Gated Electron Transfer in Copper(II)/(I) Systems

铜 (II)/(I) 系统中的门控电子转移

• 批准号: 9218391
• 负责人: David Rorabacher
• 金额: $ 30万
• 依托单位: Wayne State University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1993
• 资助国家: 美国
• 起止时间: 1993-03-15 至 1997-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9218391&HistoricalAwards=false
• 关键词: Gated; Electron; Transfer; Copper; II

With this award, the Inorganic, Bioinorganic, and Organometallic Chemistry Program provides support for a collaborative research project involving Drs. David B. Rorabacher and Ronald R. Schroeder of the Chemistry Department, Wayne State University, and Dr. Leo A. Ochrymowycz of the Chemistry Department, University of Wisconsin-Eau Claire. They will synthesize a series of copper thiaether, thiaamine, and thiapyridine complexes in which both copper(I) and copper(II) oxidation states are accessible. Using cyclic voltammetry, stopped-flow kinetics, NMR line broadening studies, and selected structural determinations, they will investigate the relationship between ligand geometric changes and transfer of electrons to and from the copper centers in these complexes. It is expected that under some conditions the rate of the reaction in one direction will be "gated" by the requirement for the intermediate to undergo a conformational change. %%% Complexes of copper(I) and copper(II) are known to have different geometries, so that upon oxidation or reduction it is likely that conformational changes will occur. A conformational change creates an energy barrier to electron transfer. If this energy barrier can be controlled, then it becomes possible for electron transfer to occur in one direction, that is, to be "gated." This topic is of considerable current interest in biological chemistry, because it may be important in the reactions of metalloproteins. This research will help to answer questions about the extent to which conformational changes in the proteins or around the metal binding site are involved in this effect.

通过这一奖项，无机化学、生物无机化学和金属有机化学计划为韦恩州立大学化学系的David B.Rorabacher博士和Ronald R.Schroeder博士以及威斯康星大学Eau Claire大学化学系的Leo A.Ochrymowycz博士的合作研究项目提供了支持。他们将合成一系列铜的硫醚、硫胺和硫代吡啶的络合物，其中铜(I)和铜(II)的氧化态都是可访问的。利用循环伏安法、停流动力学、核磁共振谱线展宽研究和选择性结构测定，他们将研究配体几何变化与电子在这些配合物中进出铜中心的转移之间的关系。预计在某些条件下，一个方向的反应速度将被中间体发生构象变化的要求所“控制”。已知铜(I)和铜(II)的络合物具有不同的几何构型，因此在氧化或还原时很可能会发生构象变化。构象变化对电子转移造成了能量障碍。如果这个能垒可以被控制，那么电子转移就有可能发生在一个方向上，也就是说，被“选通”。这一主题目前在生物化学中引起了相当大的兴趣，因为它可能在金属蛋白的反应中发挥重要作用。这项研究将有助于回答有关蛋白质或金属结合部位周围的构象变化在多大程度上参与这一效应的问题。