Electron-transfer reactions play a key role in oxidative phosphorylation and respiration, drug and carcinogen metabolism and activation, immune response, collagen synthesis, and intermediary metabolism.
Our aim i s to probe some of the factors that control the rates of long-range electron-transfer processes in metalloenzymes: driving force, temperature, site-to-site distance, and the nature of the protein medium and the electron acceptor site. We intend to study intramolecular long-range electron-transfer reactions in ruthenium (II/III) derivatives of three structurally well-characterized copper proteins: P. aeruginosa azurin, bovine erythrocyte superoxide dismutase, and Cu(II)-substituted horse liver alcohol dehydrogenase. During the next three years we propose to: (1) prepare highly purified and well-characterized samples of the above three proteins labelled at selected surface histidine residues with ruthenium (II/III) reagents: (2) determine by flash photolysis experiments the rates of electron transfer from the surface-bound ruthenium (II) reagents to the copper (II) sites in the interiors of these proteins, thereby providing important kinetic information relating directly to electron tunnelling through proteins; and (3) measure the pH and temperature dependences of the reduction potentials in the native and modified copper proteins by spectroelectrochemical techniques, which will give us a detailed picture of the factors that control the thermodynamics of these long-range electron-transfer reactions.
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