28 February 2024 | Hailin Fu1,2, Jingyi Huang1,3, Joost J. B. van der Tol1,2, Lu Su4, Yuyang Wang1,5, Swayandipta Dey1,5,6, Peter Zijlstra1,5,6, George Fytas1,7,8, Ghislaine Vantomme1,2, Patricia Y. W. Dankers1,3 & E. W. Meijer1,2,9
Liquid-liquid phase separation (LLPS) of biopolymers has been shown to play a central role in the formation of membraneless organelles with various biological functions. Synthetic supramolecular polymers, which are non-covalent analogs of macromolecules, have not been reported to undergo LLPS. This study demonstrates that continuously growing fibrils from supramolecular polymerizations of synthetic components can form highly anisotropic aqueous liquid droplets (tactoids) through an entropy-driven pathway. The crowding environment, regulated by dextran concentration, affects both the kinetics of supramolecular polymerizations and the properties of LLPS, including phase-separation kinetics, morphology, internal order, fluidity, and mechanical properties. Additionally, substrate-liquid and liquid-liquid interfaces can accelerate LLPS, allowing the generation of a variety of three-dimensional-ordered structures, including highly ordered arrays of micrometre-long tactoids at surfaces. The generality and potential 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 to nanoscopic soft matter.Liquid-liquid phase separation (LLPS) of biopolymers has been shown to play a central role in the formation of membraneless organelles with various biological functions. Synthetic supramolecular polymers, which are non-covalent analogs of macromolecules, have not been reported to undergo LLPS. This study demonstrates that continuously growing fibrils from supramolecular polymerizations of synthetic components can form highly anisotropic aqueous liquid droplets (tactoids) through an entropy-driven pathway. The crowding environment, regulated by dextran concentration, affects both the kinetics of supramolecular polymerizations and the properties of LLPS, including phase-separation kinetics, morphology, internal order, fluidity, and mechanical properties. Additionally, substrate-liquid and liquid-liquid interfaces can accelerate LLPS, allowing the generation of a variety of three-dimensional-ordered structures, including highly ordered arrays of micrometre-long tactoids at surfaces. The generality and potential 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 to nanoscopic soft matter.