Molecular modelling of supramolecular polymers

Nature uses self-assembly for building supramolecular materials possessing fascinating properties (self-healing, adaptive, reconfigurable and responsive) that are fundamental for many complex biological functions. Artificial supramolecular polymers, composed of monomers that self-assemble via non-covalent interactions, are attracting increasing interest as platforms for building innovative materials, as these possess similar bioinspired dynamic properties. However, their design still relies on an inefficient/expensive trial-and-error approach. A key question is how to design the monomers to control the properties of the supramolecular polymer. Most often, obtaining from the experiments molecular-level information on how to control these assemblies is prohibitively difficult. Molecular modelling is a fundamental support in this field, allowing investigation of the supramolecular polymer from a privileged point of view and at high-resolution. Such a ‘virtual microscope’ can provide information on the factors that control supramolecular polymer structure and dynamics, on the monomer–monomer interactions and their cooperativity that are precluded to the experiments, paving the way to structure–property relationships useful to advance the rational design of such materials. This review discusses the state of the art of molecular modelling and simulation of supramolecular polymers. The field is advancing quickly. But the detailed insight that can be reached and the continuous technical developments promise that this is only the beginning.