MULTI-EDGE XAS INVESTIGATION OF MONO AND BINUCLEAR CU- AND FE-CONTAINING BIOMIME

含铜和铁的单核和双核生物模拟物的多边缘 XAS 研究

• 批准号: 7954379
• 负责人: Robert Karoly Szilagyi
• 金额: $ 0.77万
• 依托单位: STANFORD UNIVERSITY
• 依托单位国家: 美国
• 财政年份: 2009
• 资助国家: 美国
• 起止时间: 2009-03-01 至 2010-02-28
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/7954379
• 关键词: Back; Biological; Biomimetics; Chemistry; Classification; Complex; Computer Retrieval of Information on Scientific Projects Database; Crystallography; Data; Electron Transport; Electronics; Funding; Grant; Hydrogenase; Institution; Investigation; Ligands; Metals; Mono-S; Nature; Nitrogenase; Oxidation-Reduction; Phosphines; Process; Research; Research Personnel; Resources; Sampling; Series; Site; Source; Structure; Sulfhydryl Compounds; United States National Institutes of Health; absorption; base; electronic structure; insight; small molecule; structural biology; synchrotron radiation; theories; thioether

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. We propose multi-edge x-ray absorption studies on a series of Cu and Fe containing biomimetic complexes to gain insights into the non-innocent nature of metal-ligand bonding interactions. While these complexes contain abiotic ligands with phosphine, phosphido, and amido groups in addition to biotic thiol and thioether groups, they provide a systematic and tunable way to probe electronic and geometric structure contributions to biological redox processes in electron-transfer CuA-sites and small-molecule activation centers such as hydrogenases and nitrogenases. The proposed XANES analyses of rising-edge features at metal L-edge and ligand K-edges will provide direct experimental information about the ligand-based redox chemistry and the extent of metal-to-ligand back-donation. The EXAFS analysis at the metal K-edge will be used to characterize the sample integrity with reference to small-molecule crystallography. The interpretation of the spectroscopic data will be aided by electronic structure calculations. Furthermore, the computational level of theory (basis set and functional) will be calibrated to metal and ligand characters that will be experimentally determined from pre-edge and rising-edge features.

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