QLC: EAGER: Toward the visualization of chemical control

QLC：EAGER：迈向化学控制的可视化

• 批准号: 1836435
• 负责人: Roseanne Sension
• 金额: $ 25万
• 依托单位: Regents of the University of Michigan - Ann Arbor
• 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: 2018-08-15 至 2022-01-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1836435&HistoricalAwards=false
• 关键词: QLC; EAGER; Toward; visualization; chemical

In this project funded by the Chemical Structure Dynamics and Mechanism (CSDM-A) program of the Chemistry Division, Professor Roseanne Sension of The University of Michigan is using x-ray techniques to develop visual images and movies of the internal motions of the atoms in molecules which have been exposed to a pulse of ultraviolet (UV) or visible (Vis) light. Pulses of UV/Vis light can cause distortions of the chemical bonds in molecules, and even cause them to break or re-form in what we call a photochemical reaction. These light-induced motions occur on very short time scales, from a few femtoseconds to a few nanoseconds (A femtosecond is one quadrillionth of a second. A nanosecond is one billionth of a second). X-ray diffraction has been used to determine molecular structure for more than a century. However, these have been molecules that are stationary in a crystal lattice. In order to capture the extremely fast motions of molecules after they have been exposed to light, Prof. Sensions is using the intense x-rays produced by free electron lasers (for example, at the LINAC Coherent Light Source at Stanford University). Professor Sension and her students are measuring how molecules absorb x-rays, and developing methods to convert x-ray absorption information into images that can be sequenced as frames in a motion picture. The visualization of photochemical reactions at the molecular level helps us understand chemical reactions in general, and also supports the long-term goal to control chemical reactions with light. The project is also training students in the use of advanced experimental facilities and in advanced computer simulation of UV/Vis and x-ray absorption. In addition, the results are being integrated into the undergraduate curriculum to help students understand the relevance of mathematics and physics to chemistry.This project uses femtosecond x-ray free electron lasers to visualize quantum wave packet motion in molecules. A short laser pulse is used to initiate and control a photochemical reaction. A polarized x-ray pulse probes the coherent structural dynamics on the excited state potential energy surface. Cobalamin photochemistry and photophysics is used as a model system for molecular visualization and quantum control with femtosecond x-ray pulses sources. The visualization of coherent excited state dynamics and the correlation of dynamics with the molecular ligands facilitate the understanding and development of cobalamin based molecular devices. The experimental observations are interpreted using quantum chemical calculations and finite difference near edge spectroscopy ab initio code to simulate x-ray absorption spectra. In addition, general simulation methods are being developed to model ultrafast x-ray spectroscopy and coherent excited state dynamics. This research project has implications for a wide range of applications in energy conversion, medical therapeutics, molecular electronics, switches, sensors, and delivery platforms. Many of these applications exploit intrinsically quantum mechanical dynamics of the molecules involved.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.

在该项目由化学部门的化学结构动力学和机制（CSDM-A）计划资助的项目中，密歇根大学的Roseanne Sension教授正在使用X射线技术来开发分子中原子的内部动作的视觉图像和电影，这些分子的内部动作已暴露于紫外（UV）或可见的脉冲（UV）或可见的脉冲（Uviolet（UV）或可见）。 紫外线/vis光的脉冲可能会导致分子中化学键的变形，甚至导致它们在我们所谓的光化学反应中破裂或重新形成。 这些光引起的运动发生在很短的时间尺度上，从几秒钟到几纳秒（秒秒是四分之一的四分之一。 X射线衍射已用于确定一个多世纪的分子结构。 但是，这些是在晶格中固定的分子。 为了捕获分子暴露在光线之后的极快运动，Sensions教授使用了自由电子激光器产生的强烈X射线（例如，在斯坦福大学的Linac Cooherent Light Source）。 Sension教授和她的学生正在测量分子如何吸收X射线，并开发将X射线吸收信息转换为图像的方法，这些方法可以在电影中将其测序为帧。 分子水平的光化学反应的可视化有助于我们一般地了解化学反应，并支持控制光的化学反应的长期目标。该项目还在培训学生使用高级实验设施以及对UV/VIS和X射线吸收的高级计算机模拟。 此外，结果正在整合到本科课程中，以帮助学生了解数学和物理学与化学的相关性。该项目使用飞秒X射线无电子激光器来可视化分子中的量子波数据包运动。短激光脉冲用于启动和控制光化学反应。极化X射线脉冲在激发状态势能表面上探测一致的结构动力学。钴胺素光化学和光体物理学用作分子可视化和使用飞秒X射线脉冲源的量子控制的模型系统。相干激发态动力学的可视化以及动力学与分子配体的相关性促进了基于钴胺素的分子装置的理解和发展。使用量子化学计算和在边缘光谱附近概述代码附近的有限差异来解释实验观察，以模拟X射线吸收光谱。另外，正在开发一般的模拟方法来对超快X射线光谱和相干激发态动力学进行建模。 该研究项目对能源转化，医学治疗学，分子电子，开关，传感器和输送平台的广泛应用有影响。这些应用中的许多应用都利用了所涉及的分子的本质量子机械动力学。该奖项反映了NSF的法定任务，并且使用基金会的知识分子优点和更广泛的影响审查标准，被认为值得通过评估来获得支持。

项目成果

Ultrafast XANES Monitors Femtosecond Sequential Structural Evolution in Photoexcited Coenzyme B 12

超快 XANES 监测光激发辅酶 B 12 中的飞秒顺序结构演化

• DOI: 10.1021/acs.jpcb.9b09286
• 发表时间: 2019
• 期刊: The Journal of Physical Chemistry B
• 作者: Miller, Nicholas A.;Michocki, Lindsay B.;Konar, Arkaprabha;Alonso-Mori, Roberto;Deb, Aniruddha;Glownia, James M.;Sofferman, Danielle L.;Song, Sanghoon;Kozlowski, Pawel M.;Kubarych, Kevin J.
• 通讯作者: Kubarych, Kevin J.

Probing the Excited State of Methylcobalamin Using Polarized Time-Resolved X-ray Absorption Spectroscopy

使用偏振时间分辨 X 射线吸收光谱法探测甲钴胺的激发态

• DOI: 10.1021/acs.jpcb.9b05854
• 发表时间: 2019
• 期刊: The Journal of Physical Chemistry B
• 作者: Michocki, Lindsay B.;Miller, Nicholas A.;Alonso-Mori, Roberto;Britz, Alexander;Deb, Aniruddha;Glownia, James M.;Kaneshiro, April K.;Konar, Arkaprabha;Koralek, Jake;Meadows, Joseph H.
• 通讯作者: Meadows, Joseph H.

Ultrafast Excited State Dynamics and Fluorescence from Vitamin B 12 and Organometallic [Co]–C≡C–R Cobalamins

维生素 B 12 和有机金属 [Co]–C–C–R 钴胺素的超快激发态动力学和荧光

• DOI: 10.1021/acs.jpcb.0c04886
• 发表时间: 2020
• 期刊: The Journal of Physical Chemistry B
• 作者: Salerno, Elvin V.;Miller, Nicholas A.;Konar, Arkaprabha;Li, Yan;Kieninger, Christoph;Kräutler, Bernhard;Sension, Roseanne J.
• 通讯作者: Sension, Roseanne J.

Watching Excited State Dynamics with Optical and X-ray Probes: The Excited State Dynamics of Aquocobalamin and Hydroxocobalamin

使用光学和 X 射线探针观察激发态动力学：水钴胺和羟钴胺的激发态动力学

• DOI: 10.1021/jacs.3c04099
• 发表时间: 2023
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Sension, Roseanne J.;McClain, Taylor P.;Lamb, Ryan M.;Alonso-Mori, Roberto;Lima, Frederico Alves;Ardana-Lamas, Fernando;Biednov, Mykola;Chollet, Matthieu;Chung, Taewon;Deb, Aniruddha
• 通讯作者: Deb, Aniruddha

Antivitamins B 12 in a Microdrop: The Excited-State Structure of a Precious Sample Using Transient Polarized X-ray Absorption Near-Edge Structure

微滴中的抗维生素 B 12：使用瞬态偏振 X 射线吸收近边缘结构研究珍贵样品的激发态结构

• DOI: 10.1021/acs.jpclett.9b02202
• 发表时间: 2019
• 期刊: The Journal of Physical Chemistry Letters
• 作者: Miller, Nicholas A.;Michocki, Lindsay B.;Alonso-Mori, Roberto;Britz, Alexander;Deb, Aniruddha;DePonte, Daniel P.;Glownia, James M.;Kaneshiro, April K.;Kieninger, Christoph;Koralek, Jake
• 通讯作者: Koralek, Jake