Supramolecular polymers form tactoids through liquid–liquid phase separation

Nature, vol. 626, pp. 1011–1018

Abstract

Abstract 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 functions 1–3 . The interplay between LLPS and macromolecular condensation is part of continuing studies 4,5 . 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.

Authors 11

1. Hailin Fu corresponding

   Eindhoven University of Technology

   Affiliation as printed

   Department of Chemistry and Chemical Engineering and Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology, Eindhoven, The Netherlands. h.fu@tue.nl

   Institute for Complex Molecular Systems, Eindhoven University of Technology, Eindhoven, The Netherlands. h.fu@tue.nl

   Institute for Complex Molecular Systems, Eindhoven University of Technology, Eindhoven, The Netherlands

2. Jingyi Huang

   Eindhoven University of Technology

   Affiliation as printed

   Department of Biomedical Engineering and Laboratory of Chemical Biology, Eindhoven University of Technology, Eindhoven, The Netherlands

   Institute for Complex Molecular Systems, Eindhoven University of Technology, Eindhoven, The Netherlands

3. Joost J. B. van der Tol

   Eindhoven University of Technology

   Affiliation as printed

   Department of Chemistry and Chemical Engineering and Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology, Eindhoven, The Netherlands

   Institute for Complex Molecular Systems, Eindhoven University of Technology, Eindhoven, The Netherlands

4. Lu Su Aachen Leiden Academic Centre for Drug Research

   Leiden University

   Affiliation as printed

   Leiden Academic Centre for Drug Research, Leiden University, Leiden, The Netherlands

5. Yuyang Wang

   Eindhoven University of Technology

   Affiliation as printed

   Department of Applied Physics and Science Education, Eindhoven University of Technology, Eindhoven, The Netherlands

   Institute for Complex Molecular Systems, Eindhoven University of Technology, Eindhoven, The Netherlands

6. Swayandipta Dey

   Eindhoven University of Technology

   Affiliation as printed

   Department of Applied Physics and Science Education, Eindhoven University of Technology, Eindhoven, The Netherlands

   Eindhoven Hendrik Casimir Institute, Eindhoven University of Technology, Eindhoven, The Netherlands

   Institute for Complex Molecular Systems, Eindhoven University of Technology, Eindhoven, The Netherlands

7. Peter Zijlstra

   Eindhoven University of Technology

   Affiliation as printed

   Department of Applied Physics and Science Education, Eindhoven University of Technology, Eindhoven, The Netherlands

   Eindhoven Hendrik Casimir Institute, Eindhoven University of Technology, Eindhoven, The Netherlands

   Institute for Complex Molecular Systems, Eindhoven University of Technology, Eindhoven, The Netherlands

8. George Fytas

   Max Planck Institute for Polymer Research · FORTH Institute of Electronic Structure and Laser · Eindhoven University of Technology

   Affiliation as printed

   Institute for Complex Molecular Systems, Eindhoven University of Technology, Eindhoven, The Netherlands

   Institute of Electronic Structure and Laser, FO.R.T.H, Heraklion, Greece

   Max Planck Institute for Polymer Research, Mainz, Germany

9. Ghislaine Vantomme

   Eindhoven University of Technology

   Affiliation as printed

   Department of Chemistry and Chemical Engineering and Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology, Eindhoven, The Netherlands

   Institute for Complex Molecular Systems, Eindhoven University of Technology, Eindhoven, The Netherlands

10. Patricia Y. W. Dankers

    Eindhoven University of Technology

    Affiliation as printed

    Department of Biomedical Engineering and Laboratory of Chemical Biology, Eindhoven University of Technology, Eindhoven, The Netherlands

    Institute for Complex Molecular Systems, Eindhoven University of Technology, Eindhoven, The Netherlands

11. Egbert W. Meijer corresponding

    UNSW Sydney · Eindhoven University of Technology

    Affiliation as printed

    Department of Chemistry and Chemical Engineering and Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology, Eindhoven, The Netherlands. E.W.Meijer@tue.nl

    Institute for Complex Molecular Systems, Eindhoven University of Technology, Eindhoven, The Netherlands. E.W.Meijer@tue.nl

    School of Chemistry and RNA Institute, University of New South Wales, Sydney, New South Wales, Australia. E.W.Meijer@tue.nl

    Department of Chemistry and Chemical Engineering and Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology, Eindhoven, The Netherlands