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，激进分子在对生物过程的讨论中越来越重要。该提案的目标是含铜酶的活性位点的生物模拟复合物的合成，载乳氧化酶氧化酶和铜胺氧化酶以及含铁酶内裂解的触发核心内核二氧酶的含铁酶的所有酶的所有酶是已知的均与racterronis contrones as the Rections Assismiss is contractians Assismiss as the Rections Assismiss的所有酶，并且这些复合物的反应性。因此，新型铜（II）苯氧基自由基复合物将被合成，以作为半乳糖氧化酶中活性位点反应性的功能模型复合物。铜胺氧化酶的反应性的再现，尤其是在活性部位中铜离子和4-氨基霉素辅因子之间发生的分子内氧化还原反应的建模，这是一项研究的目的，是针对铜络合物的目标，在该研究中，仅将其直接饲养的铜络合物或仅放置在该研究中，或者仅将其直接供应。铜离子。该提案的最后一部分集中在功能模型复合物上，该复合物解决了分子氧与铁（III）的脱甲酸物种的反应发生在催化裂解的儿茶酚二氧酶的催化失误期间发生的原因。