Understanding the stimuli responsive behavior of polyion grafted nanoparticles in the presence of salt and polyelectrolytes

The design of nanoparticles (NPs) that respond to external stimuli like pH, temperature, and electric or magnetic fields has found immense interest in various fields of nanotechnology like nanomedicine, drug delivery, and cancer therapy. Nanoparticles grafted with polymeric ligands have been extensively used as building blocks in the directed self assembly of nanoparticles. These moieties not only assemble into various morphologies but also respond to a wide range of external stimuli. In this work, we have used coarse grained molecular dynamics simulations to understand the stimuli-responsive behavior of assemblies of NPs grafted with oppositely charged polyions (PGNs) in the presence of salt and polyelectrolytes. At low grafting density, a transformation from ring morphology to form dimers/strings/dispersed NPs was observed upon addition of divalent/trivalent salts. NPs grafted with longer grafts showed higher stability to remain as rings compared to shorter grafts. The change in NP morphology was a direct consequence of preferential interaction of the polyaion grafts with the oppositely charged salt ions compared to the oppositely charged grafts on the NPs. At fixed salt valency, the size of the salt ion, concentration and molecular connectivity played a crucial role in the stimuli responsive behavior of polyion grafted NPs in solutions. Further, in the presence of polyelectrolytes, these transitions occurred at lower monomer valency due to the stronger electrostatic interactions between the grafted chains and oppositely charged free polyelectrolytes in solutions. Disordered and ordered aggregates assemblies formed at higher grafting density were broken into smaller NP assemblies in the presence of salt. Drug encapsulation studies in the presence of salt and polyelectrolytes were performed on model drug moieties in order to demonstrate the potential use of the modelled stimuli responsive nanoparticle assemblies in drug delivery applications.