Gao Jie, Ouyang Guanghui, Zhou Peng, Shang Peng, Long Haoran, Ji Lukang, Qu Zhiyuan, Guo Mengmeng, Yang Yongrui, Zhao Fenggui, Yin Xiaodong, Ke Yubin, Wei Zhongming, Zhang Zhen, Yan Xuehai, Liu Minghua, Qiao Yali, Song Yanlin
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Green Printing, CAS Research, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China.
University of Chinese Academy of Sciences, Beijing 100049, P. R. China.
J Am Chem Soc. 2024 Jul 3;146(26):18104-18116. doi: 10.1021/jacs.4c05141. Epub 2024 Jun 20.
The submarine-confined bubble swarm is considered an important constraining environment for the early evolution of living matter due to the abundant gas/water interfaces it provides. Similarly, the spatiotemporal characteristics of the confinement effect in this particular scenario may also impact the origin, transfer, and amplification of chirality in organisms. Here, we explore the confinement effect on the chiral hierarchical assembly of the amphiphiles in the confined bubble array stabilized by the micropillar templates. Compared with the other confinement conditions, the assembly in the bubble scenario yields a fractal morphology and exhibits a unique level of the chiral degree, ordering, and orientation consistency, which can be attributed to the characteristic interfacial effects of the rapidly formed gas/water interfaces. Thus, molecules with a balanced amphiphilicity can be more favorable for the promotion. Not limited to the pure enantiomers, chiral amplification of the enantiomer-mixed assembly is observed only in the bubble scenario. Beyond the interfacial mechanism, the fast formation kinetics of the confined liquid bridges in the bubble scenario endows the assembly with the tunable hierarchical morphology when regulating the amphiphilicity, aggregates, and confined spaces. Furthermore, the chiral-induced spin selectivity (CISS) effect of the fractal hierarchical assembly was systematically investigated, and a strategy based on photoisomerization was developed to efficiently modulate the CISS effect. This work provides insights into the robustness of confined bubble swarms in promoting a chiral hierarchical assembly and the potential applications of the resulting chiral hierarchical patterns in solid-state spintronic and optical devices.
由于潜艇受限气泡群提供了丰富的气/水界面，它被认为是生命物质早期进化的重要限制环境。同样，这种特定场景下限制效应的时空特征也可能影响生物体中手性的起源、转移和放大。在此，我们探索了微柱模板稳定的受限气泡阵列中两亲分子手性分级组装的限制效应。与其他限制条件相比，气泡场景中的组装产生分形形态，并表现出独特水平的手性程度、有序性和取向一致性，这可归因于快速形成的气/水界面的特征界面效应。因此，具有平衡两亲性的分子更有利于促进作用。不仅限于纯对映体，仅在气泡场景中观察到对映体混合组装的手性放大。除了界面机制外，气泡场景中受限液桥的快速形成动力学在调节两亲性、聚集体和受限空间时赋予组装体可调谐的分级形态。此外，系统研究了分形分级组装的手性诱导自旋选择性（CISS）效应，并开发了一种基于光异构化的策略来有效调节CISS效应。这项工作为受限气泡群在促进手性分级组装方面的稳健性以及所得手性分级图案在固态自旋电子和光学器件中的潜在应用提供了见解。
