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.
| Kozak, John J; Gray, Harry B; Garza-López, Roberto A (2018) Relaxation of structural constraints during Amicyanin unfolding. J Inorg Biochem 179:135-145 |
| Kretchmer, Joshua S; Boekelheide, Nicholas; Warren, Jeffrey J et al. (2018) Fluctuating hydrogen-bond networks govern anomalous electron transfer kinetics in a blue copper protein. Proc Natl Acad Sci U S A 115:6129-6134 |
| Teo, Ruijie D; Hwang, Jae Youn; Termini, John et al. (2017) Fighting Cancer with Corroles. Chem Rev 117:2711-2729 |
| Ener, Maraia E; Gray, Harry B; Winkler, Jay R (2017) Hole Hopping through Tryptophan in Cytochrome P450. Biochemistry 56:3531-3538 |
| Kozak, John J; Gray, Harry B; Garza-López, Roberto A (2016) Structural Stability of Intelectin-1. J Phys Chem B 120:11888-11896 |
| Warren, Jeffrey J; Shafaat, Oliver S; Winkler, Jay R et al. (2016) Proton-coupled electron hopping in Ru-modified P. aeruginosa azurin. J Biol Inorg Chem 21:113-9 |
| Kozak, John J; Gray, Harry B; Garza-López, Roberto A (2016) Cytochrome unfolding pathways from computational analysis of crystal structures. J Inorg Biochem 155:44-55 |
| Winkler, Jay R; Gray, Harry B (2016) Correction to Electron Flow through Metalloproteins. Chem Rev 116:8313 |
| Gray, Harry B; Winkler, Jay R (2016) The Rise of Radicals in Bioinorganic Chemistry. Isr J Chem 56:640-648 |
| Shafaat, Oliver S; Winkler, Jay R; Gray, Harry B et al. (2016) Photoactivation of an Acid-Sensitive Ion Channel Associated with Vision and Pain. Chembiochem 17:1323-7 |
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