New Biologically Relevant Sulfur Radical Cation Chemistry

通过这一奖项，化学结构、动力学和机制计划支持亚利桑那大学的理查德·S·格拉斯进行一个项目，调查有机硫自由基阳离子在各种生物意义上的反应中的作用。我们将研究由酰胺和芳香族基团参与的邻基参与这些自由基阳离子的形成和稳定的作用。降低氧化电位，从而稳定生成的硫自由基阳离子的因素，以及这些独特体系中的成键性质将被评估。为了实现这些目标，将使用一系列技术，包括使用构象受限分子、电化学、脉冲辐解、电子顺磁共振、光电子能谱和理论计算。这些研究将涉及本科生和博士后，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。该项目有望有助于理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多肽和蛋白质中蛋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.