The Mechanism of Oxygen Atom Transfer

在化学系有机动力学项目的支持下，罗伯特·D·特拉华州大学化学系的巴赫将继续对小分子和生物分子中的氧转移过程进行理论研究。这些系统很难描述，在理论和计算上都是最具挑战性的。虽然在双电子过程中氧从过酸、二环氧乙烷和氧氮杂环丙烷等经典氧供体转移到各种亲核试剂如烯烃、胺、硫化物和膦的机理现在已经相当好地理解，但关于饱和烃通过单电子氧化反应的氧化还有很多要了解。借助于对O-O键离解能的高度精确的系统研究，巴赫教授将他关于氧转移的能量学的结论建立在良好的热力学基础上。建议的工作将导致更好地理解氧化反应，使用高层次的理论和计算方法，明确检查激发单重态电子结构的过氧亚硝酸在氢原子提取过程中的潜在作用。特拉华州大学化学系的巴赫在有机动力学计划的支持下，研究氧原子转移的机制，这对理解药物在体内的代谢很重要。这项工作对于理解被称为细胞色素P-450的酶家族如何在动物中代谢药物尤其重要。

With the support of the Organic Dynamics Program in the Chemistry Division, Professor Robert D. Bach, of the Department of Chemistry at the University of Delaware, will continue theoretical studies of oxygen transfer processes in both small molecules and in biomolecules. These are systems that are difficult to characterize and among the most challenging both theoretically and computationally. While the mechanism of oxygen transfer from such classical oxygen donors as peracids, dioxiranes and oxaziridines to a variety of nucleophiles such as alkenes, amines, sulfides and phosphines in two-electron processes are now reasonably well understood, much is yet to be learned about the oxidation of saturated hydrocarbons by one-electron oxidative reactions. Aided by a highly accurate systematic study of O-O bond dissociation energies, Professor Bach has placed his conclusions about the energetics of oxygen transfer on a sound thermodynamic basis. The proposed work will lead to a better understanding of oxidation reactions using high level theoretical and computational methods to explicitly examine the potential role of the excited singlet electronic structure of peroxynitrous acid in hydrogen atom abstraction processes.Professor Robert D. Bach, of the Department of Chemistry at the University of Delaware, with the support of the Organic Dynamics Program, studies the mechanism of oxygen atom transfer, which is important in understanding the metabolism of drugs in the body. This work is especially important to understanding how the family of enzymes known as cytochrome P-450 metabolizes drugs in animals.