de Graaf Freek V, Zoister Christian, Schade Boris, Hilal Tarek, Lou Xianwen, Wijker Stefan, Schoenmakers Sandra M C, Vantomme Ghislaine, Haag Rainer, Singh Abhishek K, Meijer E W
Institute for Complex Molecular Systems, Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology, PO Box 513, 5600 MB Eindhoven, The Netherlands.
Institute of Chemistry and Biochemistry, Freie Universität Berlin, Takustraβe 3, 14195 Berlin, Germany.
J Am Chem Soc. 2025 May 21;147(20):17468-17476. doi: 10.1021/jacs.5c04047. Epub 2025 May 8.
Asymmetric structures are widespread in nature and essential for life and biointeractive materials. Although nature uniformly operates with homochirality, the hierarchical control of asymmetry in synthetic, water-soluble molecular systems is still underexplored. In this work, we present the amplification of helical asymmetry of benzene-1,3,5-tricarboxamide (BTA) supramolecular polymers by coassembly with homochiral nonionic surfactants. For these mixtures, a strong amplification of asymmetry was observed from the surfactant's molecular chirality to a preferred helicity of the coassembled polymers. This amplification showed maxima at identical stoichiometric ratios for structurally distinct chiral surfactants, demonstrating the similarity of the coassembly mechanism. Notably, the surfactant-induced asymmetry was completely overridden by the introduction of stereogenic centers into the BTA structure, emphasizing the subtlety of the amplification process. Using a combination of spectroscopy and microscopy, we found that surfactants coassemble with the supramolecular polymers to change fiber morphology from racemic double helices to single helices with a preferred handedness. Furthermore, the coassemblies showed a unique combination of structures and dynamics. Our results elucidate the consequences of supramolecular polymer-surfactant coassembly, offering valuable insights into the resulting asymmetric structures.
不对称结构在自然界中广泛存在，对生命和生物交互材料至关重要。尽管自然界以同手性均匀运作，但合成的水溶性分子体系中不对称性的分级控制仍未得到充分探索。在这项工作中，我们展示了通过与同手性非离子表面活性剂共组装来放大苯 - 1,3,5 - 三甲酰胺（BTA）超分子聚合物的螺旋不对称性。对于这些混合物，从表面活性剂的分子手性到共组装聚合物的优选螺旋性观察到了强烈的不对称性放大。这种放大对于结构不同的手性表面活性剂在相同化学计量比时显示出最大值，证明了共组装机制的相似性。值得注意的是，通过在BTA结构中引入手性中心，表面活性剂诱导的不对称性被完全克服，强调了放大过程的微妙性。通过结合光谱学和显微镜技术，我们发现表面活性剂与超分子聚合物共组装，将纤维形态从外消旋双螺旋转变为具有优选手性的单螺旋。此外，共组装体表现出独特的结构和动力学组合。我们的结果阐明了超分子聚合物 - 表面活性剂共组装的后果，为所得不对称结构提供了有价值的见解。
