Organic Chemistry in Harsh Reaction Environments

恶劣反应环境下的有机化学

• 批准号: 1362264
• 负责人: Robert McMahon
• 金额: $ 54.5万
• 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: 2014
• 资助国家: 美国
• 起止时间: 2014-08-01 至 2018-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1362264&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 will investigate 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. The proposed research will explore the chemical 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. Professor McMahon and his coworkers will also continue their engagement in a variety of science education and outreach activities. The fundamental chemical studies proposed herein would not have been possible only a few years ago. Tremendous advances in both experimental and computational techniques now permit the analysis and interpretation of the experimental spectra obtained from complex mixtures of reactive species. Direct studies of these species are challenging because these molecules typically exhibit high reactivity. Nevertheless, it is the reaction chemistry of these ephemeral intermediates that governs the chemical behavior of the system. In combustion chemistry, the determination of accurate equilibrium structures of reactive intermediates will provide important benchmarks for prototypical molecules, and theory can be further used to establish thermodynamic parameters that are important for modeling. In astrochemistry, the Atacama Large Millimeter / sub-millimeter Array (ALMA), an astronomical interferometer of radio telescopes in the Atacama Desert of northern Chile completed in 2013, is generating a deluge of new radio-astronomical data. These data 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教授将研究有机化合物在温度，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。 拟议的研究将探索这些活性分子的化学性质和化学反应。 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。 教授麦克马洪和他的同事也将继续在各种科学教育和推广活动的参与。 仅仅在几年前，这里提出的基础化学研究是不可能的。 在实验和计算技术的巨大进步，现在允许的分析和解释的实验光谱从复杂的反应物种的混合物。 这些物质的直接研究具有挑战性，因为这些分子通常表现出高反应性。 然而，正是这些短暂的中间体的反应化学决定了系统的化学行为。 在燃烧化学中，反应中间体的精确平衡结构的确定将为原型分子提供重要的基准，并且理论可以进一步用于建立对建模重要的热力学参数。 在天体化学方面，阿塔卡马大型毫米/亚毫米阵列（阿尔马）是位于智利北方阿塔卡马沙漠的射电望远镜天文干涉仪，于2013年完工，正在产生大量新的射电天文数据。 这些数据只能通过与通过拟议研究获得的实验室光谱进行比较来解释。

项目成果

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.

Photochemistry of 2-Formylphenylnitrene: A Doorway to Heavy-Atom Tunneling of a Benzazirine to a Cyclic Ketenimine

• DOI: 10.1021/jacs.7b10495
• 发表时间: 2017-12-06
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Nunes, Claudio M.;Reva, Igor;Fausto, Rui
• 通讯作者: Fausto, Rui