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Robert D. Bach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。这些系统很难表征，在理论上和计算上都是最具挑战性的。虽然氧在双电子过程中从过氧酸、二氧环烷和恶氮嘧啶等经典供氧体转移到各种亲核试剂（如烯烃、胺、硫化物和膦）的机制现在已经得到了相当好的理解，但关于饱和碳氢化合物通过单电子氧化反应氧化的机制还有待了解。在对O-O键解离能的高度精确的系统研究的帮助下，巴赫教授把他关于氧转移的能量学的结论建立在一个健全的热力学基础上。本文提出的工作将有助于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检查过氧亚硝酸的激发单线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Robert D. Bach教授在有机动力学项目的支持下，研究氧原子转移的机制，这对了解药物在体内的代谢非常重要。这项工作对于理解细胞色素P-450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.