenic from Port Kembla Harbour, NSW, Australia. J. Environ. Monit., 7, 621-630.
Chemistry Department Research Booklet Updated February 2007 Page 34
Professor William E Price email: [email protected]
Research Interests
My research interests are concerned primarily with physical properties, particularly mass transfer, in fluids and porous media such as polymers and foods. It spans both pure research, studying interactions in fluid mixtures and their effect on the properties and structure of the system and applied research targeted at specific, often industry-driven, goals. At present there are four areas in which these interests are being pursued:
Electrofunctional Materials Food Analysis and Processing Analysis of trace pollutants in the environment Dynamic processes in complex liquids and mixtures
Electrofunctional Materials
In collaboration with Prof. Gordon Wallace and other members of the Intelligent Polymers Research Institute (IPRI) and the newly formed ARC Centre of Excellence for Electromaterials Science, I am engaged in research developing novel nanostructured materials for a range of potential applications including artificial muscles, actuators, energy storage and conversion, This group is at the forefront of materials research and is the Central player in the ARC Centre of Excellence for Electromaterials Science in collaboration with Monash and Massey Universities. A major theme of this new Centre is the use of nanostructured componentsmaterials with new and enhanced chemical and physical material properties and assembly into nanostructured electromaterials. One major focus of this research has been using inherently conducting polymers (ICP), in both thin films and in composite materials. ICP have unique properties including high electrical conductivity, flexibility, low density and a diverse range of possible chemistries. In addition, these polymers change their redox state and their chemical and physical properties on application of external potential.
A major focus of my work has been the use of ICP as stationary phases and membranes or in composite materials, amongst others, to affect separations of complex mixtures. This is the basis of a new, exciting separations technology. The advantage of the conducting layer is twofold. Firstly the unique redox properties may be used to enhance transport of ions across the film - indeed selective transport of species may be turned on and off and modulated through electrical stimulation. Secondly the rich diversity of chemical moieties that may be incorporated into such conducting polymer films as counterions (or neutral species) enables a wide range of surface chemistries to be produced. The conducting polymer is able to act as a thin selective passive layer as well as having inherent conductivity and redox properties. These advantages make such materials a rich source for novel device and other applications, such as metal ion separation and recovery. Current projects are focused on metal recovery and in collaboration with Prof. Doug MacFarlane of Monash University, the use of novel ionic liquids for novel electrochemical processing.
Chemistry Department Research Booklet Updated February 2007 Page 35 Selected Publications
1. J. Ding, W. E. Price, S. F. Ralph and G. G. Wallace “Electroless Recovery of Gold Chloride Using Inherently Conducting Polymers’, Polymer International 53,681-687 (2004).
2. J. Ding, W. E. Price, S. F. Ralph and G. G. Wallace, “Electroless Recovery of Gold Cyanide Using Inherently Conducting Polymers”, Polymer International, 52, 51-55 (2003).
3. J. Ding, V. Misoska, W.E. Price, S.F. Ralph, G Tsekouras and G.G. Wallace. “Gold recovery using fabric coated with conducting polymers” Synthetic Metals 135-136, 35-36, (2003).
Food Analysis and Food Processing
Mass transfer is often the rate-limiting step in extraction from foodstuffs. Experience has been built up in this area over nearly twenty years measuring the kinetics and equilibrium behaviour of solvent extraction from foodstuffs such as tea, coffee, citrus fruit and ginger. In addition, my research interest in tea and coffee processing has engendered another interest in extraction and analysis of food components, particularly ones that are bioactive ie have some biological action. At present there are two projects in progress.
The first area is studying methods of analysis of phytooestrogens in foods and the bioavailability of these important compounds in humans. Soy and linseed products have high phyooestrogens contents, particularly isoflavanols and ligans. These compounds have been implicated in a number of studies to have significant health benefits. This work is being carried out in conjunction with Assoc. Prof. Lee Astheimer of Department of Biomedical Sciences, University of Wollongong.
Figure 1: Isoflavones – an example family of phytoesotrogens
HOH2C HO O O O O HO hydrolysis OH HO
O OH OH OH O OH genistin genistein
HOH2C HO O O HO O O O HO OH hydrolysis HO reduction O OH O OH OH daidzin daidzein equol
The second area is that of chemical and physical changes during the processing of foods. Of particular interest of late have been studies on the effects of air and osmotic dehydration of temperate and tropical fruit. This builds on some developments in techniques previously. Osmotic dehydration is used as a pre-treatment to thermal / air drying to reduce the cost and time for drying and also sometimes to change the flavour and quality characteristics of the fruit. One major focus of the current work is on investigating how the uptake of sugars during the osmotic dehydration treatment modulates the chemical changes that occur during drying. In addition, there is another focus aimed at identifying changes in volatile profile of the food during processing as a method of quality assurance and looking for markers of undesirable changes caused by for example, caramelisation or Maillard reaction. These interests utilises SPME and GC/MS techniques for flavour analysis as well as HPLC analysis of carbohydrates.
Chemistry Department Research Booklet Updated February 2007 Page 36 Selected Publications
1. M. Ngyuen and W.E. Price, “ Air-drying of Banana: influence of experimental parameters, slab thickness, banana maturity and harvesting season. “ J. Food Engineering 79(1), 200-207 (2007).
2. T.A. Larkin, L. Astheimer and W.E. Price, Health Benefits of Phytoestrogens Agro Food Hi-Tech, 12(1), 19-23, (2001).
3. W.E. Price, H.T. Sabarez, R. Storey, and P.J. Back "The role of the waxy skin layer on moisture loss during dehydration of prunes," J. Agric Food Chem 48(9), 4193-4198, (2000).
4. H.T. Sabarez, W.E. Price and J.Korth. “Monitoring volatile changes during dehydration of d'Agen prunes" J. Agric. Food Chem 48(5), 1838-1842, (2000).
Analysis of trace pollutants in the environment
With the current interest in water reuse, there is a need to analyse low levels of micropollutants in water and environmental water samples. I am currently focused at developing methodologies for the analysis of a number of classes of trace pollutants in waste water, many of them of anthropogenic origin. These include hormones, pharmaceuticals, pesticides, plasticizers, detergents and phytooestrogens. These need to be analysed at very low levels to ascertain their extent in waste water and determine the ability of tertiary treatment processes in removing them, to enable the water to be reused. We have recently completed work as part of a highly successful collaboration with partners in Europe as part of the EU Aquarec project with our work funded through DEST International Science Linkage grant (Oz-Aquarec). My interest in the area stems from work done on analyzing phytoestrogens and other bioactives from foods and has led to the group developing robust LC-MS techniques for the analysis of low levels of phytoestrogens in environmental samples.
J. Kang, L. A. Hick and W. E. Price, “Simultaneous determination of isoflavones and lignans at trace levels in natural waters and wastewater samples using liquid chromatography/electrospray ionization ion trap mass spectrometry, Rapid Communications in Mass Spectrometry 20, 2411-2418, (2006).
Dynamics in Complex Liquids and Mixtures
Experimental measurements of dynamic physical properties of complex liquids and mixtures are important in furthering our understanding of the structure of the fluid phase and also of mixing and phase separation phenomena such as detergency and micellisation. In addition, data such as transport properties as a function of temperature and pressure is needed for engineering applications. The concept of the hydrophobic interaction is of great importance in protein folding and stability, membrane formation through aggregation of biomolecules, molecular recognition and other phenomena. Hydrophobic effects play an important part in a variety of solution processes ranging from self-assembly process in solution, surfactant micelle formation in aqueous solution and detergency and other surface phenomena through kinetic solvent effects in aqueous solvent mixtures to the behaviour of natural gas hydrates.
This concerns the structure and properties of proteins in solution. α s-Casein is a mammalian milk protein which has recently been shown to have chaperone-like properties. A chaperone protein is one that prevents self-assembly and uncontrolled aggregation of other proteins. Work is currently in progress in collaboration with Prof. John Carver, School of Chemistry and Physics, Adelaide investigating protein dynamics in solution using a variety of techniques including NMR.
Selected Publication
1. P. E. Morgan T. M. Treweek, R. A. Lindner, W. E. Price and J. A. Carver, “Casein proteins as molecular chaperones” J. Agric. Food Chemistry¸ 53¸2670-2683, (2005).
Chemistry Department Research Booklet Updated February 2007 Page 37
Professor Stephen Pyne email: [email protected]
Asymmetric Synthesis of Bioactive Molecules and Natural Products
New organic and organometallic reagents are being developed for the synthesis and asymmetric synthesis of natural products and biologically active molecules. Living organisms generally interact differently with the two hands (or enantiomers) of a molecule. Since many drugs contain chiral centres (ie are handed), it is often necessary to be able to control which enantiomer of a molecule is being synthesised. A well-known example is the tragic case of Thalidomide. One enantiomer had the desired therapeutic effect and relieved the symptoms of morning sickness in pregnant women, whilst the other enantiomer caused severe birth defects to the baby. A number of projects are being developed to prepare bioactive molecules as single enantiomers (hands). These projects involve modern methods of organic and organometallic synthesis, NMR spectroscopy and computer aided molecular modelling. Particular areas of research interest are:
Asymmetric Synthesis of Stemona Alkaloids
Extracts of the plants of the Stemonaceae family (Stemona and Croomia species) have been used as traditional medicines by the Chinese and Japanese to treat respiratory diseases such as bronchitis, pertussis, and tuberculosis and as antihelmintic agents. These plants contain a large number of alkaloids that have novel polycyclic structures. These unique structural features coupled with their interesting biological properties have stimulated the development of new synthetic methodology and synthetic strategies for the synthesis of these alkaloids in my research group and others.
Asymmetric Synthesis of Polyhydroxylated Pyrrolizidine and Indolizidine Alkaloids and their Analogues
Polyhydroxylated pyrrolizidine and indolizidine alkaloids are well known potent glycosidase enzyme inhibitors. For example the pyrrolizidine alkaloids austaline and casurine, and related alkaloids, are powerful inhibitors of glycosidase enzymes and thus exhibit antiviral and anti-HIV activity by effectively inhibiting the enzymatic processing of glycoproteins. We are currently developing a common synthetic strategy to these natural products to allow a better understanding of the structural requirements for glycosidase inhibition and to develop more potent, selective and less toxic drugs.
The Development of Novel Cyclic Peptoid Antibiotics (with J. Bremner and P. Keller)
The death rate from infectious diseases in the developed world has increased over the last decade. This has been due to a number of factors, including, increasing mobility of people from developed countries to less developed ones, increasing age of the general population, increasing numbers of transplant, cancer and AIDS patients who have lowered immunities to bacterial infections and the increasing numbers of bacterial species that have become multiply resistant to antibacterial drugs. The vancomycin group of antibiotics represents a last line of defence against methicillin-resistant Staphylococcus aureus and other gram-positive microorganisms. These antibiotics interfere with cell-wall biosynthesis by binding to the D- Ala-D-Ala terminus of the disaccharyl pentapeptide of the peptidoglycan of the bacterial cell wall, resulting in cell death. Recently vancomycin resistant bacteria have appeared. These bacteria have been identified as having a D-Ala-D-lactate terminus rather than a D-Ala-D-Ala terminus of the peptidoglycan. Vancomycin has a much lower affinity (ca. 1000 fold decrease in affinity) for the D-Ala-D-lactate terminus in vancomycin resistant bacteria and consequently it is much less effective as an antibiotic. Novel cyclic peptide analogues of vancomycin are being designed and synthesised that are much
Chemistry Department Research Booklet Updated February 2007 Page 38 more synthetically accessible than vancomycin itself and have potentially a high affinity for the D-Ala-D-lactate terminus of vancomycin resistant bacteria.
Regioselective Functionalization of Fullerenes: New Three Dimensional Templates for Drug Delivery and the Design of New Pharmaceuticals and Catalytic Asymmetric Synthesis (with Dr P. Keller).
The fullerene surface potentially offers many possibilities for preparing novel multifunctionalized 3-dimensional surfaces with potential applications in drug delivery, as anti-viral agents, in photodynamic therapy and chemical asymmetric catalysis. We are thus developing chemistry to regioselectively prepare multifunctionalized fullerenes and fulleryl-amino acids and their peptide derivatives. We plan to examine their effects on biological systems.
Phytochemical and Synthetic Studies of Stemona Akaloids
In collaboration with scientists from the University of Changi Mai in Thailand we are examining the phytochemistry and biological chemistry of the root extracts of Stemona species of plants. Extracts of the roots of these plants have been used as traditional medicines by the Chinese and Japanese to treat respiratory diseases such as bronchitis, pertussis, and tuberculosis and as antihelmintic agents. Recently we discovered 3 new Stemona alkaloids, with a novel pyrido[1,2- a]azepine A,B-ring system, from a root extract of S. curtisii Hook. f., growing in Southern Thailand. We are currently examining the phytochemistry and biological activities of other Stemona plants in Thailand.
Selected Recent Publications
4. Regioselective synthesis of novel e-edge-[60]fullerenylmethanodihydropyrroles and1,2-dihydromethano[60]fullerenes, L. Chaker, G. E. Ball, G. A. Burley, B. C. Hawkins, J. R. Williams, P. A. Keller, and S. G. Pyne, Eur. J. Org. Chem. 2005, 5158-5162.
5. Phytochemical Studies on Stemona Plants: Isolation of New Stemofoline Alkaloids, T. Sastraruji, A. Jatisatienr, S. G. Pyne, A. T. Ung, W. Lie and M. C. Williams, J. Nat. Prod. 2005, 68, 1763-1767.
6. Asymmetric Synthesis of Anti-1,2-Amino Alcohols via the Borono-Mannich Reaction: A Formal Synthesis of (-)- Swainsonine, C. W. G. Au and S. G. Pyne, J. Org. Chem. 2006, 71, 7097-7099.
7. Synthesis of some cyclic indolic peptoids as potential antibacterials, V. S. Au, J. B. Bremner, J. Coates, P. A. Keller, S. G. Pyne, Tetrahedron, 2006, 62, 9373-9382.
8. Phytochemical Studies on Stemona Plants: Isolation of New Tuberostemonine and Stemofoline Alkaloids, T. Sastraruji, A. Jatisatienr, S. G. Pyne, A. T. Ung, W. Lie and M. C. Williams, Nat. Prod. Commun., 2006, 1, 813-818.
Chemistry Department Research Booklet Updated February 2007 Page 39
Dr Stephen Ralph email: [email protected]
Towards Transcription Therapy using Metallointercalators
Transcription therapy is the treatment of cancer by blocking or re-activating transcription factors displaying aberrant behaviour arising from inherent or acquired damage to DNA. The attractiveness of this approach lies in recognising while the origins of cancer are numerous; its onset is usually a result of incorrect processing of information via a small but pivotal group of over-expressed or mutated transcription factors. Our ultimate aim is to design and synthesise metallointercalators that can compete with these transcription factors for their binding sites on DNA or other proteins. As a first step we have been developing the use of electrospray ionisation mass spectrometry for studying the binding of ruthenium metallointercalators to DNA. This work is now being extended to novel metallointercalators containing other metal ions and ancillary ligands designed to enhance DNA affinity and selectivity.
Separation and Recovery of Precious Metals using Conducting Polymers
Conducting polymers are unique materials that combine the physical properties of classical polymeric materials with the electrical conductivity of metals. They are currently being intensely investigated for a variety of applications, including novel sensors, corrosion control, electrochromic displays, photovoltaic devices and artificial muscles. We are exploring several of these areas, including the ability of conducting polymer membranes, powders and composite materials to recover precious metals by an electroless mechanism. This method has already been shown to recover large amounts of gold from solutions - containing [AuCl4] in a facile and highly selective fashion. Currently we are examining the extension of this work to recovery of other metals such as silver, platinum, palladium and rhodium. In addition we are also investigating the use of conducting polymer membranes as electrochemically controllable, selectively permeable barriers to metal ions. Current efforts are aimed at enhancing the permeability and selectivity of these membranes by incorporation of metal complexing agents, or the use of nanoparticles to modify pore size.
Bioinorganic Chemistry of Metallodrugs
Cisplatin is one of the worlds most widely used anticancer drugs, and is especially effective against testicular cancer. A great deal is known about the mechanism of action of cisplatin, including its interactions with DNA. However, some recent studies have pointed to one particular DNA lesion, in which cisplatin binds to a GA sequence on one strand of DNA, being more prevalent than previously thought. We are currently examining this proposal using a combination of HPLC, electrospray ionisation mass spectrometry (ESI-MS) and nmr spectroscopy. A second project uses ESI-MS to examine the binding of antiarthritic gold drugs and their metabolites to proteins including serum albumin, hemoglobin and metallothionein.
Molecular Cages for Metal Ions
The metal ion chemistry of macrobicyclic hexaamine ligands such as sepulchrate and sarcophagine has been extensively investigated. These ligands act as molecular cages, effectively encapsulating metal ions in an organic coat and shielding them from the external environment. The tremendous stability of metal cage complexes has been exploited to enable the study of otherwise labile or unstable metal ions, and has been investigated for a number of applications including development of novel metallo-radiopharmaceuticals and treatment of heavy metal ion poisoning. We wish to explore the
Chemistry Department Research Booklet Updated February 2007 Page 40 metal ion chemistry of the cage ligands Me5tricosane and Me8tricosane, which are analogues of sepulchrate and sarcophagine featuring slightly larger internal cavities. The latter property has already resulted in some unprecedented chemistry for the metal ion complexes of these ligands. For example, the cobalt(II) complex of Me8tricosane is the only known stable Co(II) hexamine complex, while the Cd(II) and Hg(II) complexes of Me5tricosane are rare examples of hexaamine complexes with exact trigonal prismatic stereochemistry. The main focus of this project will be the exploration of the spectroscopic, structural and magnetic properties of iron complexes of both ligands, as well as a more extensive survey of the metal complexation chemistry of Me8tricosane.
Selected Publications
1. 1. J.L. Talib, J.L. Beck and S.F. Ralph, "A Mass Spectrometric Investigation of the Binding of Gold Antiarthritic Agents - and the Metabolite [Au(CN)2] to Human Serum Albumin", Journal of Biological Inorganic Chemistry, 11, 559 (2006).
2. R. Dimeska, P.S. Murray, S.F. Ralph and G.G. Wallace, "Electroless Recovery of Silver by Inherently Conducting Polymer Powders, Membranes and Composite Materials", Polymer, 47, 4520 (2006).
3. D.A. Reece, S.F. Ralph and G.G. Wallace, “Metal Transport Studies on Inherently Conducting Polymer Membranes Containing Cyclodextrin Dopants”, Journal of Membrane Science, 249, 9 (2005).
4. R. Gupta, J.L. Beck, M.M. Sheil and S.F. Ralph, “Identificationo of Bifunctional GA and AG Intrastrand Crosslinks Formed Between Cisplatin and DNA”, Journal of Inorganic Biochemistry, 99, 552 (2005).
5. J. Ding, W.E. Price, S.F. Ralph and G.G. Wallace, “Electroless Recovery of Gold Chloride Using Inherently Conducting Polymers”, Polymer International, 53, 681 (2004).
6. J.L. Beck, S. Ambehara, S.R. Yong, M.M. Sheil, J. de Jersey and S.F. Ralph, “Direct Observation of Covalent Adducts with Cys34 of Human Serum Albumin using Mass Spectrometry”, Analytical Biochemistry, 325, 326 (2004).
7. T. Urathamakul, J.L. Beck, M.M. Sheil, J.R. Aldrich-Wright and S.F. Ralph, “A Mass Spectrometric Investigation of Non- Covalent Interactions Between Ruthenium Complexes and DNA”, Dalton Transactions, 2683 (2004).
8. V. Misoska, J. Ding, J.M. Davey, W.E. Price, S.F. Ralph and G.G. Wallace, “Polypyrrole Membranes Containing Chelating Ligands: Synthesis, Characterisation and Transport Studies”, Polymer, 42(21), 8571 (2001).
9. J.L. Beck, M.L. Colgrave, S.F. Ralph and M.M. Sheil, “Electrospray Ionization Mass Spectrometry of Oligonucleotide Complexes with Drugs, Metals and Proteins”, Mass Spectrometry Reviews, 20, 61 (2001).
Chemistry Department Research Booklet Updated February 2007 Page 41
Professor Margaret M Sheil email: [email protected]
Biological Mass Spectrometry
Mass spectrometry has long held central importance as an analytical tool in chemistry and recent developments have seen it increasingly being integrated into biological and biomedical research. This has followed from the development of new techniques i.e. electrospray ionisation (ESI) and matrix-assisted laser desorption ionisation (MALDI) which have extended the range of mass spectrometry up to 200,000 Da. These techniques have opened the way for mass spectrometry to be used for the analysis and structure determination of important biological molecules, such as proteins and DNA. The Department of Chemistry has a world-class mass spectrometry facility, which includes both low and high resolution electrospray mass spectrometers (including a state-of-the-art QTOF), a MALDI-TOF mass spectrometer and facilities for GC/MS and LC/MS.
The underlying theme of Professor Sheil’s research involves the development and application of new analytical methods based on mass spectrometry for the characterisation of biopolymers, focusing particularly on systems that are not well understood and represent a significant challenge for analysis (such as DNA, large proteins and fragile macromolecular complexes). This is complemented by work in applying these methods to address important biological/chemical questions. Thus, she has a major program concerned with the study of nucleic acid (i.e. DNA) constituents and the interactions of DNA with anti-cancer drugs. The analysis of DNA by mass spectrometry requires considerable experimental and interpretive skills, and papers resulting from this work to date are likely to have broader implications for the analysis of biomolecular complexes involving DNA, especially in relation to anti-cancer drug design. Most recently, in collaboration with Dr Jennifer Beck (see her entry) this work has been directed towards the study of protein-DNA complexes and protein-protein complexes involved in DNA replication.
Selected Publications
1. P. Iannitti, M.M. Sheil and G. Wickham “High sensitivity and fragmentation specificity in the analysis of drug-DNA adducts by electrospray tandem mass spectrometry” Journal of the American Chemical Society (1997), 119, 1490-1491
2. M.L. Colgrave, P. Iannitti-Tito, G. Wickham and M.M. Sheil “Rapid determination of sequence selectivity and stability of alkylated oligonucleotide adducts by electrospray tandem mass spectrometry” Australian Journal of Chemistry (2003), 56, 401-413
3. J.L. Beck, M. L. Colgrave, S.F. Ralph and M.M. Sheil “Electrospray ionisation mass spectrometry of oligonucleotide complexes with drugs, metals and proteins” Mass Spectrometry Reviews (2001) 20, 61-87
4. A. Kapur, J.L. Beck, S.E. Brown, N.E. Dixon and M.M. Sheil “Use of electrospray ionization mass spectrometry to study binding interactions between a replication terminator protein and DNA” Protein Science (2002) 11(1), 147-57
5. O.K. Bernhard, J.A. Burgess, T. Hochgrebe, M.M. Sheil and A.L. Cunningham “Mass spectrometry analysis of CD4- associating proteins using affinity chromatography and affinity tag-mediated purification of tryptic peptides” Proteomics (2003), 3, 139-146.
Chemistry Department Research Booklet Updated February 2007 Page 42
Dr Danielle Skropeta email: [email protected]
Marine Natural Products Chemistry The research is aimed at discovery of new types of drugs based on bioactive metabolites produced by shallow and deep- sea marine organisms. The main techniques used are: bioassay-guided fractionation of marine natural product extracts; purification of bioactive metabolites using a combination of ion-exchange, gel filtration and high-performance liquid chromatography (HPLC); and structural elucidation of metabolites employing the latest experiments in high-field, 1D and 2D nuclear magnetic resonance spectroscopy and mass spectrometry (MS).
Glycosylated Natural Products from Marine Organisms O Glycosylated natural products (GNPs) have recently emerged as a leading O OH OH force in the fight against microbial infection and cancer. In fact, many drugs CH2OH currently in use are GNPs, e.g. doxorubicin. Until now, the marine environment has been largely ignored as a source of GNPs, due to the challenging nature OCH OOHO of isolating water-soluble GNPs from marine extracts. This project is aimed at 3 H C O developing high-throughput profiling of marine-derived GNPs, employing the 3 carbohydrate portion latest techniques in carbohydrate separation and identification in order to HO NH2 improve access to this valuable pool of potential new drugs. doxorubicin
The Discovery of New Anticancer Agents from Australia’s Unique Marine Fauna Sessile marine organisms rely on chemical defence for their survival by producing toxins that target their prey, predators and competitors. This project aims to harness these natural marine toxins and exploit their pharmaceutical potential as new anticancer agents. In collaboration with A/Prof. Marie Ranson (Biological Sciences), a variety of marine organisms (sponges, tunicates, echinoderms) will be screened for their cytotoxic activity. Promising extracts will be separated using bioassay-guided fractionation, purified by chromatography and their structures identified using various spectroscopic experiments. Identifying novel classes of anticancer agents from Australia’s unique marine fauna is an exciting new challenge in the area of anticancer research.
Deep-Sea Research: Metabolite Profiling of Deep-Sea Marine Invertebrates Australia’s deep-sea organisms (>100m depth) are unexplored in terms of their chemistry. In collaboration with the petroleum industry, we have access to cutting edge ROV (remotely operated vehicle) technology, capable of sampling to a depth of 3000 m. As part of a global study on the effect of drilling on the sustainability of deep-sea ecosystems, the project will examine the production of secondary metabolites by marine organisms inhabiting drill zones. Metabolite profiles of deep- sea organisms (100-500m depth) from both inside and outside drilling areas will be generated using LC-MS (electrospray ionization) and tandem LC-MS/MS, compared and analysed. High-level purification, structural elucidation and biological evaluation of metabolites of interest will also be performed. This adventurous project is bound to uncover exciting new findings about Australia’s deep-sea environment.
Chemistry Department Research Booklet Updated February 2007 Page 43 Selected publications 1. Skropeta, D., Jolliffe, K.A., Turner, P. (2004) Pseudoprolines as removable turn inducers: Tools for the cyclization of small peptides. J. Org. Chem. 69: 8804-8809. 2. Skropeta, D., Schwörer, R., Haag, T., Schmidt, R.R. (2004) Asymmetric synthesis and affinity of potent sialyltransferase inhibitors based on transition-state analogues. Glycoconjugate J. 21: 205-219. 3. Guella, G., Skropeta, D., Mancini, I., Pietra, F. (2003) Calenzanane sesquiterpenes from the red seaweed laurencia microcladia from the bay of calenzana, elba island: Acid-catalyzed, stereospecific conversion of calenzanol into indene- and guaiazulene-type sesquiterpenes. Chem. Eur. J. 9: 5770-5777. 4. Guella, G., Skropeta, D., Breuils, S., Mancini, I., Pietra, F. (2001) Calenzanol, the first member of a new class of sesquiterpene with a novel skeleton isolated from the red seaweed Laurencia microcladia.Tetrahedron Lett. 42: 723- 725. 5. Rickards, R.W., Skropeta, D. (2002) Electrocyclic processes in aromatic biosynthesis: biomimetic study of pseudorubrenoic acid A.Tetrahedron 58: 3793-3800.
Chemistry Department Research Booklet Updated February 2007 Page 44
Professor G G Wallace email: [email protected]
Intelligent Polymer Research
This large research program involves the synthesis and characterisation of novel conducting polymers based on polypyrrole, polyaniline and polythiophenes. Fundamental studies are being carried out investigating how these so-called ‘intelligent’ materials interact with their chemical and physical environment. A range of applications are also being actively explored, including their use as novel membrane and chromatographic materials in chemical separations technology, as well as their use as selective chemical and biochemical sensors and as protective coatings against, for example, corrosion. The use of these new polymers as photovoltaic coatings and artificial muscles is also under investigation. Another development (in collaboration with Professor L Kane-Maguire) is the design and synthesis of chiral conducting polymers and their use in the electrochemical asymmetric synthesis of drugs and for the separation of chiral chemicals. The research team is multidisciplined with expertise in chemistry, biochemistry, engineering, mathematics and instrumentation development. Many of our projects also involve close collaboration with industry such as BHP, Rio Tinto, Polartechnics and Cochlear Pty. Ltd. We have also formed a strategic alliance with the CSIRO Division of Chemicals and Polymers, as well as Technical Fibres and Textiles. In addition we have established international collaborative activities with research groups in the USA, Japan and Europe. Many of our graduate students spend time in our collaborator's laboratories in Australia or overseas.
Selected Publications
1. W. Lu, A.G. Fadeev, B. Qi, E. Smela, B.R. Mattes, J. Ding, G.M. Spinks, J. Mazurkiewicz, D. Zhou, G.G. Wallace, D.R. MacFarlane, S.A. Forsyth, M. Forsyth “Use of Ionic Liquids for -conjugated Polymer Electrochemical Devices” Science. 2002, 297, 983-987.
2. R. H. Baughman, C. Cui, A. A. Zakhidov, Z. Iqbal, J.N. Barisci, G. M. Spinks, G. G. Wallace, A. Mazzoldi, D. De Rossi, A. G. Rinzler et al., “Carbon nanotube actuators” Science. 1999, 284 (5418), 1340-1344.
3. G.M. Spinks, L. Liu, D. Zhou, and G.G. Wallace, “Strain response from polypyrrole actuators under load” Advanced Functional Materials. 2002, 12 (6-7), 437-440.
4. Geoffrey M. Spinks, Gordon G. Wallace, Leonard S. Fifield, Larry R. Dalton, Alberto Mazzoldi, Danilo De Rossi, Ilyas I. Khayrullin, and Ray H. Baughman, “Pneumatic Carbon Nanotube Actuators,” Advanced Materials. 2002, 14 (23), 1728- 1732.
5. M. R. Gandhi, P. Murray, G. M. Spinks, and G. G. Wallace, “Mechanism of electromechanical actuation in polypyrrole” Synth. Met. 1995, 73 (3), 247-56.
6. Sadik, O.A., Wallace, G.G. “Pulsed amperometric detection of proteins using antibody containing conducting polymers” Analytica Chimica Acta. 1993, 279, 209-212.
Chemistry Department Research Booklet Updated February 2007 Page 45 7. Majidi, M., Kane-Maguire, L., Wallace, G.G. “Enantioselective Electropolymerisation of Aniline in the Presence of (+) or (-) Camphorsulfonate Ion: A Facile Route to Conducting Polymers with One-Screw-Sense Helicity” Polymer. 1994, 35, 3113-3115.
8. Barisci, J.N., Mansouri, J. Spinks, G.M., Wallace, G.G., Kim, C.Y., Kim, D.Y., Kim, J.Y. “Electrochemical preparation of polypyrrole colloids using a flow cell” Colloids and Surfaces. 1997, 126, 129-135.
9. Innis, P.C., Norris, I.D., Kane-Maguire, L.A.P., Wallace, G.G. “Electrochemical Formation of Chiral Polyaniline Colloids Codoped with (+)- or (-)-10-Camphorsulfonic Acid and Polystyrene Sulfonate” Macromolecules. 1998, 31 (19), 6521- 6528.
10. Gao, M., Huang, S., Dai, L., Gao, R., Wang, Z., Wallace, G.G. “Aligned Coaxial Nanowires of Carbon Nanotubes Sheathed with Conducting Polymers” Angewandte Chemie. 2000, 39 (2), 3664-3667.
Chemistry Department Research Booklet Updated February 2007 Page 46
Associate Professor S R Wilson e-mail: [email protected]
Atmospheric Chemistry
A number of research areas are being currently pursued:
Isotopic signatures and emission strengths of Greenhouse gases
Quantifying the emissions of greenhouse gases is very important for the long-term management of greenhouse gases in the atmosphere. The emissions are often from a wide range of sources and difficult to quantify. We have been working on the use FTIR spectroscopy to determine both the strength of emissions from various sources, and the isotopic signature of the emitted gases. Our initial focus is on N2O, and the isotopic label of the two (chemically distinct) nitrogen atoms within the molecule. Projects underway currently are looking at the variations in the atmosphere and studies of soils, estuarine systems and anthropogenic sources. Studies are also underway using low-resolution FTIR spectroscopy to quantify concentrations of a range of key gases (N2O, CO2, CH4, CO) in urban and environments.
Ultraviolet/ Visible Solar Radiation
The measurement of UV-B radiation is important for the assessment of the impact of stratospheric ozone depletion and climate change, as UV-B radiation drives much of atmospheric chemistry. Work at the Cape Grim Baseline Air Pollution Station, Australia’s background atmospheric monitoring station is studying changes in UV photolysis rates with time. There are also studies of the changes in solar radiation with particular emphasis on the impact of aerosol (dust) on the amount of light reaching the earth’s surface, and how this is changing with time. The measurement techniques are also being used to study biomass burning emissions, combining the molecular information available from remote sensing FTIR methods and the aerosol property information provided by visible radiation measurements.
Selected publications:
1. Andrady, A., et al. (2006), Environmental effects of ozone depletion and its interactions with climate change: Progress report, 2005, Photoch Photobio Sci, 5(1), 13 - 24, DOI: 10.1039/b515670j.
2. Paton-Walsh, C., N. B. Jones, S. R. Wilson, V. Haverd, A. Meier, D. W. T. Griffith, and C. P. Rinsland (2005), Measurements of trace gas emissions from Australian forest fires and correlations with coincident measurements of aerosol optical depth, J. Geophys. Res., 110, D24305, doi:10.1029/2005JD006202.
Chemistry Department Research Booklet Updated February 2007 Page 47 3. Solomon, K.R., X. Tang, S.R. Wilson, P. Zanis, and A.F. Bais, Changes in tropospheric composition and air quality due to stratospheric ozone depletion, Photochemical and Photobiological Science, 2, 62-67, 2003.
4. Wilson, S.R., and B.W. Forgan, Aerosol optical depth at Cape Grim, Tasmania 1986-1999, Journal of Geophysical Research, 107 (D8), DOI 10.1029/20001JD000398 (8pp), 2002.
5. Turatti, F., D.W.T. Griffith, S.R. Wilson, M.B. Esler, T. Rahn, H. Zhang, and G.A. Blake, Positionally dependent 15N fractionation factors in the UV photolysis of N2O determined by high resolution FTIR spectroscopy, Geophysical Research Letters, 27 (16), 2489-2492, 2000.
6. Esler, M.B., D.W.T. Griffith, S.R. Wilson, and L.P. Steele, Precision trace gas analysis by FTIR spectroscopy 1. Simultaneous analysis of CO2, CH4, N2O and CO in air, Analytical Chemistry, 72 (1), 206-215, 2000.
7. Esler, M.B., D.W.T. Griffith, S.R. Wilson, and L.P. Steele, Precision trace gas analysis by FTIR spectroscopy 2. 13 12 The C/ C isotope ratio in CO2, Analytical Chemistry, 72 (1), 216-221, 2000.
Chemistry Department Research Booklet Updated February 2007 Page 48
MAJOR EQUIPMENT
NMR
Varian Mercury-VX 300 MHz NMR spectrometer with • 1H/19F/31P/13C + 15N 5mm Autoswitchhabe PFG probe • 1H/19F/31P/13C + 15N 5mm PFG 4NUC DM probe
Varian Inova 500 MHZ NMR spectrometer with • Triple axis gradients and triple rf channels • Ultra 40 Channel shims • FTS system temperature controller • Triax 5mm 1H/13C/15N Triple Nucleus PFG probe • gHx Nano magic angle spinning probe • DOTY 8mm-1H/13C/15N/19F/27Al/23Na broadband diffusion probe
Varian VNMRS 500 MHZ NMR spectrometer with • Dual rf channels • Z pulse-field gradients • 28 Channel shims • Liquid application module • FTS system temperature controller
• Pro-tune dual drive module • 1H 15N-31P 5mm PFG AutoX Indirect Detect probe • 1H-19F/15N-31P 5mm PFG AutoX Indirect Detect probe • 15N – 31P[1H] 4mm Broadband indirect Nano Access to probe • Bruker DMX-600 MHz NMR spectrometer (at UNSW) • Bruker Avance 800 MHz spectrometer (at ANU)
MS
Shimadzu QP 5000 GC/MS: EI, pos CI, DI Shimadzu QP 5050A GC/MS: EI, pos/neg CI, DI VG Autospec-oa-TOF high resolution mass spectrometer with EI, CI, DI and MS/MS Micromass M@LDI - MALDI Mass Spectrometer Micromass Platform LCZ: LC / MS Micromass Quattro micro LCZ: LC-MS/MS Micromass Q-TOF-ULTIMA with capillary LC and nanoelectrospray interfaces and extended mass range Thermo Finnigan LTQ: LC/MSn
Chemistry Department Research Booklet Updated February 2007 Page 49
HPLC / GC
Extensive HPLC facilities (11 units, including preparative capillary and microbore units) with a range of detection options (fluorescence, conductivity, uv-visible, refractive index, electrochemical and evaporative light scattering) Pharmacia 2D Gel electro- phoresis equipment Several gas chromatographs
Computers
Modelling computers: • SGI O2's (IRIX 6.5) • SGI Hydrogen's (IRIX 6.5) • 1 SGI Fuel (IRIX 6.5) • 1 Dell PowerEdge 2800 (Linux 2.6) • Sun Ultra20's (Linux 2.6) These computers provide access to Insight II, Catalyst, Spartan, Autodock and Gaussian '03. Grad/Postgrad computing laboratory (12 Dell Desktops with MS Windows XP)\ 3 Dell Precision Workstations (Linux 2.6) for use on NMR spectrometers
AA
Varian Spectra. AA 220 Atomic Absorption Spectrometer GA-76 Vapour generation accessory Instrumentation Lab 451 Atomic absorption spectrometer Varian Sequential ICP-OES
Electrochemical Instruments
Extensive electrochemical equipment for cyclic voltammetry, differential pulse, and anodic and cathodic stripping studies An Electrochemical Mapping Facility comprising: i.PAR/UniScan Model SVP100-P Scanning Vibrating Reference Electrode System ii. Solartron/UniScan 1275 Localised Electrochemical Impedance (LEIS) System Raman spectrometry Mapping Facility comprising: Lab Raman Infinity Spectrometer (632.8 & 784.8nm) with Confocal Microscope (Jobin Yvon) and PAR Potentiostat/Galvanostat for electrochemical Raman maping. Electrochemical Quartz Crystal Microbalance Jobin Yvon SPEX Fluorolog FL22 Spectrofluorometer (Double gratings on source and emission) Bruker EMX Electron Spin Resonance Spectrometer with an electrochemical head & cryostat. Shimadzu UV MultiSpec 1501 diode array spectrometer (190-800nm, 10Hz sample rate)
UV / VIS / IR / CD / Fluorescence
Bruker 125 high resolution FTIR spectrometer Bomem MB 100 FTIR spectrometers (5) Nicolet Avatar 360 FTIR spectrometer (3) Shimadzu uv-160 uv-visible spectrophotometer Shimadzu uv-265 uv-visible spectrophotometer Jobin Yvon CD6 circular dichroism spectrometer Shimadzu UV1601-PC uv-vis Cary500 UV/VIS/NEAR IR spectrophotometer Hitachi F4500 Fluorimeter
Chemistry Department Research Booklet Updated February 2007 Page 50
OTHERS
Isco Capillary electrophoresis system Rigaku Thermogravimetric analyser Perkin Elmer 241 polarimeter Biorad Biological Protein Purification System Waters and Shimadzu gel permeation chromatography
The Department’s extensive range of equipment may be utilised by external institutions, agencies and companies interested in the analysis of environmental, biological and industrial samples. For further information and cost estimates, please contact Dr John Korth (ph 4221 3513), Ms Louisa Willdin or Ms Carol Weall (ph 4221 3509).
Chemistry Department Research Booklet Updated February 2007 Page 51
RESEARCH FUNDING
The Department of Chemistry has been consistently successful in obtaining funding from external sources with a high proportion of both National Government Competitive Grants and Industry funding for its research activities. This funding has grown substantially as the research intensity and post-graduate numbers have increased. As a result the total external funding has typically exceeded A$2 million dollars over the last five years as shown in the graph below and increasing steadily. The graph also illustrates the range and relative contribution of both Government and Industry sponsorship. Both Australian and overseas government agencies such as the US Army and Navy research Offices have sponsored research in the Department for a number of years. The Department has been highly successful at securing industry funding and some research groups have long term research arrangements or alliances with companies. These include Avexa, BlueScope, Johnson and Johnson, Cochlear and Rio Tinto.
Department of Chemistry External funding
7.00
6.00
5.00
ARC 4.00 NHMRC OTHER GOV INDUSTRY
A$ Million A$ 3.00 TOTAL
2.00
1.00
0.00 2000 2001 2002 2003 2004 2005 Year
Chemistry Department Research Booklet Updated February 2007 Page 52 Current Successful Grants
Australian Research Council Discovery Projects
Biomass Burning Emissions? An Innovative Technique for Assessing Global Climate Impacts Dr NB Jones (Chemistry UoW) Prof DJ Jacob; Dr RM Mitchell; Mr MD Fromm; Dr SW Wood; Dr DP Edwards Total Funding (2005 to 2007) $472,000 This proposal will significantly improve our understanding of the impacts of biomass burning on climate and environmental change leading to better predictive powers and more informed political and economic responses to issues such as Australian compliance with international protocols dealing with global climate change (Kyoto). Further, it will help the development of Australian expertise in global chemical transport modelling not currently addressed by other Australian research programs.
Elucidation of key properties for device development Novel Carbon Nanotube Composite Materials Dr AI Minett (IPRI/Chemistry UoW) Total Funding (2005 to 2009) $705,000 As the former co-director of CSIRO Nanotechnology indicated to the Sydney Morning Herald in 2003, 'Nanotechnology will lead us into a very different future.' The proposed research on nanomaterial interactions and biomolecular incorporation protocols will provide a foundation for future bioelectronic devices. Imagine healthcare of human diseases when nanocomponents enable the design of new platforms for devices that give point-of-care diagnosis, or the impact on the semiconductor industry with the creation of flexible electronics. Educational outreach is an important aim of the
project, providing effective research training for
early career researchers.
Supported Molecular Catalysts for Methanol Oxidation and Other Reactions Prof GG Wallace (IPRI/Chemistry UoW); Dr J Chen (IPRI/Chemistry UoW) Dr GF Swiegers Total Funding (2005 to 2007) $361,000 Knowledge arising from these fundamental studies has the potential to place Australia at the forefront of this important area of materials science and catalysis. We expect to make discoveries that will be useful not only in the area of catalysts for the direct methanol fuel cell, but also in systematising and developing the whole field of bio-mimetic supported electrocatalysts. Relevant findings in these exciting areas will be relayed to researchers and commercialised where appropriate. This multidisciplinary project will also provide an excellent environment for research training.
Gas Phase Dynamics of a Biological Molecular Machine: Fundamentals, Stoichiometries and Stabilities Dr JL Beck; Prof MM Sheil (Chemistry, UoW) Total Funding (2006 to 2008) $260,000 Over the last twenty years advanced molecular measurement techniques have enabled the characterization of individual biological molecules (proteins and DNA) within different types of cells and diseased tissues. This project uses a new technique that literally "weighs" groups of proteins and/or DNA to help us understand how such large molecules fit together and function within cells (sometimes referred to as molecular machinery). More detailed knowledge of processes such as those involved in copying DNA when new cells are produced will, in the long term, improve our understanding and treatment of conditions or diseases that result from errors in molecular machinery.
Chemistry Department Research Booklet Updated February 2007 Page 53 Asymmetric Synthesis and Biological Evaluation of Bioactive Alkaloids and their Analogues Category: 2503 - Organic Chemistry Project Prof SG Pyne (Chemistry, UoW) Total Funding $2006 $ 2007 $ 2008 Total $135,000 $120,000 $130,000 $385,000
We propose to develop innovative methods for preparing bioactive natural products and their analogues with potential applications as new and safer therapeutic drugs and agricultural chemicals. This project would make important scientific contributions to the advancement of the fundamentals of synthetic organic chemistry and contribute to Australia's development as a knowledge-based economy. The methodology and products developed may have potential pharmaceutical and agricultural applications from which the country could benefit from in the future. This project would help developed skilled people that may develop innovative outcomes in the future, especially in the developing pharmaceutical and biotechnology industries in Australia.
Australian Research Council Linkage Projects
Novel, Cost-Effective Methods for Measuring Methane Emissions from Grazing Livestock Prof DW Griffith (Chemistry, UoW) Dr RJ Eckard; Dr C Grainger; Dr H Clark Industry Partner: Department of Primary Industry Total Funding (2005 – 2007) $144,844 Agriculture is second only to energy generation as a source of greenhouse gas emissions in Australia. Methane from cattle and sheep constitute 60% of these agricultural emissions. Their abatement is a win-win goal for the agricultural industry, reducing greenhouse emissions while increasing food efficiency. This project will develop a novel, cost- and-labour efficient method for on-farm measurements of the emissions of methane from free-grazing cattle and sheep in their undisturbed environment. The method will be used to assess the dependence of methane emissions on factors such as diet and the efficacy of proposed methods for abatement of methane emissions, as well as providing improved data to the National Greenhouse Gas Inventory.
Lipidomics Associated with Metabolic Syndrome, Aging and Metabolic Variation between Species Dr SJ Blanksby (Chemistry, UoW) A/Prof PL Else; A/Prof AJ Hulbert Industry Partner(s): AstraZeneca Total Funding (2004 to 2007) $150,000 The aim is to apply state-of-the-art mass spectrometry to identify and quantify alterations in membrane lipidomes (i.e. lipid classes, molecular species, structure alterations and by-products) related to two major health problems facing Australia i.e. the Metabolic Syndrome and an Ageing population plus insight into the variation in metabolic rate between organisms. This research offers the opportunity for the development of mass spectrometry based technologies for the early clinical diagnosis of metabolic disorders plus provides a template of information for our Linkage partner (AstraZeneca) to develop pharmaceutical therapies targeting key molecular lipid species identified as critical to particular membrane functions.
Why is ColorbondR steel greener on the other side of the fence? Designing additives to retard weathering of surface coatings Dr SJ Blanksby (Chemistry, UoW) Dr PJ Barker Industry Partners: BlueScope Steel Research Total Funding 2007 to 2009 $117,354 COLORBONDR steel, the flagship pre-painted steel product of BlueScope Steel Limited, has become an iconic part of both suburban and outback landscapes whether installed as roofing, walling or water conservation accessories (tanks, down- pipes etc). This proposal aims to provide a detailed understanding of molecular level changes in COLORBOND® steel surface coatings brought about by levels of heat and radiation encountered in-service. These insights will lead to further improvements in both lifetime and aesthetic durability of COLORBONDR steel, ensuring continuing economic success of BlueScope in the domestic building market with consequent benefits to manufacturing communities throughout the supply- chain nationwide.
Chemistry Department Research Booklet Updated February 2007 Page 54 Novel, Cost-Effective Methods for Measuring Methane Emissions from Grazing Livestock Prof DW Griffith (Chemistry, UoW) Dr RJ Eckard; Dr C Grainger; Dr H Clark Industry Partner: Department of Primary Industry Total Funding (2005 to 2007) $144,844 Agriculture is second only to energy generation as a source of greenhouse gas emissions in Australia. Methane from cattle and sheep constitute 60% of these agricultural emissions. Their abatement is a win-win goal for the agricultural industry, reducing greenhouse emissions while increasing food efficiency. This project will develop a novel, cost- and-labour efficient method for on-farm measurements of the emissions of methane from free-grazing cattle and sheep in their undisturbed environment. The method will be used to assess the dependence of methane emissions on factors such as diet and the efficacy of proposed methods for abatement of methane emissions, as well as providing improved data to the National Greenhouse Gas Inventory.
Australian Research Council Linkage Infrastructure
Ultra-High Resolution NMR Imaging System for Nanotechnology including Nanobiotechnology A/Prof WE Price (Chemistry, UoW); Prof LA Kane-Maguire (IPRI/Chemistry, UoW); Prof GG Wallace (IPRI/Chemistry UoW) Prof WS Price; Prof MA Wilson; Prof JP Conroy; Prof PA Williams; Dr R Shalliker; Dr JR Aldrich-Wright; Dr GS Kannangara; Prof PW Kuchel; A/Prof MM Harding; Dr WA Bubb; A/Prof MC Ngu; A/Prof GP Jones; A/Prof BZ Dlugogorski; A/Prof F Separovic; A/Prof AA Adesina; Prof Z Xu Collaborating Organisations: The University of Western Sydney; The University of Sydney; The University of Wollongong; The University of Newcastle; The University of New South Wales; Griffith University; The University of Melbourne; The University of Adelaide Allocation $740,000 The ultra-high resolution imaging NMR spectrometer at the centre of this application is a generation ahead of comparable facilities in Australia and will extend the research capacity of numerous research groups comprising in excess of 50 academics and postgraduate students. The aims and significance of this infrastructure lie in it being one of the centrepieces of the partner institutions? aspirations to take Australia to the cutting edge of nanotechnology and cognate disciplines many of which are areas of national priority. The expected manifold outcomes include research of the highest rank into fundamental problems of drug development through to applied outcomes such as new nanomaterials and improved horticulture/fruit preservation.
Facility for the Analysis of Biomacromolecular Interactions Dr JL Beck (Chemistry, UoW), Prof SG Pyne (Chemistry, UoW), Prof LA Kane-Maguire (IPRI/Chemistry, UoW), Dr PA Keller (Chemistry, UoW) Dr NE Dixon; Prof G Otting; Prof CJ Easton; Dr JE Gready; Prof TJ Andrews; A/Prof MR Wilson; Prof MJ Walker; Prof SF Lincoln; Prof JA Carver Collaborating Organisations: The Australian National University; The University of Wollongong; The University of Adelaide Allocation $432,474 A facility for the analysis of biological macromolecules and their interactions with ligand molecules is required to support a large number of research projects in high priority areas including mechanisms of aging, drug development and bio/nanotechnology at three different universities. The instrumentation will (i) afford quantitative measurements of binding affinities between biological and chemical macromolecules, which are available only in small quantities, and small, drug related molecules (by microcalorimetry and dual polarization interferometry), and (ii) provide equipment necessary for sample characterization and purification prior to quantitative measurements (CD spectroscopy, and FPLC equipment).
Chemistry Department Research Booklet Updated February 2007 Page 55 World-leading Elemental and Isotopic Microanalysis and Chemical Speciation Facilities for an Environmentally Sustainable Australia Dr DF Jolley (Chemistry, UoW) Prof MT McCulloch; Prof AR Chivas; Dr SM Eggins; Prof RJ Morrison; Dr J Mavrogenes; Dr C Pelejero; Dr E Calvo; Dr RG Roberts; Prof Dr R Grun; Dr EJ Rhodes Collaborating Organisations: The Australian National University; University of Wollongong Allocation $397,100 We propose to establish a world-leading centre for the study of the elemental and isotopic composition of key environmental, archaeological and mineral samples. This will be based upon ultra-short wavelength laser ablation and speciation methods, combined with new advanced ICP-MS technologies developed in Australia. This will give the centre unrivalled capabilities and allow new areas of research to be undertaken in global climate change, the impact of increased salinity and pollution on the sustainability of Australia’s inland waterways and coastal environments, and the history of the first humans who inhabited Australia. This will provide a baseline and new quantitative measures to better plan for an environmentally sustainable Australia.
New Directions in Biomolecular Mass Spectrometry Prof MM Sheil (Chemistry, UoW); Dr SJ Blanksby (Chemistry, UoW); Dr JL Beck (Chemistry, UoW); A/Prof RJ Truscott (Chemistry, UoW); Dr PA Keller (Chemistry, UoW) A/Prof JA Carver; A/Prof MR Wilson; A/Prof MJ Walker; Dr NE Dixon; Prof G Otting; Prof IG Young; Prof BG Rolfe; Prof LN Mander Collaborating Organisations: University of Wollongong; The Australian National University Allocation $550,910 The combined UoW/ANU mass spectrometry facility supports a range of research projects in high priority areas including proteomics, mechanisms of aging, anticancer drugs and pathogenicity. The facility has several key deficiencies: 1) the ability to study very high molecular weight biomolecular complexes, 2) the ability to study ion-molecule interactions that have implications in mechanisms of chemistry in nature, and 3) researchers at ANU lack essential walk-up access to high sensitivity protein sequence analysis (MS/MS). The placement of resources that address these deficiencies in one geographical region and collaboration between these institutions will produce a research interaction unique in Australia.
Electrochemical Electron Spin Resonance Spectrometer Prof GG Wallace (IPRI, Chemistry, UoW); Dr PC Innis (IPRI, Chemistry, UoW); Prof LA Kane-Maguire (IPRI, Chemistry, UoW); Prof WE Price (Chemistry, UoW); Dr SJ Blanksby (Chemistry, UoW); Dr PA Keller (Chemistry, UoW); Dr CO Too (IPRI, Chemistry, UoW ); Dr PC Dastoor; Dr JR Aldrich-Wright; Dr GR Dennis; Dr PJ Barker; Prof HK Liu Collaborating Organisations: University of Wollongong; The University of Newcastle; University of Western Sydney; BHP Steel Ltd. Allocation $148,246
Electron Spin Resonance Spectroscopy (ESR), is a reactions, organic photovoltaics and new materials for technique used to determine the presence of free nerve cell regeneration. unpaired electrons in a sample. Detection and life time studies of radical species is critical to understanding the mechanisms involved in chemical reaction, sample degradation, performance upon exposure to light and oxidation or reduction processes. Combining ESR with an electrochemical interface permits in-situ studies on how electrons are injected or removed from a sample, providing fundamental information on the processes occurring within the sample. Applications will be in the area of electrofunctional materials, complex biomolecular
Chemistry Department Research Booklet Updated February 2007 Page 56
High resolution Fourier transform infrared spectrometer for atmospheric remote sensing and laboratory spectroscopy. Prof DW Griffith (Chemistry, UoW); Dr SR Wilson (Chemistry, UoW); Prof PO Wennberg; Dr D Chen Collaborating Organisations: The University of Wollongong, The University of Melbourne, California Institute of Technology. Allocation: $250,000 Climate change is a major global concern, with the potential for major consequences in Australia. This proposal contributes directly to climate change research relevant to Australia through direct measurements of the atmosphere relevant to the understanding of phenomena such as increasing greenhouse gas concentrations and stratospheric ozone depletion. Australia's geographical position in the less populated southern hemisphere, and its advanced scientific infrastructure, mean that it has an especially important and valuable role to play in global atmospheric research. The proposed research participates in several international research programmes.
State of the art NMR Facilities
Prof SG Pyne (Chemistry, UoW); A/Prof WE Price (Chemistry, UoW); Dr SJ Blanksby (Chemistry, UoW); Prof JB Bremner (Chemistry, UoW); A/Prof PA Keller (Chemistry, UoW); Dr SF Ralph (Chemistry, UoW); Prof CJ Easton; Prof MG Banwell; Prof G Otting; Dr MG Casarotto; Prof AF Dulhunty; Prof PG Board Collaborating Organisations: The University of Wollongong, The Australian National University Allocation: $470,000 This proposal will significantly enhance the NMR research capability and capacities at UoW and ANU. These schools have internationally recognised strengths in fundamentals of synthetic organic chemistry, therapeutic drug design and synthesis, protein chemistry and structural biology. This equipment will enhance the productivity of these researchers, increase their collaborative and scientific outputs and allow for training of students in the latest technologies and importantly, contribute to Australia's development as a knowledge based economy.
Nanostructure Deposition Facility
Prof GG Wallace (IPRI/Chemistry, UoW); Dr PC Innis (IPRI/Chemistry, UoW); Dr AI Minett (IPRI/Chemistry, UoW); Dr PC Dastoor; Prof J O'Connor; Dr EJ Wanless; Dr MW Radny; Prof RN Lamb; Dr P Meredith; A/Prof MJ Ford; Dr GE Gadd; Dr PJ Evans; Dr JR Reimers; Prof MJ Crossley; Em/Prof NS Hush; Dr K Ostrikov; Prof DR McKenzie. Collaborating Organisations: The University of Newcastle, , The University of Sydney, University of Wollongong, ANSTO, The University of New South Wales, University of Technology, Sydney. Allocation: $180,240 New electronic devices and materials that exploit the properties of nanostructured surfaces are predicted to have a major impact on everyday life in areas such as information technology, biotechnology and healthcare. The Nanostructure Deposition Facility (NDF) is a unique facility, providing access to the highly specialised deposition equipment required to fabricate these important nanostructured surfaces from a variety of materials. The NFDL represents a major new joint venture between seven Australian institutions and will provide these researchers with the essential tools for developing new electronic devices, biosensors, detectors and solar cells based on nanotechnology.
National Health and Medical Research Council Development Grants
An Innovative Device for Use During Rehabilitation by Knee Replacement Patients Peter Innis (IPRI/Chemistry UoW), 2005 Julie Steele; Bridget Munro; William Humphries; Troy Coyle Total Funding $169,000 This project aims to develop a robust wearable device capable of providing immediate audible feedback with respect to knee motion for enhanced post-knee replacement surgery rehabilitation, suitable for use by older people both independently and supervised at home or in the clinic. As there is a current unmet need for such wearable biofeedback devices, this project will lead to intellectual property generation, strengthened partnerships between the involved parties and identification of an industry partner to commercialise the technology.
Chemistry Department Research Booklet Updated February 2007 Page 57 Preclinical Development of Novel Antibacterial Peptoids Targeting Antibiotic Resistant Bacteria John Bremner (Chemistry, UoW), Paul Keller (Chemistry, UoW) and Stephen Pyne (Chemistry, UoW), 2006 Total Funding: $184,500 The emergence of bacterial strains resistant to antibiotics has created a major healthcare problem in the treatment of some bacterial infections. We have developed new drugs with activity against a range of bacteria including resistant ones. It is now important to complete full pre-clinical evaluations of our compounds including demonstrating activity in vivo. This proposal will complete the development of the compounds in readiness for assessment as potential therapeutics in the clinic.
Australian Institute of Nuclear Science and Engineering Awards
The use of Scanning and Transmission Electron Microscopy to Identify Structural Changes and Cellular Fate of Copper and Zinc in Marine Dianne Jolley (Chemistry, UoW), 2005 Total Funding: $9,465
The Development of Radiolabelled EGF and VEGF Receptor Tyrosine Kinase Inhibitors as Antitumour Agents Paul Keller (Chemistry UoW), 2005 Total Funding: $28,145
New Therapeutics for the Prevention of Premature Birth Paul Keller (Chemistry, UoW), 2006 Total Funding: $17,950
Selenium in Marine Sediments: Unravelling the Relationship between Concentration, Binding Phase and Sediment Age Dianne Jolley (Chemistry, UoW), 2006 Total Funding: $6,732
The Use of Radiotracer Techniques to Determine Metal Contaminant Exposure Pathways to Organisms in Marine Ecosystems Dianne Jolley (Chemistry, UoW), 2006 Total Funding: $23,066
The use of radiotracer techniques to determine metal contaminant exposure pathways to organisms in marine ecosystems Dianne Jolley (Chemistry, UoW), 2005 Total Funding: $8,000
The development of radiolabelled EGF and VEGF receptor tyrosine kinase inhibitors as antitumour agents Paul Keller (Chemistry, UoW), Total Funding: $28,145
Chemistry Department Research Booklet Updated February 2007 Page 58
2004 - 2005 PUBLICATIONS DATA
Conference Publication
McGovern, S. T., Spinks, G. M. & Wallace, G. G. (2005). The use of embedded sensors for the monitoring of adhesive joints in marine environments. SPIE Proceedings Series: Advanced Sensor Technologies for Nondestructive Evaluation and Structural Health Monitoring (pp. 76-86). USA: SPIE International Society for Optical Engineering.
McGovern, S. T., Spinks, G. M. & Wallace, G. G. (2005). Highly processable method for the construction of miniature conducting polymer moisture sensors. "SPIE Proceedings Series: Smart Structures, Devices and Systems II\" (pp. 607- 615). USA: SPIE International Society for Optical Engineering.
Spinks, G. M., Kim, M., Lee, C., Shin, S., Lee, S., Kim, S. & Kim, S. (2005). Enhancement of the electromechanical behaviour of IPMCs based on chitosan/polyaniline ion exchange membranes fabricated by freeze-drying. Proceedings of SPIE: Smart Structures and Materials 2005 (pp. 454-463). USA: SPIE International Society for Optical Engineering.
Spinks, G. M., Xi, B., Campbell, T. E., Whitten, P. G., Mottaghitalab, V., Samani, M. & Wallace, G. G. (2005). In pursiut of high-force/high-stroke conducting polymer actuators. Proceedings of SPIE: Smart Structures and Materials 2005 (pp. 314-321). USA: SPIE International Society for Optical Engineering.
Xi, B., Mottaghitalab, V., Whitten, P. G., Spinks, G. M., Wallace, G. G. & Truong, V. (2005). Actuation behaviour of polyaniline films and tues prepared by phase inversion technique. "Proceedings of SPIE: Smart Structures, Devices and Systems II" (pp. 436-444). USA: SPIE International Society for Optical Engineering.
Xi, B., Whitten, P. G., Ding, J., Spinks, G. M., Wallace, G. G. & Truong, V. (2005). Poly (3-methylthiophene) based electrochemical actuators. "Proceedings of SPIE: Smart Structures, Devices and Systems II" (pp. 137-143). USA: SPIE International Society for Optical Engineering.
Journal Article
Aquilina, A., Benesch, J., Ding, L., Yaron, O., Horwitz, J. & Robinson, C. (2004). Phosphorylation of alphB-Crystallin Alters Chaperone Function through Loss of Dimeric Substructure. The Journal of Biological Chemistry , 279 (27), 28675-28680.
Aquilina, A., Benesch, J., Ding, L., Yaron, O., Horwitz, J. & Robinson, C. (2005). Subunit Exchange of Polydisperse Proteins: Mass Spectrometry reveals consequences of alpha-A-Crystallin Truncation. The Journal of Biological Chemistry, 280 14485-14491.
Aquilina, A., Kappe, G., Wunderink, L., Kamps, B., Robinson, C., Garate, T., Boelens, W. & de Jong, W. (2004). Tsp36, a Tapeworm Small Heat-Shock Protein with a Duplicated alpha-Crystallin Domain, Forms Dimers and Tetramers with Good Chaperone-like Activity. Proteins: Structure, Function and Bioinformatics, 57 109-117.
Barisci, J., Tahann, M., Wallace, G. G., Badaire, S., Vaugien, T., Maugey, M. & Poulin, P. (2004). Properties of Carbon Nanotube Fibers Spun from DNA-Stabilized Dispersions. Advanced Functional Materials, 14 (2), 133-138.
Chemistry Department Research Booklet Updated February 2007 Page 59 Barisci, J., Wallace, G. G., Gooding, J., Wasiowych, C., Barnett, D. & Hibbert, D. (2004). Electrochemical modulation of antigen-antibody binding. Biosensors and Bioelectronics, 20 260-268.
Barisci, J., Wallace, G. G., MacFarlane, D. & Baughman, R. (2004). Investigation of ionic liquids as electrolytes for carbon nanotube electrodes. Electrochemistry Communications, 6 22-27.
Beck, J. L., Sheil, M. M., Ralph, S. F., Urathamakul, T. & Aldrich-Wright, J. (2004). A Mass Spectrometric Investigation of Non-Covalent Interactions between Ruthenium Compounds and DNA. Dalton Transactions , 2683-2690.
Beck, J. L., Yong, S., Sheil, M. M., Ralph, S. F., Ambahera, S. & de Jersey, J. (2004). Direct observation of covalent adducts with Cys34 of human serum albumin using mass spectrometry. Analytical Biochemistry , 325 326- 336.
Berry, Y. J., Carver, J., Meehan, S., Luisi, B., Dobson, C. & MacPhee, C. (2004). Amyloid Fibril Formation by Lens Crystallin Proteins and its Implications for Cataract Formation. The Journal of Biological Chemistry, 279 (5), 3413-3419.
Blanksby, S. J., Waters, T., Zhang, L. & O'Hair, A. (2004). Formation of the heterocumulene anion SCCCN - by a cyano migration from the radical anion of 1,2-dicyanoethyleneedithiolate. Organic and Biomolecular Chemistry, 2 190-194.
Boyle, T., Bremner, J. B., Keller, P. A., Pyne, S. G. & Coates, J. (2005). A Convenient and Efficient Synthesis of (S)-Lysine and (S)-Arginine Homologues via Olefin Cross-Metathesis. Tetrahedron, 61 7271-7276.
Bremner, J. B. & Perkins, D. (2005). Synthesis of Functionalised Azecine and Azonine Derivatives via an Enolate Assisted Aza Claisen Rearrangement. Tetrahedron, 61 (10), 2659-2665.
Bremner, J. B. & Sengpracha, W. (2005). A Free Radical Cyclization Approach to Indolo-benzodiazocine Derivatives. Tetrahedron, 61 (4), 941-953.
Bremner, J. B. & Sengpracha, W. (2005). An Iodoacetamide-based Free Radical Cyclisation Approach to the 7,12-Dihydro- indolo[3,2-d][1]benzazepin-6(5H)-one (paullone) System. Tetrahedron, 61 (23), 5489-5498.
Bremner, J. B., Apisantiyakom, S., Kittakoop, P., Manyum, T., Kirtikara, K. & Thebtaranonth, Y. (2004). Novel Biologically Active Bibenzyls from Bauhinia saccocalyx Pierre. Chemistry and Biodiversity, 1 1694-1701.
Bremner, J. B., Benkendorff, K. & Pillai, R. (2004). 2,4,5- Tribromo-1-H-Imisazole in the egg masses of three Muricid Molluscs. Natural product Research, 18 427-431.
Bremner, J. B., Godfrey, C., Jensen, A. & Smith, R. (2004). Synthesis and nicotinic receptor activity of a hydroxylated tropane. Bioorganic & Medicinal Chemistry Letters, 14 271-273.
Bremner, J. B., McGinty, S. J., Finch, A., Griffith, R. & Graham, R. (2004). Synthesis and biological evaluation of bicyclic and tricyclic substituted nortropane derivatives: discovery of a novel selective - adrenergic receptor ligand. Bioorganic and Medicinal Chemistry, 12 5639-5650.
Bremner, J. B., Perkins, D., Rattanaphani, V., Rattanaphani, S. & Chairat, M. (2004). An absorption spectroscopic investigation of the interaction of lac dyes with metal ions. Dyes and Pigments, 63 141-150.
Bremner, J. B., Samosorn, S. & Ambrus, J. (2004). N- Acylation of 5-Substituted indoles with Carboxylic Acids via DCC Coupling . Synthesis: Journal of Synthetic Organic Chemistry, 16 2653-2658.
Bremner, J. B., Sengpracha, W., Southwell, I., Bourke, C., Skelton, B. & White, A. (2004). A Revised Structure for the Alkaloid, Tribulusterine, from Tribulus terrestris L. . Australian Journal of Chemistry, 57 273-276.
Bryant, G. W., Griffith, D. W., Denmead, O., Macdonald, B., Reilly, R., Stainlay, W., White, I. & Melville, M. (2005). Gaseous nitrogen losses from acid sulfate sugarcane soils on the coastal lowlands. Australian Society of Sugar Cane Technologists. Proceedings _, 27 211-219.
Chemistry Department Research Booklet Updated February 2007 Page 60 Burley, G., Chaker, L., Hawkins, W., Williams, J., Keller, P. A., Pyne, S. G. & Ball, G. (2005). Structural Reassignment of the Mono- and Bis-addition Products from the Addition Reactions of N-(diphenylmethylene)glycinate Esters to [60]fullerene under Bingel Conditions. The Journal of Organic Chemistry, 70 8572-8574.
Carver, J., Apponyi, M., Pukala, T., Brinkworth, C., Maselli, V., Bowie, J., Tyler, M. & Booker, G. (2004). Host-defence peptides of Australian anurans: structure, mechanism of action and evolutionary significance. Peptides, 25 1035-1054.
Carver, J., Price, W. E., Treweek, T. M., Lindner, R. & Morgan, P. (2005). Casein Proteins as Molecular Chaperones. Journal of Agricultural and Food Chemistry, 53 2670-2683.
Carver, J., Pukala, T., Brinkworth, C. & Bowie, J. (2004). Investigating the importance of the flexible hinge in Caerin 1.1: Solution structures and activity of two synthetically modified Caerin Peptides. Biochemistry, 43 937-944.
Chairat, M., Bremner, J. B., Rattanaphani, S. & Rattanaphani, V. (2005). An Adsorption and Kinetic Study of Lac Dyeing on Silk. Dyes and Pigments, 64 231-241.
Chaker, L., Williams, J., Burley, G., Hawkins, W., Keller, P. A., Pyne, S. G. & Ball, G. (2005). Regioselective synthesis of novel e-edge-[60]fullerenylmethanodihydropyrroles and1,2-dihydromethano[60]fullerenes. European Journal of Organic Chemistry, 5158-5162.
Chen, J., Too, C. O., Wallace, G. G. & Swiegers, G. (2004). Redox-active conducting polymers incorporating ferrocenes 2. Preparation and characterisation of polypyrroles contaiing propyl- and butyl-tethered [1.1] ferrocenophane. Electrochimica Acta, 49 691-702.
Chen, J., Too, C. O., Wallace, G. G., Burrell, A., Campbell, W. & Officer, D. (2004). Photoelectrochemical cells based on a novel porphyrin containing light harvesting conducting copolymer. Electrochimica Acta, 49 329-337.
Chen, J., Too, C. O., Wallace, G. G., Huang, J. & Swiegers, G. (2004). A readily-prepared electrocatalytic coating that is more active than platinum for hydrogen generation in 1 M strong acid. Chemical Communications, 308-309.
Chen, J., Too, C. O., Wallace, G. G., Officer, D., Pringle, J. & McFarlane, D. (2005). Photoelectrochemical Solar Cells based on Polyterthiophenes Containing Porphyrins using Ionic Liquid Electrolyte. Electrochemical and Solid-State Letters, 8 (10), A528-A530.
Chen, J., Too, C. O., Wallace, G. G., Yang, C. & Swiegers, G. (2005). Hydrogen generation using PPy-FMS modified PVDF membrane and other substrates. Synthetic Metals, 154 69-72.
Chen, J., Wallace, G. G. & Winther-Jensen, B. (2005). Stuffed. Polymer, 4464-4669.
Chen, J., Wallace, G. G., Winther-Jensen, B. & West, K. (2004). Vapor Phase Polymerization of Pyrrole and Thiphene Using Iron (III) Sulfonates as Oxidizing Agents. Macromolecules, 37 5930-5935.
Dillon, C. T., Waern, J., Harris, H., Lai, B., Cai, Z. & Harding, M. (2005). Intracellular Mapping of the Distribution of Metals Derived from the Antitumor Metallocenes. Journal of Biological Inorganic Chemistry, 10 443-452.
Ding, J., Price, W. E., Ralph, S. F. & Wallace, G. G. (2004). Electroless recovery of gold chloride using inherently conducting polymers. Polymer International, 53 681-687.
Dunse, B., Wilson, S. R., Steele, L., Fraser, P. & Krummel, P. (2005). Trace gas emissions from Melbourne, Australia, based on AGAGE observations at Cape Grim, Tasmania, 1995-2000. Atmospheric Environment, 6334-6344.
Gordon, C. & Keller, P. A. (2005). Control of Hepatitis C: A Medicinal Chemistry Perspective. Journal of Medicinal Chemistry, 48 (1), Jan-20.
Griffith, D. W. & Bernardo, C. (2005). Fourier transform spectrometer instrument lineshape (ILS) retrieval by Fourier Deconvolution. Journal of Quantitative Spectroscopy & Radiative Transfer, 141-150.
Chemistry Department Research Booklet Updated February 2007 Page 61 Griffith, D. W., Feilberg, K., Johnson, M. & Nielsen, C. (2005). The 13C and D Kinetic Isotope Effects in the Reaction of CH4 with Cl. International Journal of Chemical Kinetics, 37 (2), 110-118.
Griffith, D. W., Jones, N. B., Dils, B., De Maziere, M., Blumenstock, T., Buchwitz, M., de Beek, R. & Demoulin, P. (2005). Comparisons between SCIAMACHY and ground-based FTIR data for total columns of CO, CH4, CO2 and N2O. Atmospheric Chemistry and Physics Discussions, 5 2677-2717.
Gupta, R., Beck, J. L., Ralph, S. F., Sheil, M. M. & Aldrich-Wright, J. (2004). Comparison of the Binding Stoichiometries of Positively Charged DNA-Binding Drugs Using Positive and Negative Ion Electrospray Ionization Mass Sprectrometry. Journal of the American Society for Mass Spectrometry, 15 1382-1391.
Gupta, R., Beck, J. L., Sheil, M. M. & Ralph, S. F. (2005). Identification of bINUCLEAR GA and AG intrastrand crosslinks formed between cisplatin And Dna. Journal of Inorganic Biochemistry, 99 552-559.
Gupta, R., Sheil, M. M., Beck, J. L., Hamdan, S. & Dixon, N. (2004). Application of electrospray ionization mass spectrometry to study the hydrophobic interaction between the e & 0 subunits of DNA polymerase III. Protein Science, 13 2878-2887.
Halldorsson, J., Wallace, G. G., Stitzel, S., Brady, S. & Diamond, D. (2005). Electrochemically-induced fluid movement using polypyrrole. Synthetic Metals, 151 60-64.
Haverd, V. E., Griffith, D. W. & Toon, G. (2005). Evidence for Altitude-dependent photolysis-induced 18O isotopic fractionation in stratospheric ozone. Geophysical Research Letters, 32 1-Apr.
Haverd, V. E., Hynes, R., Angove, D., Saunders, S. & Azzi, M. (2005). Evaluation of two MCM v3.1 alkene mechanisms using indoor environmental chamber data. Atmospheric Environment, 7251-7262.
Haverd, V. E., Lewis, B., Gibson, S. & Stark, G. (2005). Rotational effects in the band oscillator strengths and predissociation linewidths for the lowest 1Pi ù X 1Sigma + g transitions of N2. Journal of Chemical Physics, 123 214304- 214312. in het Panhius, M., Kane-Maguire, L. A., Moulton, S. E., Wallace, G. G. & Innis, P. C. (2004). Stabilization of Single-Wall Carbon Nanotubes in Fully Sulfonated Polyaniline. Journal of Nanoscience and Nanotechnology, 4 (8), 976-981.
Innis, P. C., Kane-Maguire, L. A., Moulton, S. E., Wallace, G. G., Panhuis, M., Sainz, R., Benito, A. & Martinez, M. (2005). Optically Active Polymer Carbon Nanotube Composite. The Journal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces & Biophysical, 109 22725-22729.
Innis, P. C., Mazurkiewicz, J. H., Nguyen, T., Wallace, G. G. & MacFarlane, D. (2004). Enhanced electrochemical stability of polyaniline in ionic liquids. Current Applied Physics, 4 389-393.
Jones, N. B., Hase, F., Hannigan, J., Coffey, M., Goldman, A., Hopfner, M., Rinsland, C. & Wood, S. (2004). Intercomparison of retrieval codes used for the analysis of high-resolution, ground-based FTIR measurements. Journal of Quantitative Spectroscopy & Radiative Transfer, 87 25-52.
Jones, N. B., Kasai, Y., Kagawa, A., Fujiwara, A., Seki, K., Murayama, Y. & Murcray, F. (2005). Seasonal variations of CO and HCN in the troposphere measured by solar absorption spectroscopy over Poker Flat, Alaska. Geophysical Research Letters, 32 1-Apr.
Jones, N. B., Kasai, Y., Koshiro, T., Endo, M. & Murayama, Y. (2005). Ground-based measurement of strato-mesopheric CO by a FTIR spectrometer over Poker Flat, Alaska. Advances in Space Research, 35 2024-2030.
Kane-Maguire, L. A., Halldorsson, J., Kane Maguire, N. & Wallace, G. G. (2004). Photoluminescence and photo-redox reactions of poly(2-methoxyaniline-5-sulfonic acid). Current Applied Physics, 4 394-397.
Chemistry Department Research Booklet Updated February 2007 Page 62
Keller, P. A., Garner, J. A. & McCluskey, A. (2004). Corticotrophin Releasing Hormone: Chemistry and Recent Developments. Australian Journal of Chemistry, 57 393-407.
Keller, P. A., Gresser, M., Garner, J. A., Bringmann, G., Price Mortimer, A. & Breuning, M. (2005). Atroposelective Synthesis of Axially Chiral Biaryl Compounds. Angewandte Chemie (International Edition), 44 5384-5427.
Keller, P. A., Luu, T., Garner, J. A. & Griffith, R. (2005). Combining structure-based drug design and pharmacophores. Journal of Molecular Graphics and Modelling, 23 439-446.
Keller, P. A., Morgan, J., Garner, J. A., Hill, T., Odell, L. & McCluskey, A. (2004). Identification of Aminopyrimidine Regioisomers via Line Broadening Effects in 1H and 13 C NMR Spectroscopy. Australian Journal of Chemistry, 57 1079- 1083.
Kim, S., Kim, M., Shin, S., Kim, I., Kim, S., Lee, S., Lee, T. & Spinks, G. M. (2005). Enhancement of the electromechanical behavior of IPMCs based on chitosan/polyaniline ion exchange membranes fabricated by freeze-drying. Smart Materials and Structures, 14 889-894.
Korth, J., Pyne, S. G., Phutdhawong, W., Donchai, A., Picha, P., Ngamkham, J. & Buddhasukh, D. (2004). The components and anticancer activity of the volatile oil from Steblus asper. Flavour and Fragrance Journal, 19 445-447.
Lindsay, K. & Pyne, S. G. (2004). Asymmetric Synthesis of (-)-Swainsonine. Australian Journal of Chemistry, 57 669- 672.
Lindsay, K. & Pyne, S. G. (2004). Studies on the Synthesis of Croomine: Synthesis of the Tricyclic B,C,D-Ring core Structure. Synlett, 5 779-782.
Lindsay, K. & Pyne, S. G. (2004). Synthesis of (+)-(1R,2S,9S,9aR)-octahydro-1H-pyrrolo-[1,2-a]azepine-1,2,9-triol: a potential glycosidase inhibitor. Tetrahedron, 60 4173-4176.
Masdarolomoor, F., Innis, P. C., Ashraf, S. A. & Wallace, G. G. (2005). Purification and characterisation of poly(2- methoxyaniline-5-sulfonic acid). Synthetic Metals, 153 181-184.
McGovern, S. T., Spinks, G. M. & Wallace, G. G. (2005). Micro-humidity sensors based on a processable polyaniline blend. Sensors and Actuators B: Chemical: International Journal devoted to research and development of physical and chemical transducers, 107 657-665.
McGovern, S. T., Spinks, G. M. & Wallace, G. G. (2005). Micro-humidity sensors based on a processable polyaniline blend. Sensors and Actuators B: Chemical: international journal devoted to research and development of physical and chemical transducers, 107 657-665.
Meier, A., Murphy, C., Bell, W., Blumenstock, T., Hase, F., Goldman, A., Steen & Kift, R. (2005). Evidence of reduced measurement uncertainties from an FTIR instrument intercomparison at Kiruna, Sweden. Journal of Quantitative Spectroscopy & Radiative Transfer, 75-84.
Mottaghitalab, V., Spinks, G. M. & Wallace, G. G. (2005). The influence of carbon nanotubes on mechanical and electrical properties of polyaniline fibers. Synthetic Metals, 152 77-80.
Mottaghitalab, V., Spinks, G. M. & Wallace, G. G. (2005). The influence of carbon nanotubes on mechanical and electrical properties of polyaniline fibers. Synthetic Metals, 152 77-80.
Moulton, S. E., Barisci, J., Wallace, G. G., Bath, A. & Stella, R. (2004). Studies of double layer capacitance and electron transfer at a gold electrode exposed to protein solutions. Electrochimica Acta, 49 4223-4230.
Chemistry Department Research Booklet Updated February 2007 Page 63
Moulton, S. E., Innis, P. C., Kane-Maguire, L. A., Ngamna, O. & Wallace, G. G. (2004). Polymerisation and characterisation of conducting polyaniline nanoparticle dispersions. Current Applied Physics, 4 402-406.
Moulton, S. E., Minett, A. I. & Wallace, G. G. (2005). Carbon Nanotube Based Electronic and Electrochemical Sensors. Sensor Letters, 3 183-193.
Moulton, S. E., Minett, A. I., Wallace, G. G., Murphy, R., Ryan, K., McCarthy, D., Coleman, J. & Blau, W. (2005). Biomolecules as selective dispersants for carbon nanotubes. Carbon, 43 1879-1884.
Moulton, S. E., Wallace, G. G., Barisci, J., Bath, A. & Stella, R. (2005). Investigation of Ig.G Adsorption and the Effect on Electrochemical Responses at Titanium Dioxide Electrode. Langmuir, 316-322.
Muhammad, D., Price, W. E., O'Brien, G. A. & Chenhall, B. E. (2005). Fractionation of sedimentary arsenic from Port Kembla Harbour, NSW, Australia. Journal of Environmental Monitoring, 7 621-630.
Mungkornasawakul, P., Matthews, H., Ung, A. T., Pyne, S. G., Lie, W., Jatisatienr, A., Skelton, B. & White, A. (2005). Confirmation of the Structure of Oxystemokerrin by Single Crystal X-Ray Structural Analysis and a Proposed Biosynthesis. A C G C Chemical Research Communications, 19 30-33.
Murphy, C., Jones, N. B., Griffith, D. W., Goldman, A., Wood, S., Chiou, L., Meier, A. & Rinsland, C. (2005). High Spectral resolution solar absorption measurements of ethylene (C2H4) in a forest fire smoke plume using HITRAN parameters: Troposheric vertical profile retrieval. Journal of Quantitative Spectroscopy & Radiative Transfer, 96 301-309.
Murphy, C., Jones, N. B., Wilson, S. R., Haverd, V. E., Meier, A. & Griffith, D. W. (2005). Measurements of trace gas emissions from Australia forest fires and correlations with coincident measurements of aerosol optical depth. Journal of Geophysical Research, 110 1-Jun.
Murphy, C., Jones, N. B., Wilson, S. R., Meier, A., Deutscher, N., Griffith, D. W., Mitchell, R. & Campbell, S. (2004). Trace gas emissions from biomass burning inferred from aerosol optical depth. Geophysical Research Letters, 31 L05116.
Ngamna, O., Moulton, S. E., Wallace, G. G., Morrin, A., Killard, A. & Smyth, M. (2005). An Amperometric Enzyme Biosensor Fabricated from Polyaniline Nanoparticles. Electroanalysis, 17 (5-Jun), 423-430.
Ngamna, O., Moulton, S. E., Wallace, G. G., Morrin, A., Killard, A. & Smyth, M. (2005). An HRP based biosensor using sulphonated polyaniline. Synthetic Metals, 153 185-188.
Ngamna, O., Moulton, S. E., Wallace, G. G., Morrin, A., Wilbeer, F., Killard, A. & Smyth, M. (2005). Novel biosensor fabrication methodology based on processable conducting polyaniline nanoparticles. Electrochemistry Communications, 7 317-322.
Pham, T., Pyne, S. G., Skelton, B. & White, A. (2005). Synthesis of Carbocyclic Hydantocidins via Regioselective and Diastereoselective Phosphine-catalyzed [3+2]-Cycloadditions to 5-Methylenehydantoins. The Journal of Organic Chemistry, 70 6369-6377.
Pornputtkul, Y., Kane-Maguire, L. A., Innis, P. C. & Wallace, G. G. (2005). Asymmetric proliferation with optically active polyanilines. Chemical Communications, 4539-4541.
Pyne, S. G. & Tang, M. (2005). The Structure, Biological Activities and Synthesis of 3-Hydroxylpyrrolizidine Alkaloids and Related Compounds. Current Organic Synthesis, 1393-1418.
Pyne, S. G. (2005). Recent Developments on the Synthesis of (-)-Swainsonine and Analogues. Current Organic Synthesis, 39-57.
Chemistry Department Research Booklet Updated February 2007 Page 64
Pyne, S. G., Davis, A. R., Gates, N., Hartley, J., Lindsay, K., Machan, T. & Tang, M. (2004). Asymmetric Synthesis of Polyfunctionalized Pyrrolidines and Related Alkaloids. Synlett, 15 2670-2680.
Pyne, S. G., Lie, W., Ung, A. T., Jatisatienr, A., Supyen, D., Jatisatienr, C., Skelton, B. & White, A. (2004). Phytochemical and Larvicidal Studies on Stemona curtisii: Structure of a New Pyriodo[1,2-a]azepine Stemona Alkaloid. Journal of Natural Products, 67 675-677.
Ralph, S. F., Wallace, G. G. & Reece, D. (2005). Metal transport studies on inherently conducting polymer membranes containing cyclodextrin dopants. Journal of Membrane Science, 249 Sep-20.
Ralph, S. F., Wallace, G. G., Reece, D. & Pringle, J. (2005). Autopolymerization of Pyrrole in the Presence of a Host/Guest Calixarene. Macromolecules, 38 1616-1622.
Rekas, A., Aquilina, A., Carver, J., Adda, C., Barnham, K., Sunde, M., Galatis, D. & Williamson, N. (2004). Interaction of the Molecular Chaperone alpha B-Crystallin with alpha-Synuclein: Effects on Amyloid Fibril Formation and Chaperone Activity. Journal of Molecular Biology, 340 1167-1183.
Sastraruji, T., Pyne, S. G., Ung, A. T., Lie, W., Williams, M. C. & Jatisatienr, A. (2005). Phytochemical Studies on Stemona Plants: Isolation of New Stemofoline Alkaloids. Journal of Natural Products, 68 1763-1767.
Sheil, M. M., Bernhard, O. & Cunningham, A. (2004). Analysis of Proteins Copurifying with the CD4/lck Complex Using One-Dimensional Polyacrylamide Gel Electrophoresis and Mass Spectrometry: Comparison with Affinity-Tag Based Protein Detection and Evaluation of Different Solubilization Methods. Journal of American Mass Spectrometry , 15 558-567.
Sheil, M. M., Bernhard, O. & Cunningham, A. (2004). Lateral Membrane Protein Associations of CD4 in Lymphoid Cells Detected by Cross-Linking and Mass Spectrometry . Biochemistry, 43 256-264.
Spinks, G. M. & Hughes, M. (2005). Multiwalled Carbon-Nanotube Actuators. Advanced Materials, 4 443-445.
Spinks, G. M. & Truong, V. (2005). Work-per-cycle analysis for electromechanical actuators. Sensors and Actuators A: Pysical: an international Journal devoted to research and development of physical and chemical transducers, 119 455-461.
Spinks, G. M., Campbell, T. & Wallace, G. G. (2005). Force generation from polypyrrole actuators. Smart Materials and Structures, 14 406-412.
Spinks, G. M., Campbell, T. E. & Wallace, G. G. (2005). Force Generation from polypyrrole actuators. Smart Materials and Structures, 14 406-412.
Spinks, G. M., Kim, S., Shin, S., Kim, I. & Kim, S. (2005). Synthesis and Characteristics of a Semi-Interpenetrating Polymer Network Based on Chitosan/Polyaniline Under Different pH Conditions. Journal of Applied Polymer Science, 96 867-873.
Spinks, G. M., Shin, S., Park, S., Yoon, S., Kim, S. & Kim, S. (2005). Synthesis of conducting polyaniline in semi-IPN based chitosan. Synthetic Metals, 154 213-216.
Spinks, G. M., Wallace, G. G., Xi, B. & Truong, V. (2005). \"Actuation behaviour of layered composites of polyaniline, carbon nanotubes and polypyrrole\". Synthetic Materials, 151 85-91.
Spinks, G. M., Xi, B., Wallace, G. G. & Troung, V. (2005). Actuation behaviour of layered composites of polyaniline, carbon nanotubes and polypyrrole. Synthetic Metals, 151 85-91.
Spinks, G. M., Xi, B., Zhou, D., Wallace, G. G. & Truong, V. (2004). Enhanced control and stability of polypyrrole electromechanical actuators. Synthetic Metals, 140 273-280.
Chemistry Department Research Booklet Updated February 2007 Page 65 Spinks, G. M., Zhou, D., Wallace, G. G., Andrews, M. & Jansen, M. (2004). An integrated electrochemical sensor-actuator system. Sensors and Actuators A-Physical, 114 65-72.
Too, C. O., Wallace, G. G., Officer, D. & Dastoor, P. (2005). Photoelectrochemical Cells Based on Inherently Conducting Polymers. M R S Bulletin, 30 46-49.
Treweek, T. M., Rekas, A., Lindner, R., Walker, M. J., Aquilina, A., Carver, J., Robinson, C. & Horwitz, J. (2005). R120G AlphaBeta-crystallin promotes the unfolding of reduced alpha-lactalbumin and is inherently unstable. The FEBS Journal, 272 711-724.
Truscott, R. J., Ferry, G., Ubeaud, C., Lambert, P., Bertin, S., Cog, F., Chomarat, P. & Delagrange, P. (2005). Molecular evidence that melatonin is enzymatically oxidized in a different manner than tryptophan: investigations with both indoleamine 2,3-dioxygenase and myeloperoxidase. Journal of Biochemistry, 205-215.
Tsekouras, G., Ralph, S. F., Price, W. E. & Wallace, G. G. (2004). Gold Recovery using inherently conducting polymer coated textiles. Fibers and Polymers, 5 (1), 1-5.
Tsekouras, G., Too, C. O. & Wallace, G. G. (2005). Effect of growth conditions on the photovoltaic efficiency of poly(terthiophene) based photoelectrochemical cells. Electrochimica Acta, 50 3224-3230.
Ung, A. T., Pyne, S. G., Uta Batenburg-Nguyen, T., Davis, A. R., Shareef, A., Bischoff, F. & Lesage, A. (2005). Synthesis and Antagonist Activities of 4-Aryl-Substituted Conformationally Restricted Cyclopentenyl and Cyclopentanyl-Glutamate Analogues. Tetrahedron, 61 1803-1812.
Wallace, G. G. & Khalkhali, R. (2004). Effect on Solution Temperature on Electroactivity of Polypyrrole Using Cyclic Voltammetry Technique. Iranian Polymer Journal, 13 (6), 463-470.
Wallace, G. G., Badaire, S., Zakri, C., Maugey, M., Derre, A., Barisci, J. & Poulin, P. (2005). Liquid Crystals of DNA- Stabilized Carbon Nanotubes. Advanced Materials, 17 1673-1676.
Wallace, G. G., Brady, S., Lau, K., Megill, W. & Diamond, D. (2005). The Development and Characterisation of Conducting Polymeric-based Sensing Devices. Synthetic Metals, 154 25-28.
Wallace, G. G., Frohne, H., McNeill, C. & Dastoor, P. (2004). Enhancement of polymer electronics via surface states on highly doped polymeric anodes. Journal of Physics D: Applied Physics, 37 165-170.
Wallace, G. G., Lee, E., Park, J. & Bae, Y. (2004). In situ formed processable polypyrrole nanoparticle/amphiphilic elastomer composites and their properties. Polymer International, 53 400-405.
Wallace, G. G., Moulton, S. E., Too, C. O., Zhou, D. & Wu, Y. (2004). Use of inherently conducting polymers and pulsed amperometry in flow injection analysis to detect oligonnucleotides. Analyst, 129 585-588.
Wallace, G. G., Wang, J., Too, C. O. & Zhou, D. (2005). Novel electrode substrates for rechargeable lithium/polypyrrole batteries. Journal of Power Sources, 140 162-167.
Wang, J., Chen, J., Wang, C., Zhou, D., Too, C. O. & Wallace, G. G. (2005). Electrochemical synthesis of polypyrrole films using stainless steel mesh as substrate for battery application. Synthetic Metals, 153 117-120.
Wang, J., Too, C. O. & Wallace, G. G. (2005). A highly flexible polymer fibre battery. Journal of Power Sources, 150 223- 228.
Watt, S., Beck, J. L., Ozawa, K., Headlam, M., Mouradov, D., Rodgers, K., Dean, R. & Huber, T. (2005). Translational incorporation of L-3,4-dihydroxyphenylalanine into proteins. The FEBS Journal, 272 3162-3171.
Watt, S., Beck, J. L., Williams, N., Liepinsh, E., Prosselkov, P., Matthews, J., Attard, P. & Dixon, N. (2005). Stabilization of Native Protein Fold by Intein-Mediated Covalent Cyclization. Journal of Molecular Biology, 346 1095-1108.
Chemistry Department Research Booklet Updated February 2007 Page 66 Watt, S., Sheil, M. M., Beck, J. L. & Oakley, A. (2005). Comparison of negative and positive ion electrospray ionization mass spectra of calmodulin and its complex with trifluoperazine. Rapid Communications in Mass Spectrometry, 19 2123- 2130.
Watt, S., Sheil, M. M., Beck, J. L., Furlan, R., Garrido, L., Amarante-Mendes, G., Nur-e-Alam, M. & Rohr, J. (2004). DNA- Binding Properties of Cosmomycin D, an Anthracycline with Two Trisaccharide Chains. The Journal of Antibiotics , 57 647-654.
Whitten, P. G., Spinks, G. M. & Wallace, G. G. (2005). Mechanical properties of carbon nanotube paper in ionic liquid and aqueous electrolytes. Carbon, 43 1891-1896.
Whitten, P. G., Spinks, G. M. & Wallace, G. G. (2005). Mechanical properties of carbon nanotube paper in ionic liquid and aqueous electrolytes. Carbon, 43 1891-1896.
Wilson, M. R., Rekas, A., Thorn, D., Meehan, S., Sunde, M., Gras, S., MacPhee, C. & Dobson, C. (2005). Amyloid Fibril Formation by Bovine Milk kappa-Casein and Its Inhibition by the Molecular Chaperones alpha-S and Beta-Casein . Biochemistry, 44 17027-17036.
Wilson, S. R., Andrady, A., Aucamp, P., Alkivadis, F., Bais, A., Ballar, C., Bjorn, L. & Bornman, J. (2005). Environmental effects of ozone depletion and its interactions with climate change: Progress report, 2004. Photochemical & Photobiological Sciences, 22 177-184.
Wilson, S. R., Andrady, A., Aucamp, P., Bais, A., Ballare, C., Bjorn, L., Bornman, J. & Caldwell, M. (2004). Environmental effects of ozone depletion and its interactions with climate change: Progress Report 2003. Photochemical & Photobiological Sciences, 3 1-5.
Wu, J., Kreis, I., Griffiths, D. & Darling, C. (2004). Lung function changes in coke oven workers during 12 years of follow up. Occupational and Environmental Medicine, 686-691.
Wu, J., Kreis, I., Griffiths, D. & Darling, C. (2004). Respiratory Symptoms and Lung Functions of Coke Oven Workers: A Lung Function Surveillance System From 1990-2000. Journal of Occupational and Environmental Medicine, 46 (9), 906- 915.
Wu, J., Zhou, D., Too, C. O. & Wallace, G. G. (2005). Conducting polymer coated lycra. Synthetic Metals, 155 698-701.
Yong, S., Williams, M. C., Ung, A. T., Skelton, B., White, A. & Turner, P. (2005). Synthesis of 2-Azaspiro[4.4]nonan-1-ones via Phosphine-catalysed [3+2]-Cycloadditions. Tetrahedron, 61 8120-8129.
Book Chapter
Blanksby, S. J. & Bowie, J. (2005). Carbanions: Formation, Structure and Thermochemistry. In (Eds.), Encyclopedia of Mass Spectrometry, Volume 4 ( 1 ed.). (pp. 261-270). The Netherlands: Elsevier Sci Ltd.
Bremner, J. B. (2004). Biodiversity: Reasons for the Scientific and Commercial Interest. In (Eds.), Accessing Biological Resources: Complying with the Convention on Biological Diversity ( 1 ed.). (pp. 1-15). Netherlands: Kluwer Law International.
Bremner, J. B. (2004). Seven-Membered Rings. In (Eds.), Progress in Heterocyclic Chemistry - Volume 16 ( 1 ed.). (pp. 431-450). UK: Elsevier Inc.
Chemistry Department Research Booklet Updated February 2007 Page 67 Bremner, J. B. (2005). Seven-Membered Ring Systems. In (Eds.), Progress in Heterocyclic Chemistry: Volume 17 ( 1 ed.). (pp. 389-417). U.K. : Elsevier Sci Ltd.
Kell, P. M. (2005). Product Class 2: Pyridinones and Related Systems. In (Eds.), Science of Synthesis: Hetarenes and Related Ring Systems: Volume 15 ( 1 ed.). (pp. 285-387). New York: Georg Thieme Verlag.
Keller, P. A. (2005). Product Class 11: Phenanthridines. In (Eds.), Science of Synthesis: Hetarenes and Related Ring Systems: Volume 15 ( 1 ed.). (pp. 1065-1088). New York: Georg Thieme Verlag.
Keller, P. A. (2005). Product Class 12: Phenanthridinones and Related Systems. In (Eds.), Science of Synthesis: Hetarenes and Related Ring Systems: Volume 15 ( 1 ed.). (pp. 1089-1096). New York: Georg Thieme Verlag.
Spinks, G. M., Wallace, G. G., Baughman, R. & Dai, L. (2004). Carbon Nanotube Actuators: Synthesis, Properties and Performance. In (Eds.), Electroactive Polymer (EAP) Actuators as Artificial Muscles: Reality, Potential and Challenges Second Edition ( 2 ed.). (pp. 223-256). USA: International Society for Optical Engineering.
Wallace, G. G., Innis, P. C. & Kane-Maguire, L. A. (2004). Inherently Conducting Polymer Nanostructures. In (Eds.), Encyclopedia of Nanoscience and Nanotechnology ( 0 ed.). (pp. 113-130). USA: American Scientific Publishers.
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