Charge-Driven Self-Assembly of Polyelectrolyte-Grafted Nanoparticles in Solutions

Nanoparticle self-assembly in solution has gained immense interest due to the enhanced optical, chemical, magnetic, and electrical properties which manifest at the macroscale. Material properties in bulk are a direct consequence of the morphology of these nanoparticles in solutions. Precise control on the orientation, spatial arrangement, shape, size, composition, and control over the interactions of individual nanoparticles play a key role in enhancing their properties. While previous studies have used asymmetry in the nanoparticle and/or the use of linker grafts, nanoparticles grafted with polyelectrolyte grafts provide us a wide parameter space to control and tune their self-assembly in solutions. In this study, we have performed coarse-grained molecular dynamics simulations to understand the charge-driven self-assembly of spherical nanoparticles grafted with polyelectrolyte chains. Nanoparticles grafted with either positively or negatively charged polyelectrolyte chains self-assemble to different structures driven by both excluded volume and electrostatic interactions. Our study shows that by tuning the graft density, the chain length, and the charge density of the grafts, we could build and control a variety of self-assembled structures ranging from rings, dimers, strings, coil-like aggregates, and disordered-to-ordered aggregates.