Metalloenzyme Catalyzed Halogenations

该奖项的目的是阐明反应性， 两种新发现的卤过氧化物酶的作用机制 金属酶、钒溴过氧化物酶（V-BrPO）和钒溴过氧化物酶。 非血红素铁（III）溴过氧化物酶（FeNH-BrPO）， 都是从海藻中分离出来的 V-BrPO和FeNH-BrPO是 第一个被发现的非血红素卤代过氧化物酶 实验计划测试每种金属离子是否 用作刘易斯酸催化剂或电子转移催化剂 催化剂，在不同的氧化态之间穿梭。 两 V-BrPO和FeNH-BrPO催化嘧啶的溴化反应， 含有核酸、胞嘧啶和尿嘧啶。 的 两种酶的反应性将在以下方面进行研究 a）可被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 c）还原态的再氧化机理 酶的衍生物。 卤代有机物广泛存在于海洋生物中 有机体 其中一些具有令人兴奋的生物活性。 它们是一种宝贵但被忽视的自然资源。 这项拟议中的研究将帮助我们了解 形成卤代化合物。

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.