Understanding biological nitrogen fixation: an investigation of multi-electron reduction catalysis at novel iron-sulfur clusters. A new class of iron-sulfur clusters held together by a central light atom will be prepared and their reactions thoroughly studied. These clusters are important because they will have the same structure as the iron-molybdenum cluster of the enzyme nitrogenase. This enzyme fixes atmospheric nitrogen as ammonia. It is the primary route of nitrogen entry into all living s ....Understanding biological nitrogen fixation: an investigation of multi-electron reduction catalysis at novel iron-sulfur clusters. A new class of iron-sulfur clusters held together by a central light atom will be prepared and their reactions thoroughly studied. These clusters are important because they will have the same structure as the iron-molybdenum cluster of the enzyme nitrogenase. This enzyme fixes atmospheric nitrogen as ammonia. It is the primary route of nitrogen entry into all living systems. Industrially ammonia is produced in an energy-demanding process on a vast scale. The studies will provide insights into how nitrogenase works and how to design new multi-electron reduction catalysts. The research may lead to new energy-efficient routes to ammonia and to other new alternative fuel sources. Such processes would transform Australian industry and how we live.Read moreRead less
Dinuclear Ruthenium Complexes as Sequence- and Structure-Selective Binding Agents for DNA. Studies of the interaction of mononuclear metal complexes with DNA have greatly increased our understanding of the ways that small molecules recognise particular sites on DNA. However, in order to design drugs that target specific genes, and hence be potentially capable of controlling gene expression, it is necessary to study the binding of metal complexes that can associate with larger segments of DNA. ....Dinuclear Ruthenium Complexes as Sequence- and Structure-Selective Binding Agents for DNA. Studies of the interaction of mononuclear metal complexes with DNA have greatly increased our understanding of the ways that small molecules recognise particular sites on DNA. However, in order to design drugs that target specific genes, and hence be potentially capable of controlling gene expression, it is necessary to study the binding of metal complexes that can associate with larger segments of DNA. Using the combined expertise of the applicants, it is proposed to stereospecifically synthesise dinuclear complexes and study their DNA binding. This will greatly assist in the development of drugs that can selectively target genes and altered DNA.Read moreRead less
Mechanistic Studies on Biologically Active Iron Chelators. The need for orally effective drugs as alternatives to invasive treatment regimens such as subcutaneous infusion is an ongoing concern in health care. This is particularly true in people suffering iron overload. In many cases this condition is present at birth and thus the administration of vital iron chelation therapy via the oral route is a much preferred option. We have unearthed a novel series of candidates for iron chelation therapy ....Mechanistic Studies on Biologically Active Iron Chelators. The need for orally effective drugs as alternatives to invasive treatment regimens such as subcutaneous infusion is an ongoing concern in health care. This is particularly true in people suffering iron overload. In many cases this condition is present at birth and thus the administration of vital iron chelation therapy via the oral route is a much preferred option. We have unearthed a novel series of candidates for iron chelation therapy (the pyridine-2-carboxaldehyde isonicotinoyl hydrazone [PCIH] analogues) which show oral activity. These chelators undergo some interesting iron catalysed oxidation chemistry and it is vital that the mechanism of this reaction be elucidated to determine whether it will be of biological significance upon administration of these compounds as iron chelators.Read moreRead less
A new metalloprotein-inspired methodology for energy-efficient chemical reduction. Chemical reduction, a core process in chemistry and industry, is carried out on an enormous scale using present-day technology that is extremely energy wasteful and irreversibly consumes resources. This project aims to provide a new sustainable methodology for chemical reduction using sophisticated bio-inspired metal (electro) catalysts.
Renewable solar hydrogen generated from waste streams. Sunlight is the largest available carbon-neutral energy source, with enough energy striking the planet in one hour to satisfy our current requirements for about a year. With the novel catalysts designed in this project, we will use this energy to simultaneously generate hydrogen and destroy organic pollutants by oxidation.
Adding hydride punch to transition metal complexes for CO2 electroreduction. This project plans to apply an innovative methodology to the selective conversion of carbon dioxide (CO2) waste into useful C1 chemicals. The new inorganic chemistry approach is based on the invention of transition metal–organic hydride coordination complexes, which are designed to punch hydride ion (= a proton and two electrons) into metal-activated CO2-derived intermediates. The approach should naturally overcome the ....Adding hydride punch to transition metal complexes for CO2 electroreduction. This project plans to apply an innovative methodology to the selective conversion of carbon dioxide (CO2) waste into useful C1 chemicals. The new inorganic chemistry approach is based on the invention of transition metal–organic hydride coordination complexes, which are designed to punch hydride ion (= a proton and two electrons) into metal-activated CO2-derived intermediates. The approach should naturally overcome the two-electron barrier found for today's best transition metal electrocatalysts of CO2 reduction and, hence, enable the selective production of formaldehyde, a four-electron reduction product and bulk industrial feedstock chemical, or methanol, a six-electron reduction product and future transport fuel.Read moreRead less
Metal Directed Assembly of New Discrete and Framework Supramolecular Systems. An important aspect of this project is the development of strategies for assembling molecules and metals into larger units - leading to novel compounds and materials for which unusual and potentially useful properties can be anticipated. These may include materials that act as catalysts for chemical reactions or absorb and store gases (such as hydrogen for use as a fuel). More generally, the area is one that will under ....Metal Directed Assembly of New Discrete and Framework Supramolecular Systems. An important aspect of this project is the development of strategies for assembling molecules and metals into larger units - leading to novel compounds and materials for which unusual and potentially useful properties can be anticipated. These may include materials that act as catalysts for chemical reactions or absorb and store gases (such as hydrogen for use as a fuel). More generally, the area is one that will underpin the 'bottom-up' approach (building tiny components from individual molecules and ions) in the rapidly expanding field of nanotechnology. Clearly, if Australia is to remain internationally competitive in such new technologies then an understanding of processes of the type outlined in this proposal will be essential.Read moreRead less
Metal Directed Assembly of New Supramolecular Systems. An important aspect of this project is the development of strategies for assembling molecules and metals into larger units - leading to novel compounds and materials for which unusual and potentially useful properties can be anticipated. These may include materials that act as catalysts for chemical reactions or absorb and store gases (such as hydrogen for use as a fuel). More generally, the area is one that will underpin the 'bottom-up' ap ....Metal Directed Assembly of New Supramolecular Systems. An important aspect of this project is the development of strategies for assembling molecules and metals into larger units - leading to novel compounds and materials for which unusual and potentially useful properties can be anticipated. These may include materials that act as catalysts for chemical reactions or absorb and store gases (such as hydrogen for use as a fuel). More generally, the area is one that will underpin the 'bottom-up' approach (building tiny components from individual molecules and ions) in the rapidly expanding field of nanotechnology. Clearly, if Australia is to remain internationally competitive in such new technologies then an understanding of processes of the type outlined in this proposal will be essential.Read moreRead less
Nanoscale Molecular Architectures - New Metallo Cages and Capsules. The design and synthesis of novel cage and capsule-like supermolecular structures will be undertaken, including rare examples of two large cage types - one designed to incorporate two adjacent metal ions in an extended (chiral) cavity while the other utilises macrocyclic metal complexes as the 'walls' of the cage. In the latter case metal variation makes possible the alteration of the electronic environment of a guest occupying ....Nanoscale Molecular Architectures - New Metallo Cages and Capsules. The design and synthesis of novel cage and capsule-like supermolecular structures will be undertaken, including rare examples of two large cage types - one designed to incorporate two adjacent metal ions in an extended (chiral) cavity while the other utilises macrocyclic metal complexes as the 'walls' of the cage. In the latter case metal variation makes possible the alteration of the electronic environment of a guest occupying the central cavity . A third (capsule-like) system is designed to 'open' and 'close' under pH control. The present studies hold promise for underpinning the future development of nano-scale molecular devices.
Read moreRead less
Metal Directed Assembly of New Supramolecular Systems. This project is concerned with the use of designed metal-ion directed assembly for the construction of new supramolecular entities incorporating metal complexes as structural elements. A range of novel nanometre-scale architectures is planned, including supramolecular ellipses, squares, cubes and mechanically linked systems. The proposed research has implications for elucidating fundamental aspects of both supramolecular and metal complexati ....Metal Directed Assembly of New Supramolecular Systems. This project is concerned with the use of designed metal-ion directed assembly for the construction of new supramolecular entities incorporating metal complexes as structural elements. A range of novel nanometre-scale architectures is planned, including supramolecular ellipses, squares, cubes and mechanically linked systems. The proposed research has implications for elucidating fundamental aspects of both supramolecular and metal complexation behaviour. It also holds promise for the production of novel materials for which unusual and potentially useful properties can be anticipated.Read moreRead less