Supramolecular polymers form tactoids through liquid-liquid phase separation

• 成果类型: Article
• 署名作者: Fu, Hailin; Huang, Jingyi; van der Tol, Joost J. B.; Su, Lu; Wang, Yuyang; Dey, Swayandipta; Zijlstra, Peter; Fytas, George; Vantomme, Ghislaine; Dankers, Patricia Y. W.; Meijer, E. W.
• 署名单位: Eindhoven University of Technology; Eindhoven University of Technology; Eindhoven University of Technology; Eindhoven University of Technology; Eindhoven University of Technology; Leiden University; Leiden University - Excl LUMC; Eindhoven University of Technology; Eindhoven University of Technology; Max Planck Society; Foundation for Research & Technology - Hellas (FORTH); University of New South Wales Sydney; University of New South Wales Sydney
• 刊物名称: Nature
• ISSN/ISSBN: 0028-4069
• DOI: 10.1038/s41586-024-07034-7
• 发表日期: 2024-02-29
• 关键词: droplets; BEHAVIOR

摘要

Liquid-liquid phase separation (LLPS) of biopolymers has recently been shown to play a central role in the formation of membraneless organelles with a multitude of biological functions1-3. The interplay between LLPS and macromolecular condensation is part of continuing studies4,5. Synthetic supramolecular polymers are the non-covalent equivalent of macromolecules but they are not reported to undergo LLPS yet. Here we show that continuously growing fibrils, obtained from supramolecular polymerizations of synthetic components, are responsible for phase separation into highly anisotropic aqueous liquid droplets (tactoids) by means of an entropy-driven pathway. The crowding environment, regulated by dextran concentration, affects not only the kinetics of supramolecular polymerizations but also the properties of LLPS, including phase-separation kinetics, morphology, internal order, fluidity and mechanical properties of the final tactoids. In addition, substrate-liquid and liquid-liquid interfaces proved capable of accelerating LLPS of supramolecular polymers, allowing the generation of a myriad of three-dimensional-ordered structures, including highly ordered arrays of micrometre-long tactoids at surfaces. The generality and many possibilities of supramolecular polymerizations to control emerging morphologies are demonstrated with several supramolecular polymers, opening up a new field of matter ranging from highly structured aqueous solutions by means of stabilized LLPS to nanoscopic soft matter. Spontaneous liquid-liquid phase-separation behaviour of high-aspect-ratio fibrils, obtained from supramolecular polymerizations of synthetic components, forms tactoids by means of an entropy-driven pathway.