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Cu-S complexes in the heart of biological electron transfer: the homodinuclear CuA site of Cytochrome-c oxidases and N2O reductases

生物电子转移核心的 Cu-S 复合物：细胞色素 c 氧化酶和 N2O 还原酶的同双核 CuA 位点

基本信息

批准号：
175008652
负责人：
Professor Dr. Matthias Bauer
金额：
--
依托单位：
Arbeitskreis Bioanorganische Chemie und moderne Komplexchemie
依托单位国家：
德国
项目类别：
Research Units
财政年份：
2011
资助国家：
德国
起止时间：
2010-12-31 至 2016-12-31
项目状态：
已结题

来源：
https://gepris.dfg.de/gepris/projekt/175008652?language=en
关键词：
Cu complexes heart biological electron

项目摘要

The structure of cytochrome-c oxidase is fairly well known from a static (crystalline) point of view, but all attempts to assemble complexes that mimic CuA within this enzyme or to establish a simplified equivalent circuit on a complex chemical level that represents the flow of electrons from cytochrome-c to CuA failed so far. It should be noted that all previously described compounds with certain selective characteristics of CuA deviate from the biological archetype in prominent properties such as structure and redox chemistry, and thus must be improved significantly to arrive at a stage from which significant insights into dynamical aspects of the biological electron transport can be obtained.On the one hand, we will continue our work directed towards improved CuA models with bifunctional thiolate ligands and in parallel also use our novel tridentate GuaphSetS systems which have the potential to establish the biologically requested environment of the methionine-binding site of CuA by activating their NSS' donor sets a coordination which is not accessible by other ligands described in the literature.On the other hand, a novel focus will be created and directed towards photochemically excitable electron transfer cascades as equivalent circuit diagrams for the electron transfer from cytochrome-c to CuA, in which divalent ruthenium ions serve as electron sources and binuclear copper-thiolate complexes act as corresponding electron sinks.Over various stages to the end of the way, models for the CuA sites of cytochrome-c oxidases and of N2O reductases will emerge in increasing sophisticated stages which will also make decisive contributions as components of simplified equivalent circuits on a complex chemical level to a better understanding of dynamic and kinetic aspects of biological electron transport issues driven by CuA.Apart from classical methods of X-ray structure analysis and of conventional characterization by spectroscopic, (spectro)electrochemical and magneto-chemical methods, we will place particular emphasis on sophisticated spectroscopic techniques to make use of the outstanding potential of pulsed optical laser, (pulsed) free electron laser and of (pulsed) 3rd generation synchrotron sources in order to obtain time-resolved information on copper-driven biological electron transport phenomena. In this context, high-resolution X-ray absorption and emission play a central role as these techniques allow direct access to the LUMO and HOMO states of our complexes.

从静态(结晶)的观点来看，细胞色素-c氧化酶的结构是众所周知的，但到目前为止，所有在该酶内组装模拟CUA的复合体或在复杂的化学水平上建立代表电子从细胞色素-C流向CUA的简化等效电路的尝试都失败了。值得注意的是，所有先前描述的具有CUA某些选择性特征的化合物在结构和氧化还原化学等突出性质上都偏离了生物原型，因此必须进行显著的改进才能达到对生物电子传输的动力学方面的重要了解的阶段。一方面，我们将继续我们的工作，以改进具有双功能硫酸盐配体的CUA模型，同时也使用我们的新型三齿GuaffSetS系统，该系统通过激活它们的NSS的给体集来建立CUA的甲硫氨酸结合部位的生物所要求的环境，这是文献中描述的其他配体所不能达到的一个新的焦点将被创建并指向光化学可激发的电子转移级联，作为电子从细胞色素-c到CuA转移的等效电路图，其中二价钌离子作为电子源，双核铜硫酸盐络合物作为相应的电子宿。在这个过程的不同阶段，细胞色素-c氧化酶和N2O还原酶的CUA位置的模型将在越来越复杂的阶段出现，这也将作为复杂化学水平上简化等效电路的组成部分，对更好地理解由CuA驱动的生物电子传递问题的动态和动力学方面做出决定性贡献。部分来自经典的X射线结构分析方法和传统的光谱表征方法在(光谱)电化学和磁化学方法方面，我们将特别强调尖端的光谱技术，以利用脉冲光学激光、(脉冲)自由电子激光和(脉冲)第三代同步加速器源的突出潜力，以获得关于铜驱动的生物电子传输现象的时间分辨信息。在这方面，高分辨率X射线吸收和发射发挥了核心作用，因为这些技术允许直接访问我们的络合物的LUMO和HOMO状态。

项目成果

期刊论文数量（8）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

A panel of peralkylated sulfur–guanidine type bases: Novel pro-ligands for use in biomimetic coordination chemistry

一组全烷基化硫胍型碱基：用于仿生配位化学的新型前配体

DOI：
10.1016/j.ica.2015.03.015
发表时间：
2015
期刊：
Inorganica Chimica Acta
影响因子：
2.8
作者：
A. Neuba;M. Rohrmüller;R. Hölscher;W.G. Schmidt;G. Henkel
通讯作者：
G. Henkel

Synthesis of new copper(i) based linear 1-D-coordination polymers with neutral imidazolinium-dithiocarboxylate ligands

具有中性咪唑啉鎓-二硫代羧酸盐配体的新型铜(i)基线性一维配位聚合物的合成

DOI：
10.1039/c4ra09033k
发表时间：
2015
期刊：
RSC Advances
影响因子：
3.9
作者：
A. Neuba;J. Ortmeyer;D. D. Konieczna;G. Weigel;U. Flörke;G. Henkel;R. Wilhelm
通讯作者：
R. Wilhelm

Copper(I) Complexes with Thiourea Derivatives as Ligands: Revealing Secrets of Their Bonding Scheme