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Details of Grant 

EPSRC Reference: GR/M50232/01
Title: MODEL COMPOUNDS FOR RADICAL-COPPER OXIDASES
Principal Investigator: Halcrow, Professor MA
Other Investigators:
Researcher Co-Investigators:
Project Partners:
Department: Sch of Chemistry
Organisation: University of Leeds
Scheme: Standard Research (Pre-FEC)
Starts: 22 March 1999 Ends: 21 June 2002 Value (£): 165,900
EPSRC Research Topic Classifications:
Chemical Synthetic Methodology
EPSRC Industrial Sector Classifications:
No relevance to Underpinning Sectors
Related Grants:
Panel History:  
Summary on Grant Application Form
New model compounds for the radical-copper oxidases galactose oxidase (GOase) and glyoxal oxidase will be prepared. These compounds will contain square-pyramidal copper (II) centres with a base ortho-thioether-substituted phenoxide ligand, bearing an intra-molecular graphitic stacking interaction between the phenoxide group and an arene substituent from a protecting ligand. The ultimate synthetic targets will be oxidised copper (II)/phenoxyl radical species derived from our complex precursors, which will accurately mimic the active form of the GOase copper centre. The electronic structures of these radical complexes and their neutral congeners will be characterised using structural (crystallography, EXAFS), spectroscopic (UV/vis, EPR), electrochemical and theoretical methods. By selectively removing substituents from the ligand framework, we intend to dissect the constituent elements of the G0ase non-innocent tyrosyl residue, and thus understand the principles underlying its extraordinary stability. In the longer term analogues which retain the co-ordinated, pi-stacked phenoxide motif but contain a vacant copper co-ordination site will be prepared. These will have the potential for substrate binding and redox activity at the copper ion; the reactivity of these products towards alcohols and other substrates will be examined. Thus, we hope to develop an aerobic oxidation catalyst whose properties match those of GOase as closely as possible.
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Organisation Website: http://www.leeds.ac.uk