Hydrogen Abstraction in Chemical, Biochemical and Polymerization Processes. Hydrogen-abstraction reactions are of vital importance in the chemical, biochemical and polymerization processes that occur in everyday life. The objective of the proposed research is to improve our understanding of such reactions. State-of-the-art quantum chemistry calculations will be used to examine a broad range of hydrogen-abstraction reactions, and to obtain accurate information about the factors that influence suc ....Hydrogen Abstraction in Chemical, Biochemical and Polymerization Processes. Hydrogen-abstraction reactions are of vital importance in the chemical, biochemical and polymerization processes that occur in everyday life. The objective of the proposed research is to improve our understanding of such reactions. State-of-the-art quantum chemistry calculations will be used to examine a broad range of hydrogen-abstraction reactions, and to obtain accurate information about the factors that influence such reactions. Building on this work, more detailed case studies will be performed in two important areas: the hydrogen-abstraction steps in biochemical reactions mediated by coenzyme B12, and chain-transfer processes in conventional and controlled free-radical polymerization.Read moreRead less
Intervalence Transfer in Dinuclear and Oligonuclear Polymetallic Assemblies. Mixed-valence compounds (such as the pigment Prussian Blue) have been known for over two centuries, and possess important conductivity, magnetic and spectral properties. Electron transfer between the elements of different valency (intervalence charge transfer, IVCT) gives rise to absorbances in the red or near-infrared region of the spectrum which provide fundamental information on the electron migration. By design of ....Intervalence Transfer in Dinuclear and Oligonuclear Polymetallic Assemblies. Mixed-valence compounds (such as the pigment Prussian Blue) have been known for over two centuries, and possess important conductivity, magnetic and spectral properties. Electron transfer between the elements of different valency (intervalence charge transfer, IVCT) gives rise to absorbances in the red or near-infrared region of the spectrum which provide fundamental information on the electron migration. By design of target di- and higher nuclearity polymetallic species, the project will study IVCT phenomena to understand electron movement, allowing rational development of applicable materials such as catalysts, light-activated devices and non-linear optical materials.Read moreRead less
Reactivity and Spectroscopy of Gas Phase Metal Oxide Cluster Ions: Structure-Reactivity Correlations and Fundamental Insights into Heterogeneous Catalysis. This project will make use of world class ARC funded instrumentation to carry out breakthrough science. The research will contribute fundamental insights into chemical bond activation relevant to industrial catalytic processes important to national manufacturing industries. These insights will improve the efficiency and selectivity of catal ....Reactivity and Spectroscopy of Gas Phase Metal Oxide Cluster Ions: Structure-Reactivity Correlations and Fundamental Insights into Heterogeneous Catalysis. This project will make use of world class ARC funded instrumentation to carry out breakthrough science. The research will contribute fundamental insights into chemical bond activation relevant to industrial catalytic processes important to national manufacturing industries. These insights will improve the efficiency and selectivity of catalytic processes and lead to increased profitability and/or a reduction in unwanted side products and pollution. The project will train young scientists in important experimental and theoretical chemical techniques, and will enhance and contribute to Australia's international research profile.Read moreRead less
Structures and Properties of beta-R3M (M = Si, Ge, Sn)- and beta-Chalcogenyl-substituted Carbenium Ions. The benefits of this work are many-fold. The scientific knowledge gained will be invaluable to all scientists working in organic chemistry; mechanistic chemists who will learn from the science, and synthetic organic chemists who can utilise the results when planning strategies for the synthesis of complex drugs. Another major benefit of this research is in the training of young scientists. Th ....Structures and Properties of beta-R3M (M = Si, Ge, Sn)- and beta-Chalcogenyl-substituted Carbenium Ions. The benefits of this work are many-fold. The scientific knowledge gained will be invaluable to all scientists working in organic chemistry; mechanistic chemists who will learn from the science, and synthetic organic chemists who can utilise the results when planning strategies for the synthesis of complex drugs. Another major benefit of this research is in the training of young scientists. The students who work on this proposal gain invaluable experience in many areas of chemistry, ranging from synthetic chemistry to structural chemistry and theoretical chemistry. They will also gain experience in important physical techniques from NMR spectroscopy to X-ray crystallography.Read moreRead less
Nucleophilic carbenes as organocatalysts for asymmetric synthesis. Chemical compounds which come in two chiral mirror images (enantiomers) can have very different biological function. Often one form can have beneficial effects while the other can cause great harm (such as birth defects in the case of thalidomide). It is therefore very important for the drug industry to have asymmetric chemical reactions that lead specifically to only one enantiomer. The asymmetric reactions in this project ha ....Nucleophilic carbenes as organocatalysts for asymmetric synthesis. Chemical compounds which come in two chiral mirror images (enantiomers) can have very different biological function. Often one form can have beneficial effects while the other can cause great harm (such as birth defects in the case of thalidomide). It is therefore very important for the drug industry to have asymmetric chemical reactions that lead specifically to only one enantiomer. The asymmetric reactions in this project have been used previously to synthesise the anti-cancer metabolite roseophilin. The results of this project will ensure that there are many more similar success stories in the pharmaceutical and biotechnology industries.Read moreRead less
Multiblock copolymer synthesis for nano-engineered materials. This project aims to develop methodology for environmentally friendly and industrially applicable synthesis of new types of advanced polymeric materials comprising multiblock copolymers. Polymeric materials play an important role in society with applications from bulk plastics to advanced technological applications. This would enable the creation of advanced materials with specific engineering targets and applications ranging from nan ....Multiblock copolymer synthesis for nano-engineered materials. This project aims to develop methodology for environmentally friendly and industrially applicable synthesis of new types of advanced polymeric materials comprising multiblock copolymers. Polymeric materials play an important role in society with applications from bulk plastics to advanced technological applications. This would enable the creation of advanced materials with specific engineering targets and applications ranging from nanomedicine to materials science.Read moreRead less
Approaching anion solvation from the bottom up: infrared studies of negatively charged complexes and clusters. We will employ novel spectroscopic strategies to probe the structures of mass-selected anion complexes and clusters in the gas-phase with the purpose of exploring non-covalent forces responsible for anion solvation. The work is motivated by a recognition that anions serve as key participants in a host of natural and industrial chemical processes, and that their physical and chemical pro ....Approaching anion solvation from the bottom up: infrared studies of negatively charged complexes and clusters. We will employ novel spectroscopic strategies to probe the structures of mass-selected anion complexes and clusters in the gas-phase with the purpose of exploring non-covalent forces responsible for anion solvation. The work is motivated by a recognition that anions serve as key participants in a host of natural and industrial chemical processes, and that their physical and chemical properties depend critically upon interactions with solvent molecules. The experimental results should serve as a critical test for computational approaches to describing anion-neutral interactions, and provide new insights into the behaviour of electrolytes, acid-base chemistry, and fundamental bimolecular reactions.Read moreRead less
Exploiting the self-assembly of hydrophobin proteins to engineer functional nanostructuring surfaces. There is an increasing world-wide demand for advanced nano-biomaterials with novel properties. We will use natural hydrophobin proteins to coat nanodevices and make them more compatible with biological systems. Hydrophobin coatings will be applicable to biosensors, medical devices, diagnostics and drug delivery systems. The research will lead to an understanding of the basic mechanisms of protei ....Exploiting the self-assembly of hydrophobin proteins to engineer functional nanostructuring surfaces. There is an increasing world-wide demand for advanced nano-biomaterials with novel properties. We will use natural hydrophobin proteins to coat nanodevices and make them more compatible with biological systems. Hydrophobin coatings will be applicable to biosensors, medical devices, diagnostics and drug delivery systems. The research will lead to an understanding of the basic mechanisms of protein self-assembly and will have application outcomes that contribute to Australia being an important player in the field of nanotechnology. This is critical for Australia's long term competitiveness and productivity in and beyond the 21st century.Read moreRead less
Pro-Fluorescent Aryl Nitroxides: New Probes for Polymer Lifetime and Kinetics Research. Internal aryl rings present in novel probes developed for this project impart fluorescence which is efficiently and internally quenched by the presence of a paramagnetic nitroxide group. Scavenging of radicals by the nitroxide however "switches on" the fluorescence and this enables powerful new fluorescence-based detection levels for the technique of nitroxide free radical scavenging. Such sensitivity is a ....Pro-Fluorescent Aryl Nitroxides: New Probes for Polymer Lifetime and Kinetics Research. Internal aryl rings present in novel probes developed for this project impart fluorescence which is efficiently and internally quenched by the presence of a paramagnetic nitroxide group. Scavenging of radicals by the nitroxide however "switches on" the fluorescence and this enables powerful new fluorescence-based detection levels for the technique of nitroxide free radical scavenging. Such sensitivity is applicable to polymerization kinetics studies, as well as providing new means for the determination of materials lifetimes. The development of pro-fluorescent markers as indicators for polymer degradation would be a significant outcome for materials where component failure has a major negative impact.Read moreRead less
Defining Polymer Structures in Radical Polymerization Systems: Chain Birth, Chain Growth and Complex Macromolecular Architectures. The project underpins and extends Australia's leading position in the development and application of novel methods to generate advanced polymeric materials. By carefully studying the reaction pathways underpinning the polymerization processes, an in-depth picture of the polymerization is obtained. The research outcomes will strongly benefit the preparation of the com ....Defining Polymer Structures in Radical Polymerization Systems: Chain Birth, Chain Growth and Complex Macromolecular Architectures. The project underpins and extends Australia's leading position in the development and application of novel methods to generate advanced polymeric materials. By carefully studying the reaction pathways underpinning the polymerization processes, an in-depth picture of the polymerization is obtained. The research outcomes will strongly benefit the preparation of the coming generations of intelligent polymer materials of a highly controlled structure, responsive to their environment, with an even broader range of applications than existing polymers. In addition, the project has a substantial educational component providing training embedded in cutting polymer science for several honours and 1 PhD student.Read moreRead less