The Mechanism of Oxygen Atom Transfer

在化学系有机动力学项目的支持下，特拉华大学化学系的罗伯特·D·巴赫教授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系统之一。虽然在双电子过程中氧从经典的供氧体如过氧酸、二氧杂环烷和恶氮杂环烷转移到各种亲核剂如烯烃、胺、硫化物和膦的机理已经被很好地理解了，但关于饱和烃通过单电子氧化反应的氧化还没有很好的了解。在对O-O键离解能的高精度系统研究的帮助下，巴赫教授将他关于氧转移的能量学的结论建立在合理的热力学基础上。这项拟议的工作将使人们更好地理解氧化反应，使用高水平的理论和计算方法来明确地研究过亚硝酸的激发单重态电子结构在氢原子提取过程中的潜在作用。特拉华大学化学系的罗伯特·D·巴赫教授在有机动力学计划的支持下，研究了氧原子转移的机制，这对于理解药物在体内的新陈代谢非常重要。这项工作对于了解被称为细胞色素P-450的酶家族如何在动物体内代谢药物尤为重要。

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.