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螺旋沟槽聚苯乙炔衍生物二维涡状组合的中尺度手性可调
作者:小柯机器人 发布时间:2025/10/28 15:46:15


近日,北京大学张洁团队研究了螺旋沟槽聚苯乙炔衍生物二维涡状组合的中尺度手性可调。相关论文于2025年10月27日发表在《美国化学会志》上。

二维手性材料为传感与催化领域带来了广阔前景,然而在有机二维组装体中实现介观手性仍具挑战。

研究组受生物启发提出新策略:通过链间扭曲耦合,利用模拟DNA结构的螺旋沟槽聚苯乙炔衍生物制备具有介观手性的二维涡旋状片晶。通过调控溶剂交换速率与温度等组装动力学参数,他们实现了对手性方向与曲率的程序化调控。理论模拟表明:固有链螺旋性决定扭曲方向,而组装条件控制角度大小。

具有螺旋沟槽的聚合物性能优于刚性棒状类似物——其凹槽表面构成立体化学“热点”,可通过传导扭转应力实现跨平面定向耦合。介观手性对聚合物分子量的依赖性进一步证实了螺旋沟槽驱动手性放大效应的普适性。这些涡旋片晶表现出优于常规非手性二维材料的圆偏振发光特性。该研究既为理解多级手性传递机制提供了新见解,又为构建仿生介观手性材料建立了工程学框架。

附:英文原文

Title: Tunable Mesoscale Chirality in Two-Dimensional Vortex-like Assemblies of Helically Grooved Poly(phenylacetylene) Derivatives

Author: Yihan Huang, Shuming Kang, Siliang Cai, Zhehao Zhang, Peiyao Yu, Xiaoqian Sun, Xinhua Wan, Jie Zhang

Issue&Volume: October 27, 2025

Abstract: Two-dimensional (2D) chiral materials offer exciting opportunities in sensing and catalysis, yet achieving mesoscale chirality in 2D organic assemblies remains challenging. We introduce a bioinspired strategy to fabricate 2D vortex-like platelets with mesoscale chirality from DNA-mimicking helically grooved poly(phenylacetylene) derivatives via interchain twisted coupling. By tuning assembly kinetics including solvent exchange rate and temperature, we program both the handedness and curvature of mesoscopic chirality. Theoretical simulations show that inherent chain helicity dictates twist direction, while assembly conditions govern angular magnitude. Polymers with helical grooves outperform rigid rod-like analogues: their fluted surfaces serve as stereochemical “hotspots”, channeling torsional stress to enable directional coupling across the plane. Dependence of mesoscale chirality on polymer molecular weights further confirms the universality of helical-groove-driven chiral amplification. These vortex platelets exhibit enhanced circularly polarized luminescence (CPL) superior to regular achiral 2D ones. This work offers new insights into both mechanistic understanding of hierarchical chirality transfer and an engineering framework for biomimetic mesoscale chiral materials.

DOI: 10.1021/jacs.5c13610

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.5c13610

期刊信息

JACS:《美国化学会志》,创刊于1879年。隶属于美国化学会,最新IF:16.383
官方网址:https://pubs.acs.org/journal/jacsat
投稿链接:https://acsparagonplus.acs.org/psweb/loginForm?code=1000