VEPES/XAS/DFT STUDIES OF ET SITES IN BIOINORGANIC CHEMISTRY

生物无机化学中 ET 位点的 VEPES/XAS/DFT 研究

基本信息

批准号：
8170322
负责人：
EDWARD I SOLOMON
金额：
$ 0.03万
依托单位：
STANFORD UNIVERSITY
依托单位国家：
美国
项目类别：
财政年份：
2010
资助国家：
美国
起止时间：
2010-05-01 至 2011-02-28
项目状态：
已结题

项目摘要

This subproject is one of many research subprojects utilizing the resources provided by a Center grant funded by NIH/NCRR. The subproject and investigator (PI) may have received primary funding from another NIH source, and thus could be represented in other CRISP entries. The institution listed is for the Center, which is not necessarily the institution for the investigator. In studies performed during our previous proposals, we have been employing variable energy photoelectron spectroscopy in the valence and metal 2p regions to explore electronic relaxation, the change in electronic structure upon ionization of a reduced site. Thus far, this has been applied to Fe(SR)4 sites where the large electronic relaxation (ligand to M d CT) limits the charge change on oxidation and greatly reduces the geometry change (i.e. the reorganization energy of the site). We are now completing studies on a series of mononuclear Fe complexes in which we examined the effects of going from high to low spin and increased coordination number (tetrahedral vs. octahedral) as well as ligand variation to understand the contribution of heme ligation to electronic relaxation in the [Fetpp(imH)2] complex. We are now proposing to extend our PES studies of the bis-Im heme complex to the bis-met Fe(THT)2(tpp) complex and a cytochrome c model complex (Fe(C5-Im)(tpp)(THS).C6H6) where we will quantitate the effect of the met ligands on electronic relaxation and extend those results to electronic relaxation of cyt b vs. cyt c through DFT calculations and extended charge decomposition and valence bond configuration interaction analyses. In addition to PES studies of heme electron transfer sites, we will investigate covalency and electron delocalization and their contribution to electronic relaxation in blue copper, CuA, and Fe4S4 related model complexes.

该副本是利用众多研究子项目之一由NIH/NCRR资助的中心赠款提供的资源。子弹和调查员（PI）可能已经从其他NIH来源获得了主要资金，因此可以在其他清晰的条目中代表。列出的机构是对于中心，这不一定是调查员的机构。在我们以前的提案中进行的研究中，我们一直在价值和金属2p区域中采用可变的能量光电子光谱，以探索电子弛豫，在减少位点电离时电子结构的变化。到目前为止，这已应用于Fe（SR）4个位点，其中大电子松弛（配体至M d CT）限制了氧化的电荷变化，并大大降低了几何变化（即位置的重组能量）。现在，我们正在完成一系列单核FE复合物的研究，其中我们研究了从高自旋到低自旋和增加的配位数（四面体与八面体）以及配体变化的影响，以了解血红素结的贡献，以了解[FETPP（IMH）2]复合物中血红素结的贡献。 We are now proposing to extend our PES studies of the bis-Im heme complex to the bis-met Fe(THT)2(tpp) complex and a cytochrome c model complex (Fe(C5-Im)(tpp)(THS).C6H6) where we will quantitate the effect of the met ligands on electronic relaxation and extend those results to electronic relaxation of cyt b vs. cyt c through DFT calculations and extended charge decomposition和价键构型相互作用分析。除了对血红素电子转移位点的PES研究外，我们还将研究共价和电子定位域及其对蓝色铜，CUA和FE4S4相关模型复合物中电子松弛的贡献。