张亚.化学通报,2022,85(1):3-13.
两亲分子组装介导的化学反应及相关生命起源化学
Chemical Reactions Mediated by Surfactant Assemblies and Related Prebiotic Chemistry
投稿时间:2021-06-21  修订日期:2021-07-15
DOI:
中文关键词:  两亲分子组装  酶模拟  胶束  囊泡  生命起源化学
英文关键词:surfactant assemblies, enzyme mimics, micelles, vesicles, prebiotic chemistry
基金项目:
作者单位E-mail
张亚* 同济大学医学院 上海 200070 yazhang@tongji.edu.cn 
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中文摘要:
      化学反应会受其所处微环境影响,因此不同分子间相互作用对反应进程的调控不容忽视。水溶液作为优良的反应介质,其应用常受到反应物溶解性差的限制。在水溶液中引入胶束或囊泡等两亲分子组装,可在一定程度上克服这种不足。这些均匀分散的动态组装,提供了有别于本体水溶液的微环境,以非共价的方式,将单体结合到其极性表面或疏水内核。通过加速特定的化学反应,并改变反应路径,这些超分子组装最终可提高目标产物的产量,达到与酶类似的催化效果。除实际应用外,这一概念或许也适用于生命起源相关的基础研究:早期地球可能存在包括氨基酸前体或磷脂前体在内的两亲分子组装,它们可能在生命起源化学中加速和指导化学反应。为详细阐明这一概念,本文综述了一些两亲分子组装介导化学反应的经典案例,具体包括水解反应,有机合成和共轭聚合物的合成等,最后对相关生命起源研究进行了讨论与展望。
英文摘要:
      Since chemical reaction processes are strongly influenced by their local environments, the roles that diverse molecular interactions may play in fostering reactions should not be underestimated. Aqueous solution is known as excellent, environmentally friendly reaction media, but its application often suffer from poor reactant solubility. This defect can be overcome by the introduction of surfactant assemblies, such as micelles and vesicles. These homogeneously distributed dynamic assemblies, which are reminiscent of enzymes, provide different local environments compared with the bulk solution. By selective non-covalent binding reactants to hydrophobic cavities or polar interfaces, and accelerating specific chemical transformations of the bound reactants, micelles, vesicles and cubic phases not only accelerate reactions selectively but also change reaction pathways, i.e. guiding chemical reactions toward desired products. Besides practical applications, this concept might also be serviceable for the fundamental research of the origin of life. Since the early earth may contain soft assemblies of amphiphilic compounds, including amino acids and phospholipid precursors, the soft assemblies may act as enzymes in prebiotic chemistry: accelerating and controlling chemical reactions. In this review, the concept is illustrated with typical examples including enzyme mimics, hydrolysis reactions, the synthesis of conjugate polymers, organic syntheses and prebiotic chemistry.
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