Hydride Transfer Between NAD+ Analogues

有机动力学计划的这笔赠款支持 莫里斯·M教授的继续工作。Kreevoy在 明尼苏达大学。 实验和理论研究 氢化物对NAD+的贡献和从NADH的提取将是 研究了 一个半经验势能面， 氢同位素的转移将适合于 实验数据和这个表面的预测能力 将检查氘化物转移中的反应性。 的 计算将使用POLYRATE程序来预测 离子配对的影响和溶剂的显式包含， 速率常数和同位素效应。 %%% 一个重要的通道，电子从 有机分子包括氢离子的转移， 它是一个氢原子和一个额外的电子。实际上， 这种类型的电子转移涉及同时 电子和氢原子的转移。 新方法 将开发的氢化物提取的研究， 除了生物学上重要的分子。 这项工作将 从根本上加强我们对反应的认识， 溶液中的多原子物质，特别是 在这些反应中的溶剂。

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.