Untersuchungen zu einkernigen Kupfer- und Eisenkomplexen mit biomimetischer Relevanz zur Reaktionsweise von Radikalen in biologischen Prozessen

与生物过程中自由基反应具有仿生相关性的单核铜铁配合物的研究

• 批准号: 5183438
• 负责人: Professor Hans-Jörg Krüger, Ph.D.
• 金额: --
• 依托单位: Fachbereich Chemie
• 依托单位国家: 德国
• 项目类别: Priority Programmes
• 财政年份: 1999
• 资助国家: 德国
• 起止时间: 1998-12-31 至 2007-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/5183438?language=en
• 关键词: Untersuchungen; zu; einkernigen; Kupfer; und

In recent years radicals have gained more and more importance in the discussion of biological processes. Objectives of this proposal are the synthesis of biomimetic complexes for the active sites in the copper-containing enzymes galactose oxidase and copper amine oxidase and in the iron-containing enzyme intradiol-cleaving catechol dioxygenase - all enzymes for which radicals are either known or believed to be involved in the reaction mechanisms - and the investigation of the structural and electronic properties as well as of the reactivity of these complexes. Thus, novel copper(II) phenoxyl radical complexes will be synthesized to serve as functional model complexes for the reactivity of the active site in galactose oxidase. The reproduction of the reactivity of copper amine oxidase and especially the modelling of the intramolecular redox reaction occurring between the copper ion and the 4-aminoresorcine cofactor in the active site are the objectives of a study focusing on copper complexes in which a 2-hydroxy-1,4-quinone unit or derivatives thereof are either directly coordinated to the copper ion or only placed in the proximity of the copper ion. The last part of this proposal concentrates on functional model complexes which address the reasons why the reaction of molecular oxygen with an iron(III) catecholate species occurs during catalytic turnovers of intradiol-cleaving catechol dioxygenases.

近年来，自由基在生物过程的讨论中变得越来越重要。该提案的目的是合成含铜酶半乳糖氧化酶和铜胺氧化酶以及含铁酶内二醇裂解儿茶酚双加氧酶活性位点的仿生复合物——所有酶的自由基都是已知的或被认为是参与反应机制 - 以及这些配合物的结构和电子特性以及反应性的研究。因此，将合成新型苯氧基铜(II)自由基络合物作为半乳糖氧化酶活性位点反应性的功能模型络合物。铜胺氧化酶反应性的再现，特别是铜离子和活性位点中的 4-氨基间苯二酚辅因子之间发生的分子内氧化还原反应的建模，是专注于铜配合物的研究的目标，其中 2-羟基- 1,4-醌单元或其衍生物直接与铜离子配位或仅位于铜离子附近。该提案的最后一部分集中于功能模型复合物，该复合物解决了在二醇裂解儿茶酚双加氧酶的催化转换过程中分子氧与儿茶酚酸铁（III）物质发生反应的原因。