Bioinspired crowding directs supramolecular polymerisation

Crowding effects are crucial to maintaining functionality in biological systems, but little is known about their role in analogous artificial counterparts. Within the growing field of supramolecular polymer science, crowding effects have hitherto remained underappreciated. Herein, we show that crowding effects exhibit strong and distinct control over the kinetics, accessible pathways and final outcomes of supramolecular polymerisation processes. In the presence of a pre-formed supramolecular polymer as crowding agent, a model supramolecular polymer dramatically changes its self-assembly behaviour and undergoes a morphological transformation from bundled fibres into flower-like hierarchical assemblies, despite no co-assembly taking place. Notably, this new pathway can only be accessed in crowded environments and when the crowding agent exhibits a one-dimensional morphology. These results allow accessing diverse morphologies and properties in supramolecular polymers and pave the way towards a better understanding of high-precision self-assembly in nature. Crowding effects have long been established as powerful guiding forces in natural assembly processes. Here the authors report a bioinspired approach translating this phenomenon to artificial supramolecular polymers.

Automated summary

Crowding effects play a crucial role in the functionality of biological systems, but their role in artificial systems has been largely unexplored. In this study, the authors demonstrate that crowding effects have a strong and distinct control on the kinetics, pathways, and outcomes of supramolecular polymerization processes. The presence of a pre-formed supramolecular polymer as a crowding agent causes a model supramolecular polymer to undergo a morphological transformation in its self-assembly behavior, resulting in flower-like hierarchical assemblies. These results highlight the potential of accessing diverse morphologies and properties in supramolecular polymers by leveraging crowding effects.