Organic Chemistry in Harsh Reaction Environments

恶劣反应环境下的有机化学

• 批准号: 1664912
• 负责人: Robert McMahon
• 金额: $ 56.5万
• 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: 2017-08-01 至 2021-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1664912&HistoricalAwards=false
• 关键词: Organic; Chemistry; Harsh; Reaction; Environments

In this project funded by the Chemical Structure, Dynamics & 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 harsh 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 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 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). The project supports the education of graduate and undergraduate students. Training in mechanistic organic chemistry provides a valuable foundation for subsequent careers in industry or academia. Professor Robert J. McMahon has been a major contributor in developing the Department's Plan for Broadening Participation and participated in the National Diversity Equity Workshop series. Professor Robert J. McMahon is also a champion of STEM education on the UW-Madison campus. This proposal addresses issues 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) quantum mechanical tunneling in organic chemistry, 2) spectroscopy and photochemistry of carbon-chain molecules, and 3) generation, detection, and characterization of key chemical targets by rotational spectroscopy. 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, much of which can be interpreted only by comparison with laboratory spectra of the type that will be obtained through the proposed studies.

在这个由化学部化学结构、动力学和机理B项目资助的项目中，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温度、压力或辐射等恶劣条件下的行为。这些条件类似于火焰（燃烧）或太空中的条件，导致有机化合物的降解并产生高度反应产物的复杂混合物。这项研究为理解两个截然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。有机燃料的燃烧是我国能源供应和国民经济的核心。对燃烧的基本理解提供了提高燃料燃烧的能源效率和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，已知有数百种不同的有机化合物存在于整个星系的环境中，这些环境非常恶劣，因为它们太热（靠近恒星）或因为它们太冷（远离恒星）。该项目支持研究生和本科生的教育。机械有机化学的培训为随后在工业界或学术界的职业生涯提供了宝贵的基础。罗伯特·j·麦克马洪教授一直是制定新闻部扩大参与计划的主要贡献者，并参加了国家多样性平等讲习班系列。Robert J. McMahon教授也是威斯康星大学麦迪逊分校STEM教育的倡导者。本提案解决了机械有机化学中与我们对恶劣反应环境的理解相关的问题。目前的提案沿着三个主要方向发展这些问题：1)有机化学中的量子力学隧道效应，2)碳链分子的光谱学和光化学，以及3)通过旋转光谱学产生，检测和表征关键化学靶点。拟议研究的科学影响超出了化学范畴，并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型电学和磁学性能的新型有机材料的基础。对活性有机物质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（ALMA）是一个由美国国家科学基金会资助的位于智利北部的射电望远镜天文干涉仪，它正在产生大量新的射电天文数据，其中大部分数据只能通过与实验室光谱的比较来解释，这些光谱将通过拟议的研究获得。

项目成果

Conformer-Specific Heavy-Atom Tunneling in the Rearrangement of Benzazirines to Ketenimines

苯并氮杂环重排为烯酮亚胺中的构象特异性重原子隧道效应

• DOI: 10.1021/acs.joc.9b02482
• 发表时间: 2019
• 期刊: The Journal of Organic Chemistry
• 作者: Schleif, Tim;Mieres-Perez, Joel;Henkel, Stefan;Mendez-Vega, Enrique;Inui, Hiroshi;McMahon, Robert J.;Sander, Wolfram
• 通讯作者: Sander, Wolfram

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.

Millimeter-wave and infrared spectroscopy of thiazole (c-C3H3NS) in its ground state and lowest-energy vibrationally excited states (ν18, ν17, and ν13)

噻唑 (c-C3H3NS) 基态和最低能量振动激发态（δ18、δ17 和 δ13）的毫米波和红外光谱

• DOI: 10.1016/j.jms.2021.111493
• 发表时间: 2021
• 期刊: Journal of Molecular Spectroscopy
• 影响因子: 1.4
• 作者: Esselman, Brian J.;Zdanovskaia, Maria A.;Adkins, Taylor K.;Billinghurst, Brant E.;Zhao, Jianbao;Woods, R. Claude;McMahon, Robert J.
• 通讯作者: McMahon, Robert J.

The 130–370 GHz rotational spectrum of phenyl isocyanide (C 6 H 5 NC)

苯基异氰化物 (C 6 H 5 NC) 的 130 – 370 GHz 旋转光谱

• DOI: 10.1063/1.5100805
• 发表时间: 2019
• 期刊: The Journal of Chemical Physics
• 作者: Zdanovskaia, Maria A.;Esselman, Brian J.;Woods, R. Claude;McMahon, Robert J.
• 通讯作者: McMahon, Robert J.

Synthesis and Characterization of Cyanobutadiene Isomers—Molecules of Astrochemical Significance

氰基丁二烯异构体——具有天体化学意义的分子的合成和表征

• DOI: 10.1021/acs.joc.9b03388
• 发表时间: 2020
• 期刊: The Journal of Organic Chemistry
• 作者: Kougias, Samuel M.;Knezz, Stephanie N.;Owen, Andrew N.;Sanchez, Rodrigo A.;Hyland, Grace E.;Lee, Daniel J.;Patel, Aatmik R.;Esselman, Brian J.;Woods, R. Claude;McMahon, Robert J.
• 通讯作者: McMahon, Robert J.