Non-Trivial Stimuli-Responsive Collective Behaviours Emerging from Microscopic Dynamic Complexity in Supramolecular Polymer Systems

Supramolecular polymers are composed of monomers that self-assemble non-covalently generating distributions of fibers in continuous exchange-and-communication with each other and the surrounding. Intriguing collective properties may emerge in such molecular-scale complex systems, following mechanisms often difficult to ascertain. Here we show how non-trivial collective behaviors may emerge in dynamical supramolecular polymer systems already at low-complexity levels. We combine minimalistic models, simulations, and advanced statistical analyses investigating how cooperative and non-cooperative supramolecular polymer systems respond to a specific stimulus: i.e., the addition of molecular sequestrators perturbing their equilibrium. Our data show how, while in a non-cooperative system all assemblies populating the system suffer uniformly the perturbation, in a cooperative system the larger/stronger assemblies survive at the expense of the smaller/weaker entities. Collective behaviors typical of larger-scale and more complex (social, economic, etc.) systems may thus emerge even in relatively simple self-assembling systems from the internal (microscopic) dynamic heterogeneity of their ensembles.