Problems in Bioinorganic and Metal Cluster Chemistry

无机化学、生物无机化学和有机金属化学项目的这一奖项将支持哈佛大学的R.H.霍尔姆教授在生物无机化学的几个领域继续研究。有待研究的领域包括1)钼氧转移酶，包括兔肝醛氧化酶类似物的合成和同位素标记研究；2)固氮酶辅助因子模型的合成；3)镍酶氢酶和CO脱氢酶的功能模型。在所有的模拟研究中，重点放在提供酶作用的功能模拟的合成模型上。在一个生物相关性较低的领域，将研究从可溶性硫代金属酸盐合成分子查尔原胺簇，并通过从不可溶的非分子固体中切除片段来合成分子查尔原胺簇。许多酶的性质是这样的，精确的分子结构和机理细节不能用传统的物理技术来确定。已经发展出各种间接方法，可以用来推断酶的结构，并帮助确定其催化机制中涉及的各个化学步骤。这些间接方法的应用和发展是本研究的目的。

This award in the Inorganic, Bioinorganic and Organometallic Chemistry Program will support continued studies by Professor R. H. Holm of Harvard University in several areas of bioinorganic chemistry. Areas to be investigated include 1) molybdenum oxotransferases including synthesis of analogues and isotopic labeling studies of rabbit liver aldehyde oxidase; 2) synthesis of models for the cofactors of nitrogenase; 3) functional models of the nickel enzymes hydrogenase and CO dehydrogenase. In all analogue studies emphasis is on synthetic models that provide functional mimics of the enzyme action. In a less biologically related area investigations of the synthesis of molecular chalogenide clusters from soluble thiometallates and by excision of fragments from insoluble, nonmolecular solids will be undertaken. %%% The nature of many enzymes is such that precise molecular structures and mechanistic details cannot be determined by conventional physical techniques. A variety of indirect methods have evolved that can be used to infer enzyme structures and to help define the individual chemical steps involved in their catalytic mechanisms. The application and development of these indirect methods is the purpose of this research.