Emerging Trends in Polymerization-Induced Self-Assembly.

In this Perspective, we summarize recent progress in polymerization-induced self-assembly (PISA) for the rational synthesis of block copolymer nanoparticles with various morphologies. Much of the PISA literature has been based on thermally initiated reversible addition-fragmentation chain transfer (RAFT) polymerization. Herein, we pay particular attention to alternative PISA protocols, which allow the preparation of nanoparticles with improved control over copolymer morphology and functionality. For example, initiation based on visible light, redox chemistry, or enzymes enables the incorporation of sensitive monomers and fragile biomolecules into block copolymer nanoparticles. Furthermore, PISA syntheses and postfunctionalization of the resulting nanoparticles (e.g., cross-linking) can be conducted sequentially without intermediate purification by using various external stimuli. Finally, PISA formulations have been optimized via high-throughput polymerization and recently evaluated within flow reactors for facile scale-up syntheses.