Electronic Structure Studies of Molybdenum Oxotransferases

9316557柯克这个奖项是柯克博士的博士后研究奖学金在化学的启动补助金增量。该研究的主旨是在生物和无机体系中通过第VI族金属进行氧转移的实验和理论研究。利用变温、变场磁圆二色性、单晶偏振吸收和共振拉曼光谱的组合光谱方法将探测黄嘌呤氧化酶催化中间体的Mo（V）态。这些酶的研究将补充平行调查的相关模型化合物显示的结构特征，认为是目前在酶的活性位点。激发态光谱研究将被用来评估详细的键合计算的结果，包括自洽场散射波计算，过渡态计算，密度泛函方法纳入斯莱特或高斯型基函数。 第VI族金属，特别是钼和钨，在酶和无机系统中对氧转移具有催化活性。这些研究将提供大量关于底物与金属结合模式的信息，并将直接探测从金属到底物的氧代转移的初始步骤。 ***

9316557 Kirk This award is the starter grant increment of Dr. Kirk's Postdoctoral Reseaerch Fellowship in Chemistry. The main thrust of the research is a combined experimental and theoretical study of oxygen transfer by Group VI metals in both biological and inorganic systems. A combined spectroscopic approach utilizing variable-temperature, variable-field magnetic circular dichroism, single crystal polarized absorption, and resonance Raman spectroscopies will probe the Mo(V) state of xanthine oxidase catalytic intermediates. These enzyme studies will be complemented by parallel investigations of relevant model compounds which display structural features believed to be present at the enzyme active site. Excited state spectral studies will be used in order to evaluate the results of detailed bonding calculations including self-consistent field scattered wave calculations, transition-state calculations, and density functional methods incorporating Slater or Gaussian-type basis functions. %%% Group VI metals, specifically molybdenum and tungsten are catalytically active towards oxygen transfer in both enzymatic and inorganic systems. These studies will provide a wealth of information concerning the mode of substrate binding to the metal and will directly probe the initial steps in oxo transfer from metal to substrate. ***