Scaffold-based Synthetic Models of Mono-Iron Hydrogenase: Structure and Dynamics

基于支架的单铁氢化酶合成模型：结构和动力学

• 批准号: 1808311
• 负责人: Michael Rose
• 金额: $ 42万
• 依托单位: University of Texas at Austin
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-08-01 至 2022-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1808311&HistoricalAwards=false
• 关键词: Scaffold; based; Synthetic; Models; Mono

With this award, the Chemistry of Life Processes Program in the Chemistry Division is funding Prof. Michael Rose at the University of Texas at Austin to investigate the role of the iron center in an enzyme called mono-iron hydrogenase. This enzyme is molecule important for the capture of carbon dioxide (CO2) in methanogens, which are single cell microorganisms that can be found for example in the human gut and in wetlands. These organisms are very efficient at transforming dihydrogen (H2) and CO2 from the environment in which they live into methane. In contrast, artificial way to capture and transform H2 and CO2 are much less efficient. Furthermore while the enzymes, in particular mono-iron hydrogenase, utilize earth abundant metals like iron and nickel, many synthetic analogues of the enzymes utilize precious metals like platinum, iridium or palladium. The research of Professor Rose focuses on understanding how the mono-iron hydrogenase catalyzes the chemical transformation in the methanogens and applying this understanding to developing artificial catalysts as efficient as the enzyme. Professor Rose also participates in the outreach program called H2fromH2O. He interacts with high school students in the central Texas region to demonstrate the fundamental science, environmental impact and possible applications for splitting water into hydrogen and oxygen and derive energy from this process. The students who participate in the outreach program further disseminate such lessons to their families and communities. This serves to raise awareness about the importance of developing renewable energy technologies. UT Austin undergraduates directly participate in the outreach efforts, become motivate to do research, and pursue job opportunities and graduate education in energy-related fields.The available, iron-based synthetic (artificial) systems of a molecular nature do not replicate the speed and efficiency of the naturally occurring system. This research seeks to understand how components of the natural system can be incorporated to provide for enhanced reactivity. There are three technical approaches to understanding the H2-activating and hydride transfer activity of the enzyme mono-iron hydrogenase. First, synthetic model complexes are hybridized with protein hosts to determine the effect of the protein environment on the spectroscopic properties and functional reactivity of the model complexes (versus stand-alone metal complexes). Second, the "anthracene scaffold" strategy for assembling the biomimetic fac-CNS motif is modified with more flexible "anthranoid" scaffolds to investigate the role of protein-like flexibility of the donor arms on the reactivity of the model complexes. Third, the complexes contain a biomimetic pyridine moiety, which is hypothesized to assist in H2 heterolysis as a pendant base.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

凭借该奖项，化学部的生命过程化学项目正在资助德克萨斯大学奥斯汀分校的迈克尔·罗斯教授研究铁中心在一种称为单铁氢化酶的酶中的作用。这种酶是捕获产甲烷菌中二氧化碳 (CO2) 的重要分子，产甲烷菌是单细胞微生物，可以在人类肠道和湿地中找到。这些生物体能够非常有效地将其生存环境中的氢气 (H2) 和二氧化碳转化为甲烷。 相比之下，人工捕获和转化氢气和二氧化碳的效率要低得多。此外，虽然酶，特别是单铁氢化酶利用地球上丰富的金属，如铁和镍，但酶的许多合成类似物利用贵金属，如铂、铱或钯。罗斯教授的研究重点是了解单铁氢化酶如何催化产甲烷菌的化学转化，并将这种理解应用于开发与酶一样高效的人工催化剂。 Rose 教授还参加了名为 H2fromH2O 的外展计划。他与德克萨斯州中部地区的高中生互动，展示基础科学、环境影响以及将水分解为氢气和氧气并从这一过程中获取能量的可能应用。参加外展计划的学生进一步向他们的家庭和社区传播这些课程。 这有助于提高人们对开发可再生能源技术重要性的认识。德克萨斯大学奥斯汀分校的本科生直接参与推广工作，变得有动力进行研究，并寻求能源相关领域的工作机会和研究生教育。现有的分子性质的铁基合成（人工）系统无法复制自然发生系统的速度和效率。这项研究旨在了解如何整合自然系统的组成部分以提供增强的反应性。可通过三种技术方法来了解单铁氢化酶的 H2 激活和氢化物转移活性。首先，将合成的模型复合物与蛋白质宿主杂交，以确定蛋白质环境对模型复合物的光谱特性和功能反应性的影响（相对于独立的金属复合物）。其次，用更灵活的“anthranoid”支架修改用于组装仿生fac-CNS基序的“蒽支架”策略，以研究供体臂的蛋白质样灵活性对模型复合物反应性的作用。第三，该复合物含有仿生吡啶部分，假设其作为悬垂碱基协助 H2 杂解。该奖项反映了 NSF 的法定使命，并通过使用基金会的智力价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Single‐Step Sulfur Insertions into Iron Carbide Carbonyl Clusters: Unlocking the Synthetic Door to FeMoco Analogues

• DOI: 10.1002/ange.202011517
• 发表时间: 2020-10
• 期刊: Angewandte Chemie
• 作者: C. Joseph;Caitlyn R. Cobb;Michael J. Rose

Facile hydrogen atom abstraction and sulfide formation in a methyl-thiolate capped iron–sulfur–carbonyl cluster

在硫醇甲酯封端的铁硫羰基簇中轻松提取氢原子并形成硫化物

• DOI: 10.1039/c9dt04098f
• 发表时间: 2020
• 期刊: Dalton Transactions
• 影响因子: 4
• 作者: Shupp, J. Patrick;Rose, Michael J.
• 通讯作者: Rose, Michael J.

Bioinspired CNP Iron(II) Pincers Relevant to [Fe]-Hydrogenase (Hmd): Effect of Dicarbonyl versus Monocarbonyl Motifs in H 2 Activation and Transfer Hydrogenation

与 [Fe]-氢化酶 (Hmd) 相关的仿生 CNP 铁 (II) 钳：二羰基与单羰基基序在 H 2 活化和转移氢化中的影响

• DOI: 10.1021/acs.inorgchem.9b03476
• 发表时间: 2020
• 期刊: Inorganic Chemistry
• 影响因子: 4.6
• 作者: Xie, Zhu-Lin;Chai, Wenrui;Kerns, Spencer A.;Henkelman, Graeme A.;Rose, Michael J.
• 通讯作者: Rose, Michael J.

Divergent Solution and Solid-State Structures of Mono- and Dinuclear Nickel(II) Pyridone Complexes

• DOI: 10.1021/acs.organomet.9b00799
• 发表时间: 2020-02
• 期刊: Organometallics
• 影响因子: 2.8
• 作者: Sean T. Goralski;Taylor A. Manes;S. E. A. Lumsden;V. Lynch;Michael J. Rose

Construction of Synthetic Models for Nitrogenase-Relevant NifB Biogenesis Intermediates and Iron-Carbide-Sulfide Clusters

固氮酶相关 NifB 生物发生中间体和碳化铁硫化物簇的合成模型的构建

• DOI: 10.3390/catal10111317
• 发表时间: 2020
• 期刊: Catalysts
• 影响因子: 3.9
• 作者: Joseph, Chris;Shupp, John Patrick;Cobb, Caitlyn R.;Rose, Michael J.
• 通讯作者: Rose, Michael J.