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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 Source: Journal of the American Chemical Society, 2024; ISSN: 00027863, E-ISSN: 15205126; DOI: 10.1021/jacs.4c05141; Publisher: American Chemical Society

Articles not published yet, but available online Article in Press

Author affiliation:

Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Green Printing, CAS Research, Institute of Chemistry, Chinese Academy of Sciences, Beijing; 100190, China

University of Chinese Academy of Sciences, Beijing; 100049, China

Beijing National Laboratory of Molecular Sciences, CAS Key Laboratory of Colloid, Interface and Thermodynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing; 100190, China

State Key Laboratory of Biochemical Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing; 100190, China

Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Molecular Reaction Dynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing; 100190, China

State Key Laboratory of Superlattices and Microstructures, Institute of Semiconductors, Chinese Academy of Sciences, Beijing; 100083, China

Key Laboratory of Cluster Science, Ministry of Education of China, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing; 102488, China

Spallation Neutron Source Science Center, Dongguan; 523803, China

Abstract:

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.