MODELS FOR NON HEME DIIRON ENZYME INTERMEDIATES

非血红素二铁酮酶中间体的模型

基本信息

批准号：
6164746
负责人：
STEVEN J LANGE
金额：
$ 1.16万
依托单位：
UNIVERSITY OF MINNESOTA
依托单位国家：
美国
项目类别：
财政年份：
2000
资助国家：
美国
起止时间：
2000-02-16 至
项目状态：
未结题

来源：
https://reporter.nih.gov/project-details/6164746
关键词：
Mossbauer spectrometry Raman spectrometry X ray crystallography chemical models enzyme activity enzyme complex enzyme model iron compounds metal complex methane monooxygenase model design /development oxygen

项目摘要

A new class of binucleating ligands for modeling oxygen activating non heme diiron metalloenzymes, including methane monooxygenase and the R2 protein of ribonucleotide reductase, will be developed with the support of this fellowship. The target ligands are based on an easily modified naphthalene bridge that will separate two iron binding compartments and will provide two distinct advantages over current binucleating ligands: 1) the compounds will have flexibility to allow for structural changes concomitant with dioxygen binding and 2) the ligands will allow for biomimetic oxo- and hydroxo- bridges between iron ions instead of enforcing an alkoxo or phenoxo bridge that many current binuclear ligands provide. High valent diiron (IV) compounds obtained by reaction of the diiron (II) and diiron (III) complexes with dioxygen and peroxide will be examined in detail. Fundamental knowledge will be gained about the structure and reactivity of these high valent (IV) species through characterization by extended X-ray absorbance fine structure analysis, resonance Raman spectroscopy, single crystal X-ray diffraction, EPR spectroscopy, and magnetic susceptibility measurements. The ability of the high valent diiron compounds to catalyze the oxidation of hydrocarbon substrates will be examined in detail.

用于模拟氧活化非的新型双核配体血红素二铁金属酶，包括甲烷单加氧酶和 R2 核糖核苷酸还原酶的蛋白质，将在以下支持下开发这个团契。目标配体基于易于修饰的萘桥将分隔两个铁结合隔室和与目前的双核配体相比，它将提供两个明显的优势：1) 该化合物将具有允许结构变化的灵活性伴随双氧结合并且2)配体将允许铁离子之间的仿生氧桥和羟基桥代替加强烷氧基或苯氧基桥，许多当前的双核配体提供。通过反应得到的高价二铁(IV)化合物二铁 (II) 和二铁 (III) 与分子氧和过氧化物的络合物将详细检查了。将获得有关以下方面的基本知识这些高价（IV）物质的结构和反应性通过扩展 X 射线吸收精细结构分析进行表征，共振拉曼光谱、单晶X射线衍射、EPR 光谱学和磁化率测量。的能力高价二铁化合物催化碳氢化合物的氧化底物将被详细检查。