研究领域

Inorganic Chemistry

The Vincent group are interested in understanding details of catalysis and reactions at metal centres in proteins. Redox enzymes play key roles as catalysts in biological cycling of hydrogen, carbon and nitrogen and energy. Their active sites are built from common metals such as iron, nickel and copper, and the reactivity achieved at these centres is often difficult to replicate under ambient conditions with synthetic catalysts. We are interested in understanding details of the redox chemistry and mechanisms of catalysis occurring at enzyme active sites. A central theme in our research is attachment of enzymes to electrically conducting surfaces (electrodes or conducting particles). This provides precise control over enzyme reactions in direct electrochemical and spectroelectrochemical studies, but it also provides an immediate route to applying biological redox catalysis in hydrogen technologies and in specialised catalysis. Our studies target a range of metalloproteins including hydrogenases, nitrogenase and carbon monoxide dehydrogenase. We are particularly interested in the efficient catalysis of H2 oxidation and production by microbial hydrogenase enzymes at [FeFe] or [NiFe] active centres. Ligands at the active site of hydrogenases, CO and CN-, give rise to fairly intense absorption bands in the Infrared spectrum. This has inspired us to develop a suite of FTIR surface spectroelectrochemical methods for studying hydrogenase active site chemistry under electrochemical control. Understanding and exploiting selective enzyme catalysis should provide inspiration for new hydrogen energy technologies and development of novel catalytic materials. One application we have developed and patented is a system for recycling the biological cofactors NAD(P)+ and NAD(P)H with H2 as electron source or sink using graphite particles modified with enzyme moieties. Kylie Vincent's research is supported by the RCUK, the European Research Council (ERC) and the EPSRC.

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Grabarczyk, D.B., Ash, P.A., Vincent, K.A. 'Infrared Spectroscopy Provides Insight into the Role of Dioxygen in the Nitrosylation Pathway of a [2Fe2S] Cluster Iron-Sulfur Protein' J. Am. Chem. Soc., 2014, 136, 11236-11239. Link Hexter, S.V., Chung, M.-W., Vincent, K.A., Armstrong, F.A.'Unusual Reaction of [NiFe]-Hydrogenases with Cyanide' J. Am. Chem. Soc., 2014, 136, 10470-10477. Link McPherson, I.J., Vincent, K.A. 'Electrocatalysis by hydrogenases: lessons for building bio-inspired devices' J. Braz. Chem. Soc., 2014, 25, 427-441. Link Healy, A.J., Ash, P.A., Lenz, O., Vincent, K.A. 'Attenuated total reflectance infrared spectroelectrochemistry at a carbon particle electrode; unmediated redox control of a [NiFe]-hydrogenase solution' Phys Chem Chem Phys, 2013, 15, 7055-7059. Link Lauterbach, L., Lenz, O., Vincent, K.A. 'H2-driven cofactor regeneration using NAD(P)+-reducing hydrogenases' FEBs Journal, 2013, 280, 3058-3068. Link Reeve, H.A., Vincent, K.A., 'Bioelectrocatalysis for Direct Alcohol Fuel Cells' in Z.-X. Liang and T.S. Zhao (Eds.), Catalysts for Alcohol-Fuelled Direct Oxidation Fuel Cells, RSC, 2012. Link Reeve, H.A., Lauterbach, L., Ash, P.A., Lenz, O., Vincent, K.A., 'A modular system for regeneration of NAD cofactors using graphite particles modified with hydrogenase and diaphorase moieties' Chem. Commun. 2012, 48 (10), 1589-1591. Link. Ash, P.A., Vincent, K.A. 'Spectroscopic analysis of immobilised redox enzymes under direct electrochemical control' Chem. Commun., 2012, 48 (10), 1400-1409.Link. Lauterbach, L., Idris, Z., Vincent, K.A., Lenz, O. 'Catalytic properties of the isolated diaphorase fragment of the NAD+-reducing [NiFe]-hydrogenase from Ralstonia eutropha' PLoS ONE, 2011, 6, (10): e25939. Link. Healy, A.J., Reeve, H.A., Parkin, A., Vincent, K.A. 'Electrically conducting particle networks in polymer electrolyte as three-dimensional electrodes for hydrogenase electrocatalysis' Electrochimica Acta (2011) 56, 28, 10786-10790. Link. Lauterbach, L., Liu, J., Horch, M., Hummel, P., Schwarze, A., Haumann, M., Vincent, K.A., Lenz, O., Zebger, I. 'The hydrogenase subcomplex of the NAD+-reducing [NiFe]-hydrogenase from Ralstonia eutropha: insights into catalysis and redox interconversions' Eur. J. Inorg. Chem., 2011, 1067-1079. Link Healy, A.J., Reeve, H.A., Vincent, K.A. 'Development of an infrared spectroscopic approach for studying metalloenzyme active site chemistry under direct electrochemical control' Faraday Discussions. (2011) 148 345 - 357. Link Presented at Faraday Discussion 148: Spectroscopy, Theory and Mechanism in Bioinorganic Chemistry, 2010, University of Nottingham Lubner, C.E., Knorzer, P., Silva, P.J.N., Vincent, K.A., Happe, T., Bryant, D.A., Golbeck, J.H. 'Wiring an [FeFe]-Hydrogenase with Photosystem I for Light-Induced Hydrogen Production' Biochemistry 2010 49 10264-10266. Link In Biochemistry's Most Read Rapid Reports of 2011 Danyal, K., Inglet, B.S., Vincent, K.A., Barney, B.M., Hoffman, B.M., Armstrong, F.A., Dean, D.R., Seefeldt, L.C. 'Uncoupling Nitrogenase: Catalytic Reduction of Hydrazine to Ammonia by a MoFe Protein in the Absence of Fe Protein-ATP' J. Am. Chem. Soc. (2010) 132 13197-13199. Link Highlighted in a JACS Select collection focused on chemical mechanisms in biochemistry Vincent, K.A. 'Triggered Infrared spectroscopy for investigating metalloprotein chemistry' Philosophical Transactions of the Royal Society A (2010) 368, 3713-3731. Link Stripp, S., Goldet, G., Brandmayr, C., Sanganas, O., Vincent, K.A., Haumann, M., Armstrong, F.A., Happe, T. 'How Oxygen attacks [FeFe] Hydrogenases from photosynthetic Organisms' Proc. Natl Acad. Sci. USA (2009) 106, 17331-17336. Link Vincent, K.A., Barton, S.C., Canters, G.W., Heering, H.A. 'Electrocatalysis for fuel cells at protein-modified electrodes' in Koper, M. (Ed.) Fuel Cell Catalysis: A Surface Science Approach, John Wiley & Sons, USA, 2009. (Book Chapter). Link Woolerton, T.W., Vincent, K.A. 'Oxidation of dilute H2 and H2 / O2 mixtures by hydrogenases and Pt' Electrochimica Acta (2009) 54, 5011-5017. Link Ludwig, M., Cracknell, J.A., Vincent, K.A., Armstrong, F.A., Lenz, O. 'Oxygen-Tolerant H2 Oxidation By Membrane-Bound [NiFe]-Hydrogenases of Ralstonia species: Coping with Low-Level H2 in Air' J. Biol. Chem. (2009) 284, 465-477. Link Best, S.P., Borg, S.J., Vincent, K.A., 'Infrared Spectroelectrochemistry' in Kaim, W. and Klein, A. (Eds) Spectroelectrochemistry, Royal Society of Chemistry, 2008. (Book Chapter). Link