Copper Sulfide Model Complexes for Small Molecule Activation

用于小分子活化的硫化铜模型配合物

• 批准号: 9172495
• 负责人: Neal P Mankad
• 金额: $ 19.08万
• 依托单位: UNIVERSITY OF ILLINOIS AT CHICAGO
• 依托单位国家: 美国
• 财政年份: 2016
• 资助国家: 美国
• 起止时间: 2016-08-01 至 2021-05-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/9172495
• 关键词: Active Sites; Address; Aerobic; Architecture; Area; Biological; Biological Models; Biological Sciences; Carbon; Carbon Dioxide; Carbon monoxide dehydrogenase; Chemicals; Chemistry; Communities; Complex; Copper; Coupling; Data; Environment; Environmental Pollutants; Enzymes; Exhibits; Fostering; Future; Goals; Health; Human; Individual; Knowledge; Lead; Ligands; Literature; Mediating; Metalloproteins; Metals; Methods; Mission; Modeling; Molybdenum; Nature; Outcome; Oxidation-Reduction; Oxygen; Pathway interactions; Positioning Attribute; Process; Public Health; Reaction; Regulation; Research; Role; Scheme; Site; Structure; Study models; Sulfides; Sulfur; System; Work; base; biological systems; catalyst; computer studies; covalent bond; design; electronic structure; frontier; greenhouse gases; improved; innovation; knowledge base; nitrous oxide reductase; novel; oxidation; research study; small molecule; stoichiometry; Active Sites; Address; Aerobic; Architecture; Area; Biological; Biological Models; Biological Sciences; Carbon; Carbon Dioxide; Carbon monoxide dehydrogenase; Chemicals; Chemistry; Communities; Complex; Copper; Coupling; Data; Environment; Environmental Pollutants; Enzymes; Exhibits; Fostering; Future; Goals; Health; Human; Individual; Knowledge; Lead; Ligands; Literature; Mediating; Metalloproteins; Metals; Methods; Mission; Modeling; Molybdenum; Nature; Outcome; Oxidation-Reduction; Oxygen; Pathway interactions; Positioning Attribute; Process; Public Health; Reaction; Regulation; Research; Role; Scheme; Site; Structure; Study models; Sulfides; Sulfur; System; Work; base; biological systems; catalyst; computer studies; covalent bond; design; electronic structure; frontier; greenhouse gases; improved; innovation; knowledge base; nitrous oxide reductase; novel; oxidation; research study; small molecule; stoichiometry

Atmospheric concentrations of CO2 and N2O, the #1 and #2 most consequential greenhouse gases on earth, both are regulated in part by metalloproteins containing multimetallic copper-sulfide active sites. The nature of multimetallic cooperativity in these active sites and the role of the conserved copper-sulfide structure as it relates to enzymatic function are poorly understood. The objective of this application is to use synthetic model studies to understand the role of nature's privileged copper-sulfide cluster motif in facilitating multimetallic cooperativity associated with multielectron/multiproton regulation of both CO2 and N2O. Our central hypothesis is that the bridging sulfur atoms both covalently mediate redox coupling of the individual metal sites, and also participate in covalent activation of the small molecule substrates. Our rationale for pursuing this objective is that it will inform and motivate future catalyst designs for crucial multielectron redox transformations that depend on CO2, N2O, and other small-molecule substrates. We will work towards achieving the overall objective by pursuing the following specific aims: 1) develop synthetic methods for tetracopper, dicopper, and copper-molybdenum clusters with single sulfur atom bridges; 2) conduct combined spectroscopic- computational studies of electronic structure across different cluster oxidation states; 3) investigate stoichiometric and catalytic reactions with CO2, N2O, and related model substrates. The proposed research is significant because the synthetic difficulty in accessing such model complexes has precluded their careful study until now, and so our team is in a unique position to make important contributions that advance the field vertically. This approach is innovative because it gives us a unique ability to address biologically relevant coordination chemistry questions with structurally faithful model systems constructed through rational design. Attaining the objective of the proposal will positively impact the chemical community, as multielectron/multiproton transformations of small molecules are crucial not only to biological systems but also to many frontier areas including alternative energy conversion and storage.

二氧化碳和N2O的大气浓度，地球上＃1和＃2最重要的温室气体， 两者都部分通过含有多金属硫化活性位点的金属蛋白蛋白来调节。的本质 这些活性位点的多功能合作以及保守的铜硫化结构的作用 与酶促功能有关的相关知识很少。该应用的目的是使用合成模型 了解自然特权铜硫化物聚类图案在促进多功能方面的作用 与二氧化碳和N2O的多电体/多元子调节相关的合作性。我们的中心假设 是桥接硫原子都共价介导各个金属位点的氧化还原耦合，也可以 参与小分子底物的共价激活。我们追求这一目标的理由是 它将为关键的多电源氧化还原转换的未来催化剂设计提供信息并激励未来的催化剂设计 取决于CO2，N2O和其他小分子底物。我们将致力于实现总体 通过追求以下特定目的的目标：1）为四副手，迪科珀和 带有单硫原子桥的铜溶血簇； 2）共同进行光谱 跨不同集群氧化态的电子结构的计算研究； 3）调查 与CO2，N2O和相关模型底物的化学计量和催化反应。拟议的研究是 意义重大，因为访问此类模型复合物的合成困难使他们谨慎 到目前为止学习，因此我们的团队处于独特的位置，以做出重要的贡献来推进领域 垂直。这种方法具有创新性，因为它赋予了我们独特的解决生物学相关的能力 通过合理设计构建的结构忠实模型系统的协调化学问题。 达到提案的目标将对化学界产生积极影响，因为 小分子的多电体/多元子转化不仅对生物系统至关重要，而且至关重要 到许多边境区域，包括替代能源转换和存储。