The oxidation-reduction chemistry of manganese (II,III,IV) complexes is to be investigated by electrochemical, spectroscopic, magnetic, and stopped-flow methods in aqueous and in aprotic solvents. One goal of the research is to discover manganese complexes and solution conditions which result in oxidation-reduction chemistry that mimics that of mitochondrial superoxide dismutase (SOD), of the water-oxidizing species associated with photosystem II in green-plant photosynthesis, and of neurological manganese. The ligands proposed for study are 3,5-di-tert-butylactechol, 2,2'-bipyridine, o-aminophenol, triethanolamine, pyrophosphate ion, sorbiotl, catecholamine, L-DOPA, and 8-quinolinol. Determination of the oxidation-reduction thermodynamics, reaction kinetics, and solution structures for the various manganese complex-solvent systems will be the means of characterization. Studies of the reaction chemistry and the chemistry of the reaction products for the various manganese complexes in combination with O2, O2 minus, and H2O2 are a major part of the project. The oxidation-reduction potentials for manganese, iron and copper-zinc superoxide dismutases will be determined. A model complex for the manganese cofactor of photosystem II will be prepared and evaluated in relation to the efficient oxidation of H2O to O2.
| Logothetis, D E; Kim, D H; Northup, J K et al. (1988) Specificity of action of guanine nucleotide-binding regulatory protein subunits on the cardiac muscarinic K+ channel. Proc Natl Acad Sci U S A 85:5814-8 |
| Sugimoto, H; Spencer, L; Sawyer, D T (1987) Ferric chloride-catalyzed activation of hydrogen peroxide for the demethylation of N,N-dimethylaniline, the epoxidation of olefins, and the oxidative cleavage of vicinal diols in acetonitrile: a reaction mimic for cytochrome P-450. Proc Natl Acad Sci U S A 84:1731-3 |
| Cofre, P; Sawyer, D T (1986) Electrochemical reduction of dioxygen to perhydroxyl (HO2.) in aprotic solvents that contain Bronsted acids. Anal Chem 58:1057-62 |
| Yamaguchi, K S; Spencer, L; Sawyer, D T (1986) Tris(picolinato)manganese(II): a chemical model for the mechanism and function of mitochondrial superoxide dismutase. FEBS Lett 197:249-52 |
