Zhao Jianjian, Dou Wei-Tao, Cui Wanding, Shi Xueliang, Li Xiaodong, Fang Junfeng, Qian Xuhong, Yang Hai-Bo, Xu Lin
State Key Laboratory of Petroleum Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Shanghai Frontiers Science Center of Molecule Intelligent Syntheses, School of Chemistry and Molecular Engineering, East China Normal University, 3663 N. Zhongshan Road, Shanghai, 200062, P.R. China.
School of Physics and Electronic Science, Engineering Research Center of Nanophotonics & Advanced Instrument, Ministry of Education, East China Normal University, Shanghai, 200241, P.R. China.
Angew Chem Int Ed Engl. 2025 Jul;64(27):e202503284. doi: 10.1002/anie.202503284. Epub 2025 May 8.
Chirality plays a vital role in material properties, and precise control of chiral signals is key to designing functional materials. Supramolecular self-assembly offers an efficient means to integrate chiral building blocks with chromophores, yet controlling the assembly pathway remains challenging due to the complexity of non-covalent interactions. Here, we introduce a continuous parallel-laminar-assisted self-assembly strategy that exploits solvent ordering and solute diffusion in confined environments to regulate chiral signals in multi-component peptide co-assemblies. Notably, six nonpolar amino acids exhibit significantly enhanced chiroptical responses, as confirmed by circular dichroism (CD) and circularly polarized luminescence (CPL) spectroscopy. Intriguingly, Fmoc-Ala and 1-aminopyrene (AP) co-assemblies formed in a microfluidic chip show a reversed chiroptical signal compared to those from batch reactions. Molecular dynamics (MD) simulations and COMSOL modeling suggest that velocity gradients and shear forces in microfluidics induce ordered non-covalent interactions, altering excimer stacking and modulating chiroptical properties. This study presents an effective strategy for controlling chiral optical signals in confined environments, offering an interesting approach for supramolecular chiral transfer and regulation.
手性在材料性质中起着至关重要的作用，精确控制手性信号是设计功能材料的关键。超分子自组装提供了一种将手性构建单元与发色团整合的有效方法，但由于非共价相互作用的复杂性，控制组装途径仍然具有挑战性。在这里，我们介绍了一种连续平行层流辅助自组装策略，该策略利用受限环境中的溶剂有序化和溶质扩散来调节多组分肽共组装中的手性信号。值得注意的是，六种非极性氨基酸表现出显著增强的手性光学响应，这通过圆二色性（CD）和圆偏振发光（CPL）光谱得到证实。有趣的是，在微流控芯片中形成的Fmoc-Ala和1-氨基芘（AP）共组装体与批量反应形成的共组装体相比，显示出相反的手性光学信号。分子动力学（MD）模拟和COMSOL建模表明，微流控中的速度梯度和剪切力诱导有序的非共价相互作用，改变准分子堆积并调节手性光学性质。这项研究提出了一种在受限环境中控制手性光学信号的有效策略，为超分子手性转移和调控提供了一种有趣的方法。
