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星际模拟冰中前体物的合成和异构化:乙醛亚胺、乙酰胺及其烯醇互变异构体。

Prebiotic Synthesis and Isomerization in Interstellar Analog Ice: Glycinal, Acetamide, and Their Enol Tautomers.

机构信息

Department of Chemistry, University of Hawaii at Manoa, Honolulu, HI 96822, USA.

W. M. Keck Research Laboratory in Astrochemistry, University of Hawaii at Manoa, Honolulu, HI 96822, USA.

出版信息

Angew Chem Int Ed Engl. 2023 Mar 13;62(12):e202218645. doi: 10.1002/anie.202218645. Epub 2023 Feb 9.

Abstract

Glycinal (HCOCH NH ) and acetamide (CH CONH ) are simple molecular building blocks of biomolecules in prebiotic chemistry, though their origin on early Earth and formation in interstellar media remain a mystery. These molecules are formed with their tautomers in low temperature interstellar model ices upon interaction with simulated galactic cosmic rays. Glycinal and acetamide are accessed via barrierless radical-radical reactions of vinoxy (⋅CH CHO) and acetyl (⋅C(O)CH ), and then undergo keto-enol tautomerization. Exploiting tunable photoionization reflectron time-of-flight mass spectroscopy and photoionization efficiency (PIE) curves, these results demonstrate fundamental reaction pathways for the formation of complex organics through non-equilibrium ice reactions in cold molecular cloud environments. These molecules demonstrate an unconventional starting point for abiotic synthesis of organics relevant to contemporary biomolecules like polypeptides and cell membranes in deep space.

摘要

甘氨酰基(HCOCHNH )和乙酰胺基(CHCONH )是前生物化学中生物分子的简单分子构建块,尽管它们在早期地球上的起源和在星际介质中的形成仍然是一个谜。这些分子在与模拟银河宇宙射线相互作用时,在低温星际模型冰中以它们的互变异构体形成。甘氨酰基和乙酰胺基通过自由基-自由基反应的无势垒反应生成,反应涉及乙烯氧基(⋅CHCHO)和乙酰基(⋅C(O)CH ),然后经历酮-烯醇互变异构。利用可调谐光致电离反射飞行时间质谱和光致电离效率(PIE)曲线,这些结果证明了通过冷分子云环境中非平衡冰反应形成复杂有机物的基本反应途径。这些分子为深太空中与当代生物分子(如多肽和细胞膜)相关的生物无机合成提供了一个非传统的起点。

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