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
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
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
The mechanism of water splitting in photosynthesis. Sunlight reaching the earth is used by the vast body of plants and algae living in surface waters and on the land to drive photosynthesis. One of the most fundamental contributions that photosynthesis provides to the Biosphere is the gaseous oxygen produced by its water-splitting chemistry - ~300 gigatons of O2 are released into the atmosphere per year. However, the mechanism behind water-splitting is not precisely known. We will use a range o ....The mechanism of water splitting in photosynthesis. Sunlight reaching the earth is used by the vast body of plants and algae living in surface waters and on the land to drive photosynthesis. One of the most fundamental contributions that photosynthesis provides to the Biosphere is the gaseous oxygen produced by its water-splitting chemistry - ~300 gigatons of O2 are released into the atmosphere per year. However, the mechanism behind water-splitting is not precisely known. We will use a range of unique experimental approaches to determine the molecular mechanism of the photosynthetic water-splitting chemistry. The understanding of this reaction will provide the molecular blueprint for the development of efficient biocatalysts to generate H2 and O2 from water.Read moreRead less
Reaction transition states of halide-cluster complexes via velocity-map imaging of photoelectrons. This study will investigate the transition point between the reactants and products of a chemical reaction using a novel photoelectron imaging technique, velocity-map imaging. It is this region of chemical reactions that is the least understood. By combining the use of weakly bound negatively charged clusters and laser photodetachment of these clusters, information can be gleaned about these transi ....Reaction transition states of halide-cluster complexes via velocity-map imaging of photoelectrons. This study will investigate the transition point between the reactants and products of a chemical reaction using a novel photoelectron imaging technique, velocity-map imaging. It is this region of chemical reactions that is the least understood. By combining the use of weakly bound negatively charged clusters and laser photodetachment of these clusters, information can be gleaned about these transition states. The technique will be applied to an important class of halide-cluster complexes that form a set of prototypical reactions. These species also play important roles ranging from ozone depletion through to industrial chemistry.Read moreRead less
Imaging chemical reaction dynamics from the transition state to reaction products. Chemical reactions play a key role in many atmospheric, environmental and industrial processes. An understanding of reactions at the molecular level will lead to significant economic benefits, through more efficient reaction control, and through the identification of the key environmental factors which influence why particular reactions proceed. Our study of chemical reaction dynamics has been driven by technolo ....Imaging chemical reaction dynamics from the transition state to reaction products. Chemical reactions play a key role in many atmospheric, environmental and industrial processes. An understanding of reactions at the molecular level will lead to significant economic benefits, through more efficient reaction control, and through the identification of the key environmental factors which influence why particular reactions proceed. Our study of chemical reaction dynamics has been driven by technological advances which enable key stages of a reaction to be imaged and studied at the molecular level. Read moreRead less
A Midas touch for electrophiles in new reaction development. This project aims to address the lack of knowledge about how high-value organic molecules are formed in gold-catalysed reactions by advancing a novel mode of catalysis. This project expects to generate new knowledge about these gold-catalysed reactions using an innovative, interdisciplinary approach incorporating computational and synthetic techniques. Expected outcomes of this project include the optimisation and development of import ....A Midas touch for electrophiles in new reaction development. This project aims to address the lack of knowledge about how high-value organic molecules are formed in gold-catalysed reactions by advancing a novel mode of catalysis. This project expects to generate new knowledge about these gold-catalysed reactions using an innovative, interdisciplinary approach incorporating computational and synthetic techniques. Expected outcomes of this project include the optimisation and development of important organic reactions and enhancing collaboration nationally and internationally between computational and synthetic chemists. This should provide significant benefits in the form of improved chemical reactions for chemists to prepare new pharmaceuticals, agrochemicals and materials.Read moreRead less
Switchable and stereocontrolled photoredox catalysis. This project aims to develop new catalytic synthetic reactions for the rapid and more direct functionalisation of organic compounds under mild conditions with the use of visible light. An integrated experimental and computational approach will be used to design potent visible-light photocatalysts that retain the advantages of standard photoredox catalysis but with the added ability to intercept and, thus control, reactive intermediates in sit ....Switchable and stereocontrolled photoredox catalysis. This project aims to develop new catalytic synthetic reactions for the rapid and more direct functionalisation of organic compounds under mild conditions with the use of visible light. An integrated experimental and computational approach will be used to design potent visible-light photocatalysts that retain the advantages of standard photoredox catalysis but with the added ability to intercept and, thus control, reactive intermediates in situ. This will enable the control of stereochemistry in photoredox reactions – not possible with standard catalysts - and establish other useful synthetic transformations. These strategies will make it easier to prepare valuable classes of organic molecules – efficiently, safely, and cost-effectively.
Read moreRead less
A new route to linear alpha olefins - catalytic isomerisation of internal olefins. Linear alpha olefins are an extremely important class of chemical building blocks used for everyday consumer products, such as plastics, detergents and lubricants. This research aims to develop a new platform technology for the production of these materials from low cost precursors.
Accurate gas-surface chemistry from first principles. Many aspects of gas-surface chemistry remain unexplained, despite around 90% of industrial chemical production relying on heterogeneous catalysis. A major problem is that common simulation methods used to study gas-surface chemistry do not adequately incorporate the effect of the motion of the atoms in the solid catalyst surface, preventing accurate study of surface temperature and vibrational energy transfer effects. This project aims to de ....Accurate gas-surface chemistry from first principles. Many aspects of gas-surface chemistry remain unexplained, despite around 90% of industrial chemical production relying on heterogeneous catalysis. A major problem is that common simulation methods used to study gas-surface chemistry do not adequately incorporate the effect of the motion of the atoms in the solid catalyst surface, preventing accurate study of surface temperature and vibrational energy transfer effects. This project aims to develop methods to incorporate surface atom motion in realistic atomistic simulations of gas-surface interactions. The unexplained physics and chemistry of industrially-important catalysis will be investigated. A better understanding of the physics and chemistry of molecules reacting on catalytic surfaces has the potential to allow for improved industrial production, new functional coatings on materials and, for example, enhanced engineering of corrosion resistance.Read moreRead less