Hydride Transfer Between NAD+ Analogues

来自有机动力学项目的这笔赠款支持了明尼苏达大学莫里斯·M·克里沃伊教授的继续工作。我们将对氢化物对NAD+的贡献和对NADH的提取进行实验和理论研究。氢同位素转移的半经验势能面将与实验数据相吻合，并将检验该势能面预测氢化物转移反应性的能力。计算将使用POLYRATE程序来预测离子配对和显式包含的溶剂对速率常数和同位素效应的影响。电子进出有机分子的一个重要途径是氢化物离子的转移，即一个氢原子和一个附加电子的转移。实际上，这种类型的电子转移包括一个电子和一个氢原子的同时转移。将开发新的方法来研究氢化物从生物重要分子中提取和加成的过程。这项工作将从根本上加强我们对多原子物质在溶液中反应的认识，特别是溶剂在这种反应中的作用。

This grant from the Organic Dynamics Program supports the continuing work of Professor Maurice M. Kreevoy at the University of Minnesota. An experimental and theoretical study of hydride donation to NAD+ and abstraction from NADH will be studied. A semi-empirical potential energy surface for the transfer of the hydrogen isotope will be fit to the experimental data and the ability of this surface to predict the reactivity in deuteride transfer will be examined. The computations will use the POLYRATE program to predict the effect of ion pairing and the explicit inclusion of solvent on rate constants and isotope effects. %%% An important pathway for the transfer of electrons to and from organic molecules involves the transfer of a hydride ion, whichis a hydrogen atom with an additional electron. In effect, this type of electron transfer involves the simultaneous transfer of an electron and a hydrogen atom. New methodology will be developed for the study of hydride abstraction from and addition to biologically iomportant molecules. This work will fundametally strengthen our knowledge of reactions of polyatomic substances in solution, and particulary the role of the solvent in such reactions.