Metalloenzyme Catalyzed Halogenations

金属酶催化卤化反应

• 批准号: 8716229
• 负责人: Alison Butler
• 金额: $ 24.35万
• 依托单位: University of California-Santa Barbara
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1988
• 资助国家: 美国
• 起止时间: 1988-01-01 至 1992-03-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=8716229&HistoricalAwards=false
• 关键词: Metalloenzyme; Catalyzed; Halogenations

The goal of this award is to elucidate the reactivities and mechanisms of two newly discovered haloperoxidase metalloenzymes, a vanadium bromoperoxidase (V-BrPO) and a non-heme iron (III) bromoperoxidase (FeNH-BrPO) which are both isolated from marine algae. V-BrPO and FeNH-BrPO are the first non-heme haloperoxidases to be discovered. Experiments are planned to test whether each metal ion functions as a Lewis acid catalyst or as an electron transfer catalyst, shuttling between different oxidation states. Both V-BrPO and FeNH-BrPO catalyze the bromination of pyrimidine- containing nucleic acids, cytosine and uracil. The reactivities of the two enzymes will be studied in terms of a) the types of organic compounds that can be brominated, b) the catalase and superoxide dismutase activity of the enzymes and c) the mechanism of reoxidation of the reduced derivatives of the enzymes. Halogenated organic compounds occur widely in marine organisms. Some of them have exciting biological activity. They represent a valuable, but neglected natural resource. The proposed research will help us understand how the myriad halogenated compounds are formed.

该奖项的目的是阐明两种新发现的卤代过氧化物酶金属酶的反应性和机制，即钒溴过氧化物酶 (V-BrPO) 和非血红素铁 (III) 溴过氧化物酶 (FeNH-BrPO)，这两种酶均从海藻中分离出来。 V-BrPO 和 FeNH-BrPO 是第一个被发现的非血红素卤过氧化物酶。 计划进行实验来测试每种金属离子是否充当路易斯酸催化剂或电子转移催化剂，在不同氧化态之间穿梭。 V-BrPO 和 FeNH-BrPO 均催化含嘧啶的核酸、胞嘧啶和尿嘧啶的溴化。 两种酶的反应性将根据以下方面进行研究：a) 可溴化的有机化合物的类型，b) 酶的过氧化氢酶和超氧化物歧化酶活性，以及​​ c) 酶的还原衍生物的再氧化机制。 卤代有机化合物广泛存在于海洋生物中。 其中一些具有令人兴奋的生物活性。 它们代表了一种宝贵但被忽视的自然资源。 拟议的研究将帮助我们了解无数卤代化合物是如何形成的。