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天体化学中的氢抽象:在 H 原子与乙酰胺(CHCONH)的反应中形成˙CHCONH,以及在固体正氢中通过˙CHCONH 的光解形成烯酮(CHCO)。

Hydrogen abstraction in astrochemistry: formation of ˙CHCONH in the reaction of H atom with acetamide (CHCONH) and photolysis of ˙CHCONH to form ketene (CHCO) in solid para-hydrogen.

机构信息

Department of Applied Chemistry and Institute of Molecular Science, National Chiao Tung University, Hsinchu 30010, Taiwan.

Department of Chemical Science, Faculty of Science, Universiti Tunku Abdul Rahman, Jalan University, Bandar Barat, 31900 Kampar, Perak, Malaysia.

出版信息

Phys Chem Chem Phys. 2020 Mar 18;22(11):6192-6201. doi: 10.1039/c9cp06279c.

Abstract

Acetamide (CH3CONH2) is the largest molecule containing an amide bond that has been detected in an interstellar medium; it is considered to be a precursor for complex organic molecules (COM). We utilized the advantages of a para-hydrogen (p-H2) quantum-solid matrix host to perform efficient reactions of hydrogen atoms with CH3CONH2. The H-abstraction reaction from the methyl group of CH3CONH2 to produce the 2-amino-2-oxoethyl radical, ˙CH2CONH2, was observed as the sole reaction channel in solid p-H2 at 3.3 K, consistent with theoretical predictions that this reaction has the smallest barrier among all possible channels. Our results show that the amide bond of acetamide is unaffected by hydrogen exposure, but the hydrogen abstraction activates this molecule to react with other species on its methyl site to extend its size or to include other functional groups as a first step to form COM under prebiotic or abiotic conditions. This previously neglected path should be considered in the astrochemical modeling. The photolysis of ˙CH2CONH2 at wavelengths 380-450 nm produces ketene; this step might provide a plausible mechanism to explain the anti-correlated abundance of ketene and acetamide in some astronomical observations.

摘要

乙酰胺(CH3CONH2)是在星际介质中检测到的含有酰胺键的最大分子,它被认为是复杂有机分子(COM)的前体。我们利用氘气(p-H2)量子固体基质宿主的优势,使 CH3CONH2 与氢原子发生高效反应。在 3.3 K 的固态 p-H2 中,观察到 CH3CONH2 的甲基上的 H 提取反应,生成 2-氨基-2-氧代乙基自由基˙CH2CONH2,这是唯一的反应通道,这与理论预测一致,即该反应在所有可能的通道中具有最小的势垒。我们的结果表明,乙酰胺的酰胺键不受氢暴露的影响,但氢提取会激活该分子,使其与甲基上的其他物质反应,从而扩展其大小或包含其他官能团,作为在原始或非生物条件下形成 COM 的第一步。在天体化学模拟中应该考虑到这一以前被忽视的途径。在 380-450nm 波长下的˙CH2CONH2 的光解会产生乙烯酮;这一步骤可能提供了一种合理的机制,可以解释在一些天文观测中乙烯酮和乙酰胺的反相关丰度。

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