Photogeneration of Protein Radicals for Enzyme Catalysis

用于酶催化的蛋白质自由基的光生作用

• 批准号: 6729021
• 负责人: STEPHEN M CONTAKES
• 金额: $ 2.99万
• 依托单位: CALIFORNIA INSTITUTE OF TECHNOLOGY
• 依托单位国家: 美国
• 财政年份: 2002
• 资助国家: 美国
• 起止时间: 2002-04-01 至 2004-10-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/6729021
• 关键词: acidity /alkalinity; amine oxidase (copper); aminoacid analog; catalyst; chemical kinetics; chemical synthesis; cofactor; colorimetry; electron spin resonance spectroscopy; enzyme mechanism; enzyme model; enzyme substrate; enzyme substrate complex; flash photolysis; free radicals; hydroquinones; intermolecular interaction; model design /development; molecular site; oxidation reduction reaction; photochemistry; protein structure function; technology /technique development; ultraviolet spectrometry; zinc

DESCRIPTION: (provided by applicant) The project goal is to develop a photochemical method for investigating and modifying the mechanism of protein-based enzyme catalysis. The method will be demonstrated in the copper amine oxidase system. Catalytically-relevant topa quinone (TPQ) radical will be generated in protein which has been modified by replacing the redox active copper cofactor with an organic substrate linked through a hydrocarbon chain to a photochemical sensitizer on the outside of the enzyme. The influence of the active site metal and pH on the structure and reactivity of the TPQ radical will be studied using a combination of metal replacement experiments and chemical modification of the substrate. The method will be extended to perform photocatalysis of amine oxidation under anaerobic conditions.

描述：（由申请人提供）项目目标是开发 用于研究和修改机制的光化学方法 基于蛋白质的酶催化。该方法将在铜中进行演示 胺氧化酶系统。与催化相关的TOPA喹酮（TPQ）自由基将是 通过替换氧化还原活性来修饰的蛋白质产生 铜辅因子的有机基材通过碳氢化合物链连接到 酶外部的光化学敏化剂。影响 活性位点金属和pH在TPQ自由基的结构和反应性上 将使用金属替代实验和 底物的化学修饰。该方法将扩展到执行 在厌氧条件下胺氧化的光催化。