Gradient Polymerization-Induced Self-Assembly: A One-Step Approach.

In this work, the authors report a novel single-step, one-pot process for the synthesis of self-assembled nanoparticles using a polymerization-induced self-assembly (PISA) mechanism. In contrast to conventional approaches employing a pre-formed macromolecular stabilizer, the disparate reactivities between two monomers, oligo(ethylene glycol) methyl ether methacrylate (OEGMA) and diacetone acrylamide (DAAm), are exploited instead to synthesize a gradient copolymer directly in aqueous solution. Due to the hydrophobicity of poly(DAAm), these gradient copolymers can self-assemble in situ to form spheres and worms stabilized by the OEGMA residues. A surprisingly broad range of parameters are identified in which the worm morphology can be stabilized, which is highlighted by significant gelation of the reaction mixture in situ. This single-step gradient copolymerization approach to PISA is more efficient than conventional two-step syntheses. These results demonstrate improved reproducibility owing to the production of self-assembled nanoparticles directly in a one-pot and single-step synthesis.