Polymer Nanoparticles: Shape-Directed Monomer-to-Particle Synthesis

Well-defined dumbbell and tripartite organic nanoparticles (30-60 nm) were produced via a one-pot direct synthesis of branched amphiphilic block copolymers, avoiding the need for postsynthesis self-assembly steps. We show the mechanism of dumbbell formation is largely a concerted process of particle growth during polymerization, although data suggest that particle-particle linking also occurs, particularly at higher monomer conversions. Dumbbell particles formed using a disulfide bifunctional initiator lead to cleavable structures, underlining the role of initiator functionality in shape control and the potential for functionality placement. Trifunctional initiators allow the direct one-pot synthesis of tripartite clover-leaf shaped nanoparticles which would be difficult to achieve through conventional synthesis/self-assembly/cross-linking strategies.