中国科学院化学研究所刘鸣华团队近日研究了自组装大环柱[5]芳烃成环形、莫比乌斯带状纳米环和圆偏振发光。该项研究成果发表在2025年7月10日出版的《国家科学评论》杂志上。
大环分子独特的空间结构为实现多层次组装水平的精确手性控制提出了重大挑战,特别是在制造拓扑手性纳米结构方面。
研究组用两亲性谷氨酰胺单元功能化柱[5]芳烃,并探索了它们的自组装行为,成功地获得了手性纳米环和M双条状纳米结构。通过光谱分析、电子显微镜、扫描电子显微镜和原子力显微镜的结合,研究组阐明了驱动分子聚集形成具有明确手性的环形拓扑结构的潜在机制。
这些纳米结构表现出蓝色圆偏振发光(CPL)。值得注意的是,当非手性发光团(如TPPS或CBS)吸附在环形纳米结构上时,它们分别被诱导发出红色或蓝色CPL,而其他囊状或球形组装则不能。这项工作弥补了分子级大环手性和纳米级拓扑手性之间的差距,为设计先进的手性材料提供了新的可能性。
附:英文原文
Title: Self-assembling macrocyclic pillar[5]arene into toroidal, Mbius strips-like nanoring and circularly polarized luminescence
Author: Lu, Jie, Wang, Yuan, Jin, Jingjun, Liu, Minghua
Issue&Volume: 2025-07-10
Abstract: The unique spatial structure of macrocyclic molecules presents significant challenges in achieving precise chirality control across multiple hierarchical assembly levels, particularly in the fabrication of topologically chiral nanostructures. In this study, we functionalized pillar[5]arene with amphiphilic glutamide units and explored their self-assembly behavior, successfully obtaining chiral nanotoroids and Mbius strip-like nanostructures. Through a combination of spectroscopic analysis, electron microscopy, scanning electron microscopy and atomic force microscopy, we elucidated the underlying mechanism driving molecular aggregation to the formation of toroidal topologies with well-defined chirality. These nanostructures exhibit blue circularly polarized luminescence (CPL). Notably, when achiral luminophores such as TPPS or CBS are adsorbed onto the toroidal nanostructures, they are induced to emit red or blue CPL, respectively, while the other vesicular or spherical assemblies could not. This work bridges the gap between molecular-level macrocycle chirality and nanoscale topological chirality, offering new possibilities for the design of advanced chiroptical materials.
DOI: 10.1093/nsr/nwaf280
Source: https://dx.doi.org/10.1093/nsr/nwaf280
National Science Review:《国家科学评论》,创刊于2014年。隶属于牛津学术数据库,最新IF:20.6
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