Effects of precursor topology and synthesis under crowding conditions on the structure of single-chain polymer nanoparticles

Abstract

By means of molecular dynamics simulations, we investigate the formation of single-chain nanoparticles through intramolecular cross-linking of polymer chains, in the presence of their precursors acting as purely steric crowders in concentrated solution. In the case of linear precursors, the structure of the resulting SCNPs is weakly affected by the density at which the synthesis is performed. Crowding has significant effects if ring precursors are used: higher concentrations lead to the formation of SCNPs with more compact and spherical morphologies. Such SCNPs retain in the swollen state (high dilution) the crumpled globular conformations adopted by the ring precursors in the crowded solutions. Increasing the concentration of both the linear and ring precursors up to 30% leads to faster formation of the respective SCNPs, prior to deceleration expected at higher densities. The results presented here propose promising new routes for the synthesis of globular SCNPs, which are usually elusive by conventional methods.