Synthesis of Oxygenated Hydrocarbons by Cytochrome P-450 Electroenzymology

这项工作的目的是开发一种经济合成含氧碳氢化合物的方法，该方法使用固定化在工作电极上的活性细胞色素P-450。研究的直接目标是确定NADH驱动的P-450羟基化碳氢化合物的化学计量学、产物分布和动力学，开发用于P-450再生的修饰电极，并比较NADH和电化学再生的细胞色素P-450的产物、速率和产量。研究了两种形式的细胞色素：P-450cam和P-450soy；对其异同进行了分析。碳氢化合物底物包括去樟脑、-蒎烯、1,2,3,4-四氢萘（四氢萘）、十氢萘（十氢萘）和萘。研究了区域特异性和立体特异性，测量了细胞色素的周转率，并建立了该过程的模型。这将导致一种节能的生物电化学过程，将电催化剂的效率与酶的特异性结合起来，从而产生高产量的高价值产品，几乎没有不必要的副反应。该项目是与杜邦公司合作完成的。

Vincent Vilker 9313009 This work is directed toward development of an economical synthesis of oxygenated hydrocarbons using active cytochrome P-450 immobilized on a working electrode. The immediate objectives are to determine stoichiometries, product distributions, and kinetics of the hydroxylation of hydrocarbons by NADH-driven P-450, to develop modified electrodes for the regeneration of P-450, and to compare products, rates, and yields of the NADH and electrochemically regenerated cytochrome P-450. Two forms of cytochrome are studied: P-450cam and P-450soy; the similarities and differences are examined. Hydrocarbon substrates include norcamphor, -pinene, 1,2,3,4-tetrahydronaphthalene (tetralin), decahydronaphthalene (decalin), and naphthalene. Regiospecificity and stereospecificity are examined, turnover rates on the cytochrome are measured, and models of the process are developed. This should lead to an energy-efficient bioelectrochemical process that combines the efficiency of electrocatalysts with the specificity of enzymes, thus producing good yields of high-value products with little unwanted side reaction. The project is done in collaboration with the duPont Company.