Electrochemical Reactions Involving Large Structural Change

这项主要在本科院校(PUI)的研究项目是在分析和表面化学的一般领域，以及生物电化学的子领域。这一创新计划的目标是表征在电子转移过程中经历分子结构巨大变化的过渡金属络合物的电化学行为。这项研究的实验结果将用于测试当前的电子转移反应理论，并了解与结构变化相关的异常氧化还原行为的例子。将使用动态伏安技术、低温电化学和微电极来研究电极反应的速率和机理。X射线吸收精细结构(EXAFS)光谱电化学将被用来确定由于电子转移而发生的金属-配体键长的变化。被研究的化合物包括氧钼(VI)络合物、轴向取代的铁卟啉和钴大环、金属-金属键合的钼和钨二聚体以及从固氮酶中提取的铁-钼辅助因子。这些研究的结果将有助于我们理解金属酶催化的电子转移反应，并对生物技术和体内过程都有意义。

This Research in Primarily Undergraduate Institutions (PUI) project is in the general area of analytical and surface chemistry and in the subfield of bioelectrochemistry. The goal of this innovative program is to characterize the electrochemical behavior of transition metal complexes that experience a large change in molecular structure during electron transfer. Experimental results from this research will be used to test current theories of electron transfer reactions and to understand examples of unusual redox behavior associated with structural change. Rates and mechanisms of electrode reactions will be investigated using dynamic voltammetric techniques, low temperature electrochemistry, and microelectrodes. X-ray absorption fine structure (EXAFS) spectroelectrochemistry will be used to determine changes in metal-ligand bond distances that occur as a result of electron transfer. Compounds to be investigated include oxomolybdenum (VI) complexes, axially substituted iron porphyrins and cobalt macrocycles, metal-metal bonded dimers of molybdenum and tungsten, and the iron-molybdenum cofactor extracted from nitrogenase enzyme. The results of these investigations should contribute significantly to our understanding of metalloenzyme-catalyzed electron transfer reactions and have relevance to both biotechnological and in vivo processes.