Structure and Dynamics of CO Binding to Nitrogenase via Ultrafast Vibrational Spectroscopy

通过超快振动光谱研究 CO 与固氮酶结合的结构和动力学

• 批准号: 1905395
• 负责人: Nien-Hui Ge
• 金额: $ 47.5万
• 依托单位: University of California-Irvine
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2019
• 资助国家: 美国
• 起止时间: 2019-08-01 至 2024-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1905395&HistoricalAwards=false
• 关键词: Structure; Dynamics; CO; Binding; Nitrogenase

Nitrogenases are important enzymes that catalyze the conversion of nitrogen to ammonia and play key roles in the global nitrogen cycle. Recently, they have also been shown to convert carbon monoxide (CO) to hydrocarbons and, therefore, are recognized as important candidates for the production of biofuels. With this award, the Chemistry of Life Processes Program in the Division of Chemistry at NSF is funding Professor Nien-Hui Ge from the University of California, Irvine, to investigate how CO binds to and interacts with nitrogenases. Although nitrogenases have been well studied, the detailed mechanisms for CO binding and reactions are still lacking. This project will apply state-of-the-art ultrafast vibrational spectroscopy to capture molecular motions using laser pulses at "shutter speeds" faster than one-trillionth of a second. These snap-shots provide new and much needed information on the molecular structure and transient dynamics of CO and nitrogenases as they bind and interact with each other. Graduate students participating in the research gain valuable training with advanced laser techniques and core physical sciences to strengthen their career development. This project is also integrated with outreach efforts that engage K-12 students through scientific demonstrations. This project is undertaken to gain a molecular picture of CO binding to molybdenum- and vanadium-dependent nitrogenases by novel applications of ultrafast two-dimensional infrared spectroscopy and a variety of transient measurements. The high time resolution of these techniques allows the study of rapid structural fluctuations and transitions of the enzyme. When combined with computational modeling, these experiments reveal the structure of CO at binding sites, elucidate local environment around the cofactor, and establish connectivities between different CO species. Detailed structural and dynamic information obtained from this project provides new insight and helps to establish a unified mechanism for CO binding to nitrogenases.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.

固氮酶是催化氮转化为氨的重要酶，在全球氮循环中起着关键作用。最近，它们还被证明可以将一氧化碳（CO）转化为碳氢化合物，因此被认为是生产生物燃料的重要候选者。有了这个奖项，NSF化学部的生命过程化学计划正在资助加州大学欧文分校的葛念辉教授，研究CO如何与固氮酶结合并相互作用。虽然固氮酶已经得到了很好的研究，CO结合和反应的详细机制仍然缺乏。该项目将应用最先进的超快振动光谱学，以快于万亿分之一秒的“快门速度”使用激光脉冲捕获分子运动。这些快照提供了新的和急需的信息的分子结构和瞬态动力学的CO和固氮酶，因为它们结合和相互作用。参与研究的研究生获得了先进激光技术和核心物理科学的宝贵培训，以加强他们的职业发展。该项目还与通过科学演示吸引K-12学生的外联工作相结合。 该项目是进行获得一氧化碳结合钼和钒依赖固氮酶的超快二维红外光谱和各种瞬态测量的新应用的分子图片。这些技术的高时间分辨率允许研究酶的快速结构波动和转变。当与计算建模相结合，这些实验揭示了CO在结合位点的结构，阐明当地的环境周围的辅因子，并建立不同的CO物种之间的连接。 从这个项目中获得的详细的结构和动力学信息提供了新的见解，并有助于建立一个统一的机制，CO结合固氮酶。这个奖项反映了NSF的法定使命，并已被认为是值得通过评估使用基金会的智力价值和更广泛的影响审查标准的支持。

项目成果

Photobase-Triggered Formation of 3D Epitaxially Fused Quantum Dot Superlattices with High Uniformity and Low Bulk Defect Densities

• DOI: 10.1021/acsnano.1c11130
• 发表时间: 2022-02-22
• 期刊: ACS NANO
• 影响因子: 17.1
• 作者: Qian, Caroline;Abelson, Alex;Law, Matt
• 通讯作者: Law, Matt

Ultrafast vibrational dynamics of the tyrosine ring mode and its application to enkephalin insertion into phospholipid membranes as probed by two-dimensional infrared spectroscopy

二维红外光谱探测酪氨酸环模式的超快振动动力学及其在脑啡肽插入磷脂膜中的应用

• DOI: 10.1063/5.0054428
• 发表时间: 2021
• 期刊: The Journal of Chemical Physics
• 作者: Vinogradov, Ilya;Feng, Yuan;Kumar, S. K. Karthick;Guo, Chenxu;Udagawa, Nina Saki;Ge, Nien-Hui
• 通讯作者: Ge, Nien-Hui

Wavelength and Polarization Dependence of Second-Harmonic Responses from Gold Nanocrescent Arrays

金纳米月牙阵列二次谐波响应的波长和偏振依赖性

• DOI: 10.1021/acs.jpcc.0c05548
• 发表时间: 2020
• 期刊: The Journal of Physical Chemistry C
• 作者: Maekawa, Hiroaki;Drobnyh, Elena;Lancaster, Cady A.;Large, Nicolas;Schatz, George C.;Shumaker-Parry, Jennifer S.;Sukharev, Maxim;Ge, Nien-Hui
• 通讯作者: Ge, Nien-Hui