Cosolute partitioning in polymer networks: Effects of flexibility and volume transitions

Abstract: We study the partitioning of cosolute particles in a thin film of a semi-flexible polymer network by a combination of coarse-grained (implicit-solvent) stochastic dynamics simulations and mean-field theory. We focus on a wide range of solvent qualities and cosolute-network interactions for selected polymer flexibilities. Our investigated ensemble (isothermal-isobaric) allows the network to undergo a volume transition from extended to collapsed state while the cosolutes can distribute in bulk and network, correspondingly. We find a rich topology of equilibrium states of the network and transitions between them, qualitatively depending on solvent quality, polymer flexibility, and cosolute-network interactions. In particular, we find a novel cosolute-induced' collapsed state, where strongly attractive cosolutes bridge network monomers albeit the latter interact mutually repulsive. Finally, the cosolutes' global partitioninglandscape', computed as a function of solvent quality and cosolute-network interactions, exhibits very different topologies depending on polymer flexibility. The simulation results are supported by theoretical predictions obtained with a two-component mean-field approximation for the Helmholtz free energy that considers the chain elasticity and the particle interactions in terms of a virial expansion. Our findings have implications on the interpretation of transport processes and permeability in hydrogel films, as realized in filtration or macromolecular carrier systems.