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阐明前生物意义上的碳-碳键形成的迭代过程。

Elucidation of an iterative process of carbon-carbon bond formation of prebiotic significance.

机构信息

Laboratoire de Biogéochimie Moléculaire, Université de Strasbourg, Institut de Chimie de Strasbourg UMR7177, ECPM, Strasbourg, France.

出版信息

Astrobiology. 2010 Dec;10(10):973-88. doi: 10.1089/ast.2009.0441.

DOI:10.1089/ast.2009.0441
PMID:21162677
Abstract

Laboratory experiments carried out under plausible prebiotic conditions (under conditions that might have occurred at primitive deep-sea hydrothermal vents) in water and involving constituents that occur in the vicinity of submarine hydrothermal vents (e.g., CO, H(2)S, NiS) have disclosed an iterative Ni-catalyzed pathway of C-C bond formation. This pathway leads from CO to various organic molecules that comprise, notably, thiols, alkylmono- and disulfides, carboxylic acids, and related thioesters containing up to four carbon atoms. Furthermore, similar experiments with organic compounds containing various functionalities, such as thiols, carboxylic acids, thioesters, and alcohols, gave clues to the mechanisms of this novel synthetic process in which reduced metal species, in particular Ni(0), appear to be the key catalysts. Moreover, the formation of aldehydes (and ketones) as labile intermediates via a hydroformylation-related process proved to be at the core of the chain elongation process. Since this process can potentially lead to organic compounds with any chain length, it could have played a significant role in the prebiotic formation of lipidic amphiphilic molecules such as fatty acids, potential precursors of membrane constituents.

摘要

在水相条件下,于可能存在于原始深海热液喷口的类似原始条件下进行的实验室实验,以及涉及到在海底热液喷口附近存在的成分(例如 CO、H(2)S、NiS),揭示了一个 Ni 催化的 C-C 键形成的迭代途径。这条途径从 CO 出发,形成了各种有机分子,特别是硫醇、烷基单硫化物和二硫化物、羧酸以及含有多达四个碳原子的相关硫酯。此外,对含有各种官能团的有机化合物(如硫醇、羧酸、硫酯和醇)进行类似的实验,为这一新颖合成过程的机制提供了线索,其中还原金属物种,特别是 Ni(0),似乎是关键催化剂。此外,通过与氢甲酰化相关的过程形成醛(和酮)作为不稳定中间体,被证明是链延伸过程的核心。由于这个过程可能导致具有任何链长的有机化合物的形成,因此它可能在原始脂质两亲分子(如脂肪酸)的形成中发挥了重要作用,脂肪酸是膜成分的潜在前体。

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