New Synthetic Routes to the Immobilisation of Mixed Valence Transition Metal Complexes on Conducting Metal Oxides. Highly coloured, electrochemically active transition metal dyes may find application electrochromic devices, where they may switch between contrasting coloured forms through a simple redox reaction. A prerequisite is that the dye be immobilised onto a solid conducting support whilst preserving the electrochemical and optical properties of the dye found in solution. This project tack ....New Synthetic Routes to the Immobilisation of Mixed Valence Transition Metal Complexes on Conducting Metal Oxides. Highly coloured, electrochemically active transition metal dyes may find application electrochromic devices, where they may switch between contrasting coloured forms through a simple redox reaction. A prerequisite is that the dye be immobilised onto a solid conducting support whilst preserving the electrochemical and optical properties of the dye found in solution. This project tackles this problem through a combination of organic and inorganic synthesis to develop new electrochromic dyes that may be attached to mesoporous titania.Read moreRead less
Electrochemically Driven Molybdoenzyme Catalysis. Enzymes that catalyse oxidation and reduction reactions need to exchange electrons with their substrate and this supply of electrons needs to be sustained. Artificially reconstituted systems can be developed where the enzyme is coupled with an electrode and the current (electrons) exchanged during the reaction are measured directly. In this project we will reveal whether some unusual and unexplained electrochemical phenomena seen before are relat ....Electrochemically Driven Molybdoenzyme Catalysis. Enzymes that catalyse oxidation and reduction reactions need to exchange electrons with their substrate and this supply of electrons needs to be sustained. Artificially reconstituted systems can be developed where the enzyme is coupled with an electrode and the current (electrons) exchanged during the reaction are measured directly. In this project we will reveal whether some unusual and unexplained electrochemical phenomena seen before are related to the properties of the enzymes themselves or the ways in which their experiments have been conducted.Read moreRead less
Molybdenum enzyme electrochemical communication. This project aims to understand the activity of three novel, but related, molybdenum enzymes, human mARC and its bacterial homologs YcbX and YiiM. The role of mARC in humans remains unknown twelve years after its discovery. All three enzymes catalyse the reduction of potentially harmful N-hydroxylated compounds and there is interest in this area from the perspective of drug design. This project will apply an electrochemical methodology to rapidly ....Molybdenum enzyme electrochemical communication. This project aims to understand the activity of three novel, but related, molybdenum enzymes, human mARC and its bacterial homologs YcbX and YiiM. The role of mARC in humans remains unknown twelve years after its discovery. All three enzymes catalyse the reduction of potentially harmful N-hydroxylated compounds and there is interest in this area from the perspective of drug design. This project will apply an electrochemical methodology to rapidly identify enzyme substrates and inhibitors. Molybdenum enzymes pervade all life forms and the outcomes of this research include a unified understanding of an emerging enzyme class involved in drug metabolism.Read moreRead less
Bioelectrochemical interconversion of the building blocks of life. This project aims to harness the efficiency of enzymes (Nature’s catalysts) by coupling them with an electrode for the electrochemical interconversion of carbon dioxide, carbon monoxide and formate; the organic building blocks of life. The significance of this research is that the efficient capture and reduction of carbon dioxide is an important quest in the environment and energy sectors. The expected outcomes of this project wi ....Bioelectrochemical interconversion of the building blocks of life. This project aims to harness the efficiency of enzymes (Nature’s catalysts) by coupling them with an electrode for the electrochemical interconversion of carbon dioxide, carbon monoxide and formate; the organic building blocks of life. The significance of this research is that the efficient capture and reduction of carbon dioxide is an important quest in the environment and energy sectors. The expected outcomes of this project will be an understanding of the reactivity of these enzymes and the conditions under which they may be utilised as part of a renewable electrochemical system. Benefits of this research should emerge in energy efficient technologies for generating fuels (formic acid) from waste products (carbon dioxide).Read moreRead less
Development of Nanostructured TiO2 Electrodes for Photoelectrocatalytic Degradation of Organic and Microbial Pollutants in Wastewater. Australia is one of the driest continents and re-use of water/wastewater has been an urgent issue. Photoelectrocatalytic oxidation processes based on nanostructured TiO2 electrode are able to mineralize common aquatic organic and microbial pollutants. The proposed technology has the advantages of strong oxidation power and cheap production cost, and it is chemi ....Development of Nanostructured TiO2 Electrodes for Photoelectrocatalytic Degradation of Organic and Microbial Pollutants in Wastewater. Australia is one of the driest continents and re-use of water/wastewater has been an urgent issue. Photoelectrocatalytic oxidation processes based on nanostructured TiO2 electrode are able to mineralize common aquatic organic and microbial pollutants. The proposed technology has the advantages of strong oxidation power and cheap production cost, and it is chemically stable, robust under UV illumination, and most importantly, environmentally friendly. The success of the project can place Australia in a leading position of developing cutting-edge TiO2 nano-material-based photoelectrochemical technologies for environmental wastewater treatment and drinking water disinfection. Read moreRead less
The fate of copper in atom transfer radical reactions. Copper (Cu) complexes of poly-amine ligands have emerged as extremely active homogeneous catalysts in atom transfer radical reactions, forming organic radicals from alkyl halide precursors, and they are now employed extensively in polymer and organic chemistry. The catalyst cycles between its Cu(I) and Cu(II) oxidation states reversibly yet both forms are susceptible to side reactions, particularly with solvents which can lead to loss of cat ....The fate of copper in atom transfer radical reactions. Copper (Cu) complexes of poly-amine ligands have emerged as extremely active homogeneous catalysts in atom transfer radical reactions, forming organic radicals from alkyl halide precursors, and they are now employed extensively in polymer and organic chemistry. The catalyst cycles between its Cu(I) and Cu(II) oxidation states reversibly yet both forms are susceptible to side reactions, particularly with solvents which can lead to loss of catalytic activity. This project aims to apply a multifaceted approach to interrogate the catalysts in both their Cu(I) and Cu(II) oxidation states and identify for the first time the pathways that lead to undesirable side reactions and provide new ways of optimising catalyst performance.Read moreRead less
Enzyme Electrochemical Communication. The ways that redox enzymes communicate with an electrochemical electrode are poorly understood and most systems rely on small molecule mediators as electron shuttles to complete the circuit. The few examples where direct (unmediated) enzyme electrochemistry has been achieved have relied on empirical experimental approaches in electrode modification. In this project a rational approach will be taken, starting with a mediated enzyme electrochemical system whi ....Enzyme Electrochemical Communication. The ways that redox enzymes communicate with an electrochemical electrode are poorly understood and most systems rely on small molecule mediators as electron shuttles to complete the circuit. The few examples where direct (unmediated) enzyme electrochemistry has been achieved have relied on empirical experimental approaches in electrode modification. In this project a rational approach will be taken, starting with a mediated enzyme electrochemical system which is then systematically deconstructed to produce a minimal enzyme-electrode that is stabilised by non-covalent forces and functions without a mediator. This rational approach will provide new routes to the direct enzyme electrochemistry of other enzyme systems as yet unexplored.Read moreRead less
Short circuiting redox enzymes. Enzymes that catalyse oxidation or reduction reactions can be integrated with an electrode in the development of biosensors. A key challenge is enabling an electrical current between the enzyme and the electrode and this project aims to probe this phenomenon to provide an enzyme system that operates with greater efficiency than in nature.
Sodium ion interactions with biomass-derived hard carbon electrodes. This project aims to investigate sodium ion behavior when electrochemically interacting with hard carbon electrode materials by using both in-situ and ex-situ techniques in combination with advanced computational methods. This project expects to generate new knowledge and establish structure-property-performance correlations, thus providing guidelines and strategies for synthesising cost-effective electrode materials from bioma ....Sodium ion interactions with biomass-derived hard carbon electrodes. This project aims to investigate sodium ion behavior when electrochemically interacting with hard carbon electrode materials by using both in-situ and ex-situ techniques in combination with advanced computational methods. This project expects to generate new knowledge and establish structure-property-performance correlations, thus providing guidelines and strategies for synthesising cost-effective electrode materials from biomass for developing sustainable sodium-ion batteries. The intended outcome of this project includes knowledge advancement, enhanced capability to build international collaborations, training of early career researchers and students, and positioning Australia on the world map as a world-leading nation in energy storage.Read moreRead less
Pioneering stable copper carbanions for new C-C bond forming paradigms. The stabilisation of highly reactive carbanions underpins advances in chemical synthesis of new compounds including polymers, agrichemicals and pharmaceuticals. This project aims to deliver an innovative chemical reactivity platform, underpinned by copper carbanion complexes accessed via synthetic electrochemistry. Carbanions are essential components of carbon-carbon bond forming reactions but their high reactivity can be pr ....Pioneering stable copper carbanions for new C-C bond forming paradigms. The stabilisation of highly reactive carbanions underpins advances in chemical synthesis of new compounds including polymers, agrichemicals and pharmaceuticals. This project aims to deliver an innovative chemical reactivity platform, underpinned by copper carbanion complexes accessed via synthetic electrochemistry. Carbanions are essential components of carbon-carbon bond forming reactions but their high reactivity can be problematic. Expected outcomes of this project are an understanding of why these novel copper compounds are stable and how they can be utilised as synthetic reagents. This should provide significant benefits in unlocking the synthetic potential of a new class of chemical compound that has until now remained unexplored.Read moreRead less