通过随机成核从外消旋溶液中自发产生同手性悬浮液

IF 15.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Leif-Thore Deck, Mercedeh Sadat Hosseinalipour, Marco Mazzotti
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引用次数: 0

摘要

同手性是生命的标志,它在生命起源前的地球上的出现仍然难以捉摸。在这里,我们展示了一个自发的途径,形成团簇的手性物质(N-(2-甲基苄基)-苯基甘氨酸酰胺,NMPA)从初始的完美对称状态,即外消旋溶液,发展到完全的同手性状态,其中悬浊液中只有单手性的对映不纯晶体存在。它首先需要建立过饱和条件,例如,由于溶剂蒸发或冷却,然后对映纯晶体的随机成核作为对称破坏事件,最后通过外消旋溶液中的温度波动进行不对称扩增和完全去消旋(由于碱1,8-重氮杂环[5.4.0]十一-7-en, DBU的存在)。在开发了随机建模平台和实验设置之后,我们通过详细的模拟和实验室实验证实了这一途径的可行性。我们还展示了如何从各种不同手性的局部同手性状态通过合并和去消酰基化产生全局同手性状态。由于通过温度循环触发过饱和形成、成核和去中心化的外部条件在生命起源前的地球上也一定存在,因此所提出的自发途径可能在地球上生命的出现中发挥了合理的作用。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Spontaneous Emergence of Homochiral Suspensions from Racemic Solutions via Stochastic Nucleation

Spontaneous Emergence of Homochiral Suspensions from Racemic Solutions via Stochastic Nucleation
Homochirality represents a hallmark of life, and its emergence on the prebiotic Earth remains elusive. Here, we demonstrate a spontaneous pathway to homochirality, where a conglomerate-forming chiral species (N-(2-methylbenzylidene)-phenylglycine amide, NMPA) evolves from an initial perfectly symmetric state, i.e., a racemic solution, to a fully homochiral state, where only enantiopure crystals of one handedness are present in the suspension. It entails first the establishment of supersaturated conditions, e.g., because of either solvent evaporation or cooling, then stochastic nucleation of enantiopure crystals as the symmetry-breaking event, and finally asymmetry amplification and complete deracemization via temperature fluctuations in a racemizing solution (thanks to the presence of the base 1,8- diazabicyclo[5.4.0]undec-7-en, DBU). After developing a stochastic modeling platform and an experimental setup, we confirm the plausibility of this pathway through both detailed simulations and laboratory experiments. We also show how from a variety of local homochiral states of different handedness a global homochiral state may emerge via merging and deracemizing. Because the external conditions triggering supersaturation creation, nucleation, and deracemization via temperature-cycling must have existed also on the prebiotic Earth, the proposed spontaneous pathway may have plausibly played a role in the emergence of life on Earth.
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来源期刊
CiteScore
24.40
自引率
6.00%
发文量
2398
审稿时长
1.6 months
期刊介绍: The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.
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