NEW COPPER(I) CHEMISTRY-MODELS FOR METALLOPROTEINS

金属蛋白的新铜 (I) 化学模型

• 批准号: 3276363
• 负责人: KENNETH D. KARLIN
• 金额: $ 10.02万
• 依托单位: STATE UNIVERSITY OF NEW YORK AT ALBANY
• 依托单位国家: 美国
• 财政年份: 1981
• 资助国家: 美国
• 起止时间: 1981-04-01 至 1988-03-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/3276363
• 关键词: catechols; chelating agents; chemical models; chemical structure function; chemical synthesis; copper; dopamine beta monooxygenase; electron transport; hemocyanin; ligands; metalloenzyme; metalloproteins; monophenol monooxygenase; oxidation reduction reaction; oxidoreductase; phenols

The principal objective of the proposed research is the development of the coordination chemistry of Cu(I) in order to provide model compounds of possible relevance to the structures and activity of the copper ion sites in a number of redox active copper enzymes. The structural and chemical information obtained from studies of new Cu(I) chemical systems will be used to establish the chemistry of analogous Cu(II) compounds which are derived by electron transfer and/or dioxygen reactions. This will give insight into the essential nature of (a) Cu(I)-Cu(II) redox processes, and (b) Cu(I)-O2 (dioxygen) interactions and reactions. The copper centers and enzymes of immediate interest are; (a) the type 1 copper ion in the "blue" electron carriers and oxidases, (b) the type 3 copper center in the oxidase laccase, (c) hemocyanin and tyrosinase, and (d) dopamine beta-hydroxylase. A number of common features are apparent in the nature of the copper active sites of the proteins under discussion. They are: (1) the existence of "Cu(I)-like" sites in the proteins; (2) the reduced state of copper interacts/reacts with molecular oxygen in many of the copper enzymes. Specifically, our aims for the requested period of support are to: (1) design, synthesize and characterize new copper(I) complexes of polydentate ligand systems. These will be mononuclear and polynuclear, with nitrogen and/or sulfur donor groups, having coordination numbers of two through four. Systematic studies will establish tendencies in Cu(I) chemistry. (2) Characterize analogous C(II) derivatives. Through structural, electrochemical and other characterization, establish structural-redox relationships in Cu(I)-Cu(II) systems derived by electron transfer or from oxidation (oxygenation) by O2 of Cu(I). (3) Characterize the reaction chemistry of these copper complexes. Particular emphasis will be placed upon interactions and reactions with molecular oxygen and relevant substrates (phenols and catechols). This area includes synthetic and mechanistic studies of a monooxygenase model system.

拟议研究的主要目标是开发 铜(I)的配位化学，以提供模型化合物 可能与铜离子中心的结构和活性有关 在许多氧化还原活性铜酶中。结构和化学 从研究新的铜(I)化学体系中获得的信息将是 用于建立类似的铜(II)化合物的化学 由电子转移和/或氧气反应产生。这会给你带来 洞察(A)铜(一)-铜(二)氧化还原过程的本质，以及 (B)铜(I)-氧(O2)的相互作用和反应。 直接相关的铜中心和酶是：(A)类型1 “蓝色”电子载体和氧化酶中的铜离子，(B)类型3 氧化漆酶中的铜中心，(C)血蓝蛋白和酪氨酸酶 (D)多巴胺β-羟基酶。中有许多明显的常见特征 正在讨论的蛋白质的铜活性部位的性质。 它们是：(1)蛋白质中“类铜”部位的存在；(2) 铜的还原状态在许多情况下与分子氧相互作用/反应 铜酶。 具体地说，我们在请求的支持期内的目标是：(1) 新型多齿铜(I)配合物的设计、合成与表征 配基系统。这些将是单核和多核的，带有氮 和/或硫给体基团，配位数为2至 四。系统的研究将确立铜(I)化学的趋势。 (2)刻画了类似的C(II)衍生物。通过结构， 电化学和其他表征，建立结构-氧化还原 铜(I)-铜(II)体系中电子转移或电子转移的关系式 氧对铜(I)的氧化(氧化)(3)表征反应 这些铜的络合物的化学。我们将特别强调 关于与分子氧的相互作用和反应以及相关 底物(苯酚和儿茶酚)。这一领域包括合成和 单加氧酶模型体系的机理研究。