STUDIES ON MECHANISTICALLY CRYPTIC ENZYMATIC REACTIONS

两种微生物酶对脂环的作用机制 将从立体化学的观点研究代谢。 环己酮 加氧酶是一种黄素蛋白，其催化微生物形式的 Baeyer-Villager反应，在辅助下将环酮转化为内酯 分子氧。 该酶已被分离和表征;然而， 它的作用机制仍然是一个猜测的问题， 大多数需要黄素的酶。 环丙烷羧酸水解酶催化 环丙烷羧酸的肉毒碱衍生物的水解开环 酸，最终得到4-羟基丁酸。 这种酶还没有被 它是纯化的，关于它的作用机制知之甚少。 建议通过研究这两种酶的作用机制， 底物和产物之间的立体化学关系。 权会 be：（a）合成区域特异性和立体特异性标记的底物 氚，和（B）化学降解和酶分析手性标记的 产品. 研究的药学和环境意义 讨论了这种分解代谢过程。

The mechanisms of action of two microbial enzymes involved in alicyclic ring metabolism will be studied from a stereochemical point of view. Cyclohexanone oxygenase is a flavoprotein which catalyzes, a microbiological version of the Baeyer-Villager reaction, transforming cyclic ketones into lactones with the aid of molecular oxygen. The enzyme has been isolated and characterized; however its mechanism of action is still a matter of much speculation, as is true for most flavin-requiring enzymes. Cyclopropane carboxylate hydrolase catalyzes the hydrolytic ring cleavage of the carnitine derivative of cyclopropane carboxylic acid, ultimately affording 4-hydroxybutyric acid. The enzyme has not been purified, and very little is known regarding its mechanism of action. It is proposed to study the mechanisms of both enzymes through investigation of the stereochemical relationships between substrates and products. Involved will be: (a) synthesis of substrates regio- and stereospecifically labeled with tritium, and (b) chemical degradation and enzymic analysis of chirally-labeled products. The pharmaceutical and environmental significance of the study of such catabolic processes is discussed.