Coherent Multidimensional Spectroscopy of the Oxygen Evolving Complex in Photosystem II

光系统 II 中放氧复合物的相干多维光谱

• 批准号: 1709060
• 负责人: John Wright
• 金额: $ 51万
• 依托单位: University of Wisconsin-Madison
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2017
• 资助国家: 美国
• 起止时间: 2017-09-01 至 2022-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1709060&HistoricalAwards=false
• 关键词: Coherent; Multidimensional; Spectroscopy; Oxygen; Evolving

With support from the Chemical Measurement and Imaging Program in the Division of Chemistry, Professor Wright at University of Wisconsin continuously develops coherent multidimensional spectroscopy (CMDS) by expanding its capability of measuring molecular motions. CMDC is a spectroscopic technique to fingerprint a molecule, which helps scientists to distinguish different molecules present in complex samples. In this project, Professor Wright uses a pair of laser pulses to create specific responses from different electrons in a molecule and then follow the change of their energy levels over a very wide range of time scales. He then uses this technique to study how vitamin B12 works and how green plants use sunlight to make oxygen at the molecular level. Studying these two questions could help us to better understand how human body works and how to harness solar energy more effectively. Professor Wright also works with an instrument company on the commercialization of the CMDS technique by reducing the cost and make it easier to use by other scientists. Through this project, Professor Wright provides research opportunities to graduate, undergraduate, and secondary school students. He is also passionate about using active learning methods to prepare future STEM students for better national competitiveness and works closely with summer students from Spelman College. Professor Wright's project has two specific goals - understanding the enzymatic mechanism for vitamin B12's catalysis of ethanolamine degradation and the mechanism by which the oxygen evolving complex in photosystem II makes oxygen. The vitamin B12 mechanism serves as a model for understanding enzymatic reactions. The OEC mechanism is one of the grand challenges of chemistry, particularly for developing solar energy. For both systems, Professor Wright uses CMDS to create quantum mechanical superpositions of vibrational and electronic states that provide the selectivity and structural details required to define the mechanisms with quantum state resolution. Specifically, he is working to (1) develop a pump-CMDS probe to create a 3D spectrum; (2) to study the Co-C bond cleavage in a cobalamin-ethanolamine ammonida lyase (EAL)-ethanolamine (EA) complex to investigate the enzymatic reaction converting ethanolamine to acetaldehyde and ammonia; and (3) to characterize the electronic and vibrational states of oxygen evolving complexes (OEC) in photosystem II to understand the water oxidation mechanism. In addition, Professor Wright (1) continues his development of active learning methods in undergraduate and graduate courses; (2) works with students from Spelman College through a REU program; and (3) plans to disseminate CMDS through web site tutorials, educational materials, publications and conferences.

在化学系化学测量和成像项目的支持下，威斯康星大学赖特教授通过扩展其测量分子运动的能力，不断开发相干多维光谱（CMDS）。 CMDC 是一种分子指纹光谱技术，可帮助科学家区分复杂样品中存在的不同分子。 在这个项目中，赖特教授使用一对激光脉冲来产生分子中不同电子的特定响应，然后在很宽的时间尺度内跟踪它们的能级变化。 然后，他利用这项技术研究维生素 B12 的工作原理以及绿色植物如何利用阳光在分子水平上制造氧气。 研究这两个问题可以帮助我们更好地了解人体如何运作以及如何更有效地利用太阳能。 Wright 教授还与一家仪器公司合作，通过降低成本并使其更容易被其他科学家使用来实现 CMDS 技术的商业化。通过这个项目，赖特教授为研究生、本科生和中学生提供研究机会。 他还热衷于使用主动学习方法为未来的 STEM 学生提高国家竞争力做好准备，并与斯佩尔曼学院的暑期学生密切合作。 Wright 教授的项目有两个具体目标：了解维生素 B12 催化乙醇胺降解的酶机制，以及光系统 II 中的释氧复合物产生氧气的机制。 维生素 B12 机制可作为理解酶反应的模型。 OEC 机制是化学领域的重大挑战之一，特别是对于开发太阳能而言。 对于这两个系统，Wright 教授使用 CMDS 创建振动态和电子态的量子力学叠加，提供定义具有量子态分辨率的机制所需的选择性和结构细节。 具体来说，他正在致力于 (1) 开发泵浦 CMDS 探针来创建 3D 光谱； (2)研究钴胺素-乙醇胺氨裂合酶(EAL)-乙醇胺(EA)复合物中Co-C键的断裂，以研究乙醇胺转化为乙醛和氨的酶促反应； (3) 表征光系统 II 中析氧配合物 (OEC) 的电子和振动状态，以了解水氧化机制。此外，赖特教授 (1) 在本科生和研究生课程中继续发展主动学习方法； (2) 通过 REU 项目与斯佩尔曼学院的学生合作； (3) 计划通过网站教程、教育材料、出版物和会议传播 CMDS。

项目成果

Fundamental Studies of Relationships between Experimental Nonlinear Coherent Vibrational Spectroscopies

实验非线性相干振动光谱之间关系的基础研究

• DOI: 10.1021/acs.jpclett.9b01280
• 发表时间: 2019-06
• 期刊: The Journal of Physical Chemistry Letters
• 作者: Wright; John C.
• 通讯作者: John C.

Schrödinger Cat State Spectroscopy—A New Frontier for Analytical Chemistry

薛定谔猫态光谱——分析化学的新领域

• DOI: 10.1021/acs.analchem.0c01662
• 发表时间: 2020-07
• 期刊: Analytical Chemistry
• 影响因子: 7.4
• 作者: Wright; John C.
• 通讯作者: John C.

WrightTools: a Python package for multidimensional spectroscopy

WrightTools：用于多维光谱的 Python 包

• DOI: 10.21105/joss.01141
• 发表时间: 2019-01
• 期刊: Journal of Open Source Software
• 作者: Thompson, Blaise;Sunden, Kyle;Morrow, Darien;Kohler, Daniel;Wright, John
• 通讯作者: Wright, John

Three Dimensional Triply Resonant Sum Frequency Spectroscopy Revealing Vibronic Coupling in Cobalamins: Toward a Probe of Reaction Coordinates

三维三重共振和频谱揭示钴胺素中的振动耦合：探索反应坐标

• DOI: 10.1021/acs.jpca.8b07678
• 发表时间: 2018-11
• 期刊: The Journal of Physical Chemistry A
• 作者: Handali, Jonathan D.;Sunden, Kyle F.;Thompson, Blaise J.;Neff;Kaufman, Emily M.;Brunold, Thomas C.;Wright, John C.
• 通讯作者: Wright, John C.

Interference and phase mismatch effects in coherent triple sum frequency spectroscopy

相干三和频谱中的干扰和相位失配效应

• DOI: 10.1016/j.chemphys.2018.05.023
• 发表时间: 2018-06
• 期刊: Chemical Physics
• 影响因子: 2.3
• 作者: Handali, Jonathan D.;Sunden, Kyle F.;Kaufman, Emily M.;Wright, John C.
• 通讯作者: Wright, John C.