Electronic Structure Studies of Molybdenum Oxotransferases

9316557柯克这一奖项是柯克博士化学博士后研究奖学金的首次授予。这项研究的主要目的是对生物和无机体系中第VI族金属的氧转移进行实验和理论相结合的研究。利用变温、变场磁圆二色谱、单晶偏振吸收光谱和共振拉曼光谱相结合的光谱方法，可以探测黄嘌呤氧化酶催化中间体的Mo(V)状态。这些酶研究将得到相关模型化合物的平行研究的补充，这些模型化合物显示出据信存在于酶活性部位的结构特征。激发态谱研究将被用来评估详细的成键计算的结果，包括自洽场散射波计算、过渡态计算以及结合斯莱特或高斯型基函数的密度泛函方法。%第VI族金属，特别是钼和钨，在酶和无机体系中都对氧转移具有催化活性。这些研究将提供关于底物与金属结合方式的丰富信息，并将直接探索从金属到底物的氧转移的初始步骤。***

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. ***