New Biologically Relevant Sulfur Radical Cation Chemistry

有了这个奖项，化学结构，动力学和机制计划支持理查德S。Glass在一个项目中研究了有机硫自由基阳离子在各种生物学重要反应中的作用。 将研究相邻基团参与的影响，由酰胺和芳香族基团，在这些自由基阳离子的形成和稳定。将评估降低氧化电位的因素，从而稳定所得硫自由基阳离子，以及这些独特系统中的键合性质。为了实现这些目标的技术，包括使用构象约束的分子，电化学，脉冲辐解，电子顺磁共振，光电子能谱和理论计算的组合，将被使用。这些研究将涉及本科生和博士后学生，以及与堪萨斯大学、弗里堡大学和圣母大学的研究人员合作。 该项目预计将有助于了解生物学中的远程电子转移，阿尔茨海默病的化学基础以及肽和蛋白质中甲硫氨酸残基的氧化机制。

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.