Dynamic transformation of bio-inspired single-chain nanoparticles at interfaces

Abstract

The interfacial behavior of macromolecules dictates their intermolecular interactions, which can impact the processing and application of polymers for pharmaceutical and synthetic use. Using molecular dynamics simulations, we observe the evolution of a random heteropolymer in the presence of liquid–liquid interfaces. The system of interest forms single-chain nanoparticles through hydrophobic collapse in water, lacking permanent crosslinks and making their morphology mutable in new environments. Complex amphiphilic polymers are shown to be capable of stabilizing high interfacial tension water–hexane interfaces, often unfolding to maximize surface coverage. Despite drastic changes to polymer conformation, monomer presence in the water phase is generally maintained and most changes are due to increased hydrophobic solvent exposure toward the oil phase. These results are then compared to the behavior at the water–graphene interface, where the macromolecules adsorb but do not remodel. The polymer’s behavior is shown to depend significantly on both its own amphiphilic character and the deformability of the interface.