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Dinuclear and polynuclear metal centres in biology: enzymes and synthetic analogues

Ziel

This project aims at making interdisciplinary contribution to the clarification of the role of metal ions at the active sites of several proteins and enzymes containing multimetal sites, particularly those containing iron and copper. The functions of these proteins span the activation and catalytic reactions of small molecules like dioxygen, dihydrogen, inorganic nitrogen and sulphur compounds, and electron transfer processes. The experimental approach involves detailed investigations of the spectroscopic properties of the proteins and several their derivatives, the mechanism of their activities, and the development of small molecule analogues for the multimetal active sites, which is based on intensive biomimetic chemistry on dinuclear and polynuclear complexes with suitable ligands. The latter systems should enable the derivation of structural-spectral, structural-magnetic, and structure-reactivity correlations of extreme importance for protein studies, and the design of new catalytic systems for chemical transformations of substrates of synthetic and environmental interest.
Various spectroscopic, kinetic and structural studies performed on the proteins have led to the characterization of various forms of hemocyanins and their tyrosinase like activity, the identification of the substrate binding site of ascorbate oxidase, the complete X-ray and solution structure of desulphuredoxin, the X-ray structure of the molybdenum/iron protein idehyde oxidoreductase, and the characterization of the multihaem proteins formate dehydrogenase and nitrite reductase. Synthetic analogues for the active sites of dinulclear copper and haem-copper proteins have been obtained using polydentate nitrogen ligands, and fuctional models of copper monooxygenase, superoxide dismutase and nitrite reductase enzymes have been developed. Dinuclear iron and manganese complexes with relavance to the non-haem iron proteins and the catalytic centre of photosystem II have also been studied, together with their oxidative activity. The reactivity of peroxynitrite towards a series of metal complexes has been investigated. New theoretical models have been developed to account for the magnetic interaction in dinuclear and polynuclear iron-containing clusters.

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CSC - Cost-sharing contracts

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UNIVERSITA DEGLI STUDI DI PAVIA
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Via Taramelli, 12
27100 PAVIA
Italien

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Letzte Aktualisierung: 7 Oktober 1998

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Permalink: https://cordis.europa.eu/project/id/CHRX920014/de

European Union, 2024