Organic Chemistry in Harsh Reaction Environments

恶劣反应环境下的有机化学

• 批准号: 1954270
• 负责人: Robert McMahon
• 金额: $ 60万
• 依托单位: University of Wisconsin-Madison
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-07-01 至 2024-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1954270&HistoricalAwards=false
• 关键词: Organic; Chemistry; Harsh; Reaction; Environments

In this project funded by the Chemical Structure, Dynamics, and Mechanism-B Program of the Chemistry Division, Professor Robert J. McMahon of the Department of Chemistry at the University of Wisconsin-Madison investigates the behavior of organic compounds under extreme conditions of temperature, pressure, or radiation. These conditions, which are similar to the conditions found in flames (combustion) or in space, cause the degradation of organic compounds and generate a complex mixture of highly reactive products. This project explores the properties and chemical reactions of these reactive molecules. This research provides a foundation for understanding two very different problems – one involving combustion and another involving the chemistry of space. Combustion of organic fuels is central to our nation’s energy supply and national economy. A fundamental understanding of combustion offers the possibility of enhancing the energy efficiency of fuel combustion and minimizing pollutants (soot) that arise from incomplete combustion. In interstellar space, it is now known that hundreds of different organic compounds exist throughout the galaxy in environments that are harsh because they are so hot (near stars) or because they are so cold (far from stars). Studying these environments is a crucial step in understanding the distribution of organic material in the universe and identifying molecules that could be precursors to life. This research program supports the education of graduate and undergraduate students in the study of complex chemical problems as part of an interdisciplinary research team. Training in mechanistic organic chemistry provides a valuable foundation for subsequent careers in industry or academia. Professor McMahon and his student engage in a variety of science education and outreach activities.This proposal addresses challenges in mechanistic organic chemistry that are relevant to our understanding of harsh reaction environments. The current proposal develops these issues along three major lines: 1) generation, detection, and characterization of key chemical targets by rotational spectroscopy, 2) spectroscopy and photochemistry of carbon-chain molecules, and 3) quantum mechanical tunneling in organic chemistry. The scientific impact of the proposed research reaches beyond chemistry and cuts across diverse areas of contemporary science. Studies of spin delocalization and spin polarization underpin the development of new organic materials with novel electrical and magnetic properties. Studies of reactive organic species contribute to a fundamental understanding of combustion. The Atacama Large Millimeter Array (ALMA), an NSF-funded astronomical interferometer of radio telescopes in northern Chile, is generating a deluge of new radio-astronomical data. These data can be interpreted only by comparison with laboratory spectra of the type that are obtained in this project.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.

在这个由化学部化学结构，动力学和机制B计划资助的项目中，威斯康星大学麦迪逊分校化学系的Robert J. McMahon教授研究了有机化合物在极端温度，压力或辐射条件下的行为。 这些条件类似于火焰（燃烧）或空间中的条件，导致有机化合物降解，并产生高度反应性产物的复杂混合物。 该项目探索这些活性分子的性质和化学反应。 这项研究为理解两个非常不同的问题提供了基础-一个涉及燃烧，另一个涉及空间化学。 有机燃料的燃烧对我国的能源供应和国民经济至关重要。 对燃烧的基本理解提供了提高燃料燃烧的能源效率和最大限度地减少不完全燃烧产生的污染物（烟灰）的可能性。 在星际空间中，现在已知有数百种不同的有机化合物存在于整个银河系的恶劣环境中，因为它们非常热（靠近恒星）或因为它们非常冷（远离恒星）。 研究这些环境是了解宇宙中有机物质分布和识别可能是生命前身的分子的关键一步。 该研究计划支持研究生和本科生的教育，作为跨学科研究团队的一部分，研究复杂的化学问题。 机械有机化学的培训为随后的工业或学术界职业生涯提供了宝贵的基础。麦克马洪教授和他的学生从事各种科学教育和推广活动。这个建议解决了机械有机化学中的挑战，这些挑战与我们对恶劣反应环境的理解有关。 目前的建议发展这些问题沿着三条主线：1）生成，检测和表征的关键化学目标的旋转光谱，2）光谱和光化学的碳链分子，和3）量子力学隧道在有机化学。拟议研究的科学影响超越了化学，跨越了当代科学的各个领域。 自旋离域和自旋极化的研究是开发具有新颖电磁性能的新型有机材料的基础。 对反应性有机物种的研究有助于对燃烧的基本理解。 阿塔卡马大型毫米波阵列（阿尔马）是一个由国家科学基金会资助的射电望远镜天文干涉仪，位于智利北方，正在产生大量新的射电天文数据。 这些数据只能通过与本项目中获得的实验室光谱进行比较来解释。该奖项反映了NSF的法定使命，并被认为值得通过使用基金会的知识价值和更广泛的影响审查标准进行评估来支持。

项目成果

Precise equilibrium structures of 1 H - and 2 H -1,2,3-triazoles (C2H3N3) by millimeter-wave spectroscopy

通过毫米波光谱分析 1 H - 和 2 H -1,2,3-三唑 (C2H3N3) 的精确平衡结构

• DOI: 10.1063/5.0097750
• 发表时间: 2022
• 期刊: The Journal of Chemical Physics
• 作者: Zdanovskaia, Maria A.;Esselman, Brian J.;Kougias, Samuel M.;Amberger, Brent K.;Stanton, John F.;Woods, R. Claude;McMahon, Robert J.
• 通讯作者: McMahon, Robert J.

Rotational spectra of twenty-one vibrational states of [35Cl]-and [37Cl]-chlorobenzene

[35Cl]-和[37Cl]-氯苯的21个振动态的旋转光谱

• DOI: 10.1016/j.jms.2023.111776
• 发表时间: 2023
• 期刊: Journal of Molecular Spectroscopy
• 影响因子: 1.4
• 作者: Dorman, P. Matisha;Esselman, Brian J.;Changala, P. Bryan;McCarthy, Michael C.;Woods, R. Claude;McMahon, Robert J.
• 通讯作者: McMahon, Robert J.

Precise equilibrium structure determination of thiophene ( c -C 4 H 4 S) by rotational spectroscopy—Structure of a five-membered heterocycle containing a third-row atom

利用旋转光谱法精确测定噻吩（c -C 4 H 4 S）的平衡结构——含有第三行原子的五元杂环的结构

• DOI: 10.1063/5.0055267
• 发表时间: 2021
• 期刊: The Journal of Chemical Physics
• 作者: Orr, Vanessa L.;Ichikawa, Yotaro;Patel, Aatmik R.;Kougias, Samuel M.;Kobayashi, Kaori;Stanton, John F.;Esselman, Brian J.;Woods, R. Claude;McMahon, Robert J.
• 通讯作者: McMahon, Robert J.

Rotational Spectra of Three Cyanobutadiene Isomers (C 5 H 5 N) of Relevance to Astrochemistry and Other Harsh Reaction Environments

与天体化学和其他恶劣反应环境相关的三种氰基丁二烯异构体（C 5 H 5 N）的旋转光谱

• DOI: 10.1021/jacs.1c03777
• 发表时间: 2021
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Zdanovskaia, Maria A.;Dorman, P. Matisha;Orr, Vanessa L.;Owen, Andrew N.;Kougias, Samuel M.;Esselman, Brian J.;Woods, R. Claude;McMahon, Robert J.
• 通讯作者: McMahon, Robert J.

Precise equilibrium structure of thiazole ( c -C 3 H 3 NS) from twenty-four isotopologues

二十四种同位素体的噻唑 ( c -C 3 H 3 NS) 的精确平衡结构

• DOI: 10.1063/5.0057221
• 发表时间: 2021
• 期刊: The Journal of Chemical Physics
• 作者: Esselman, Brian J.;Zdanovskaia, Maria A.;Owen, Andrew N.;Stanton, John F.;Woods, R. Claude;McMahon, Robert J.
• 通讯作者: McMahon, Robert J.