Supramolecular morphological transition driven by nonequilibrium break-and-build self-organisation.

Abstract

Controlling the nonequilibrium dynamics in synthetic systems is an important challenge in supramolecular chemistry. Biological morphogenesis exploits nonequilibrium reaction-diffusion processes to organise differentiated cell networks and functions in space. In contrast, artificial assemblies are mostly formed under thermodynamic control, and they thus lack autonomous spatial complexity. Here, we present a supramolecular morphological transition that enables spatial control over the differentiation and decomposition of synthetic self-assembled fibres. Upon hybridisation with a surfactant, self-assembled fibres made from low-molecular-weight peptides undergo nonequilibrium break-and-build dynamics through cycles of fibre decomposition and reformation. Coupling these dynamics with surfactant diffusion generates repeated propagating waves that produce macroscopic nonlinear concentric patterns of chemically distinct fibres. These resultant patterns can be modulated by applying transient thermal pulses or by introducing multiple surfactants. This approach provides a strategy for the hierarchical organisation of supramolecular assemblies, opening up opportunities for constructing complex, functional soft materials with controlled spatial architectures.