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向列型液晶中手性聚集诱导发光分子手性放大的直接可视化

Direct Visualization of Chiral Amplification of Chiral Aggregation Induced Emission Molecules in Nematic Liquid Crystals.

作者信息

Xia Qing, Meng Luming, He Tingchao, Huang Guangxi, Li Bing Shi, Tang Ben Zhong

机构信息

Key Laboratory of New Lithium-Ion Battery and Mesoporous Material, College of Chemistry and Environmental Engineering, Shenzhen University, 1066 Xueyuan Avenue, Nanshan, Shenzhen 518055, China.

MOE Key Laboratory of Laser Life Science & Guangdong Provincial Key Laboratory of Laser Life Science, College of Biophotonics, South China Normal University, Guangzhou 510631, China.

出版信息

ACS Nano. 2021 Mar 23;15(3):4956-4966. doi: 10.1021/acsnano.0c09802. Epub 2021 Mar 4.

Abstract

Chiral amplification in liquid crystals (LCs) is a well-known strategy. However, current knowledge about the underlying mechanism was still lacking; in particular, how it was realized at the nano scale still remained to be revealed. Here, we provide systematical exploration of chiral amplification of chiral aggregation induced emission (AIE) molecules in LCs from direct visualization of their co-assemblies at the nano scale to theoretical calculation of the molecular packing modes on a single molecular level. Using AFM imaging,we directly visualized the co-assembly formed by chiral AIE molecules/LCs at the nano scale: the chiral AIE molecules self-assembled into helical fibers to serve as the helical template for LCs to bind, while the LCs helically bound to the helical fibers to form the co-assembly, giving the morphology of pearled necklaces or thick rods. Theoretical calculation suggested that chiral AIE molecules were packed into left-handed helical fibers with a large volume of empty space between neighboring molecules, which provided the binding cites for LCs. Structural analysis showed that the π-π stacking between aromatic groups from LCs and TPE groups and the σ-π hyperconjugation between LC aromatic groups and cholesterol aliphatic groups play an important role in stabilizing the binding of LCs in the confined space on the surface of the helical assemblies.

摘要

液晶(LCs)中的手性放大是一种广为人知的策略。然而,目前对于其潜在机制的了解仍然不足;特别是,它在纳米尺度上是如何实现的仍有待揭示。在这里,我们对手性聚集诱导发光(AIE)分子在液晶中的手性放大进行了系统的探索,从纳米尺度上对其共组装体的直接可视化到单分子水平上分子堆积模式的理论计算。通过原子力显微镜成像,我们在纳米尺度上直接观察到手性AIE分子/液晶形成的共组装体:手性AIE分子自组装成螺旋纤维,作为液晶结合的螺旋模板,而液晶则螺旋状地结合到螺旋纤维上形成共组装体,呈现出珍珠项链或粗棒的形态。理论计算表明,手性AIE分子堆积成左手螺旋纤维,相邻分子之间有大量的空隙,这为液晶提供了结合位点。结构分析表明,液晶中的芳基与TPE基团之间的π-π堆积以及液晶芳基与胆固醇脂肪族基团之间的σ-π超共轭在稳定螺旋组装体表面受限空间中液晶的结合方面发挥了重要作用。

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