Mechanistic Investigation of CO activation by Nitrogenase

开发可持续的碳燃料来源，同时面临碳燃料燃烧产生的碳废物(CO和CO2)的积累，是相互竞争的全球挑战。化学系的生命过程化学项目将资助加州大学欧文分校的Markus Ribbe教授和Ylin Hu教授研究固氮酶如何还原CO和CO2形成更大碳氢化合物的详细化学机制。通过这项研究获得的知识为新型催化剂的设计提供了信息，这些催化剂可以将碳废物回收为可用燃料，从而同时解决与能源和环境有关的问题。该项目为研究生研究人员、研究生和本科生提供广泛的实验和计算技术方面的多学科教育和培训。通过所有教育级别的研究机会和将微生物生物技术纳入课堂教学，将研究和教育结合在一起。各种外展活动和计划，包括加州大学欧文分校的科学星期六，旨在吸引中学生，包括那些来自代表性不足的少数族裔社区的学生，了解全球能源和环境问题，以及这些问题的潜在生物技术解决方案。无法产生不同的底物或中间结合态仍然是固氮酶机械研究的主要障碍。这一建议利用了一种新的方法来将CO或CO衍生中间体的结合从随后的周转中解耦，从而为通过受控地将电子(S)/质子(S)传递到CO或CO衍生物种而沿着CO还原反应路径生成连续快照提供了独特的工具。然后将使用化学、生物化学和光谱方法的战略组合来分析这些定义的快照，希望(1)获得将CO转化为CH4的C1途径的洞察力；(2)定义第二个CO的结合和偶合的C1构象；以及(3)确定碳链延伸的机制。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

Developing sustainable sources of carbon fuels while confronting the accumulation of carbon wastes (CO and CO2) from the combustion of carbon fuels are competing global challenges. With this award, the Chemistry of Life Processes Program in the Chemistry Division is funding Professor Markus Ribbe and Professor Yilin Hu from the University of California, Irvine, to investigate the detailed chemical mechanism for how the nitrogenase enzyme reduces CO and CO2 to form larger hydrocarbon compounds. The knowledge acquired through this research informs the design of novel catalysts that recycle carbon wastes into usable fuels, thereby simultaneously combating energy- and environment-related problems. This project provides multidisciplinary education and training across a broad range of experimental and computational techniques to postgraduate researchers, and graduate and undergraduate students. Research and education are integrated through research opportunities across all education levels and through incorporation of microbial biotechnology into classroom teaching. Various outreach events and programs are developed, including Science Saturdays at UC Irvine, to engage middle school students, including those from underrepresented minority communities, to learn about global energy and environmental problems, and potential biotechnological solutions to these problems.The inability to generate distinct substrate- or intermediate-bound states has remained a major roadblock for mechanistic investigations of nitrogenase. This proposal utilizes a novel approach to uncouple the binding of CO or CO-derived intermediates from the subsequent turnover, thereby providing a unique tool for the generation of successive snapshots along the reaction pathway of CO reduction via controlled delivery of electron(s)/proton(s) to CO or CO-derived species. A strategic combination of chemical, biochemical and spectroscopic approaches will then be used to analyze these defined snapshots in hopes of (1) obtaining insights into the C1 pathway that converts CO to CH4; (2) defining the C1 conformation for the binding and coupling of the second CO; and (3) identifying the mechanism of carbon chain extension.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.