Copper Sulfide Model Complexes for Small Molecule Activation

用于小分子活化的硫化铜模型配合物

基本信息

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
项目类别：
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

项目摘要

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.

大气中 CO2 和 N2O（地球上排名第一和排名第二的最重要温室气体）的浓度，两者都部分受到含有多金属硫化铜活性位点的金属蛋白的调节。的性质这些活性位点的多金属协同作用以及保守的硫化铜结构的作用人们对酶功能的相关性知之甚少。该应用程序的目标是使用合成模型研究了解自然界特有的硫化铜簇基序在促进多金属化方面的作用与 CO2 和 N2O 的多电子/多质子调节相关的协同性。我们的中心假设是桥硫原子共价介导各个金属位点的氧化还原偶联，并且参与小分子底物的共价活化。我们追求这一目标的理由是它将为关键的多电子氧化还原转化的未来催化剂设计提供信息和激励依赖于 CO2、N2O 和其他小分子底物。我们将努力实现总体目标通过追求以下具体目标来实现目标：1）开发四铜、二铜和铜的合成方法具有单硫原子桥的铜-钼簇； 2) 进行组合光谱- 不同簇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体的综合困难阻碍了他们的仔细研究到目前为止，我们的团队处于独特的地位，可以为推动该领域的发展做出重要贡献垂直。这种方法是创新的，因为它赋予我们解决生物学相关问题的独特能力通过合理设计构建的结构可靠的模型系统来协调化学问题。实现该提案的目标将对化学界产生积极影响，因为小分子的多电子/多质子转化不仅对生物系统至关重要，而且对生物系统也至关重要许多前沿领域，包括替代能源转换和存储。