New Biologically Relevant Sulfur Radical Cation Chemistry

点击翻译按钮获取中文摘要

With this award, the Chemical Structure, Dynamics, and Mechanisms Program supports Richard S. Glass of University of Arizona in a project investigating the role of organosulfur radical cations in various biologically significant reactions. The effect of neighboring group participation, by amide and aromatic groups, in the formation and stabilization of these radical cations will be studied. Factors that lower the oxidation potential, thereby stabilizing the resulting sulfur radical cations, and the nature of the bonding in these unique systems will be assessed. To accomplish these goals a combination of techniques, including the use of conformationally constrained molecules, electrochemistry, pulse radiolysis, electron paramagnetic resonance, photoelectron spectroscopy and theoretical calculations, will be used. These studies will involve undergraduate and postdoctoral students as well as collaborations with researchers at the University of Kansas, the University of Fribourg and the University of Notre Dame. This project is expected to contribute to an understanding of long range electron transfer in biology, the chemical basis of Alzheimer's disease and the mechanism of oxidation of methionine residues in peptides and proteins.