Stereoselectivity in Metalloprotein Electron Transfer

在无机、生物无机和 有机化学博士约翰·R。普拉杰维奇将 研究电子转移反应的程度， 金属蛋白依赖于三维结构， 另一种反应物。电子转移的速率将被比较 对于与光学异构体反应的金属蛋白，即， 含有相同原子的分子， 但它们的三维结构不同， 它们是不可重叠的镜像。的结果 这个项目可能有助于解释 在许多生物电子转移反应中表现出来。 该项目的主要目标是：（1）审查一个 金属蛋白质之间的一系列电子转移反应 和手性配位化合物， 确定了几种立体选择性的反应， 电子转移是可检测的。(2)测量的程度 在这些反应中的立体选择性。(3)确定在多大程度 立体选择性金属蛋白配位化合物 前体络合物中的离子配对有助于任何 观察到的电子转移立体选择性。(4)确定 供体-受体距离和取向在多大程度上起作用， 观察到的立体选择性的作用。(5)开发模型基于 可用的X射线晶体学数据和观察到的选择性 促进对立体化学控制的理解， 生物电子转移

With support from the Inorganic, Bioinorganic and Organometallic Chemistry Program Dr. John R. Pladziewicz will investigate the extent to which electron-transfer reactions of metalloproteins depend on the three-dimensional structure of the other reactant. Rates of electron transfer will be compared for metalloproteins reacting with optical isomers, i.e., molecules which contain the same atoms connected in the same way, but which differ in their three-dimensional structures so that they are non-superposable mirror images. The results of the project may help explain the exquisite selectivity exhibited by many biological electron-transfer reactions. The principal objectives of the project are to: (1) Examine a series of electron-transfer reactions between metalloproteins and chiral coordination compounds with the expectation of identifying several reactions for which stereoselective electron transfer is detectable. (2) Measure the extent of stereoselectivity in these reactions. (3) Determine the extent to which stereoselective metalloprotein-coordination compound ion pairing in the precursor complex contributes to any observed electron-transfer stereoselectivity. (4) Determine the extent to which donor-acceptor distance and orientaion play a role in observed stereoselectivity. (5) Develop models based on available x-ray crystallographic data and observed selectivity to advance understanding of the stereochemical control of biological electron transfer.