Over the past decade or so, polymerization-induced self-assembly (PISA) has become a versatile method for rational preparation of concentrated block copolymer nanoparticles with a diverse set of morphologies. Much of the PISA literature has focused on the preparation of well-defined linear block copolymers by using linear macromolecular chain transfer agents (macro-CTAs) with high chain transfer constants. In this review, a recent process is highlighted from an unusual angle that has expanded the scope of PISA including i) synthesis of block copolymers with nonlinear architectures (e.g., star block copolymer, branched block copolymer) by PISA, ii) in situ synthesis of blends of polymers by PISA, and iii) utilization of macro-CTAs with low chain transfer constants in PISA. By highlighting these important examples, new insights into the research of PISA and future impact these methods will have on polymer and colloid synthesis are provided.

Block copolymer vesicles loaded with active compounds have been employed as decent candidates to mimic complex biological systems that attract considerable interest in different research communities. We herein report a visible light-initiated seeded reversible addition–fragmentation chain transfer (RAFT)-mediated polymerization-induced self-assembly (PISA) for in situ preparation of enzyme-loaded cross-linked block copolymer vesicles without compromising the bioactivity. Permeability of the vesicular membrane can be regulated through changing the solution temperature, allowing further control over the enzymatic reaction rate of enzyme-loaded vesicles. Finally, non-cross-linked thermoresponsive block copolymer vesicles that can transform into worm-like micelles at low temperature are also prepared by this method, allowing the release of bimacromolecules from the vesicles under mild conditions.

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Polymerization-induced self-assembly via reversible addition-fragmentation chain transfer (RAFT)-mediated emulsion polymerization is an emerging method in which macro-RAFT agents are chain extended with hydrophobic monomers in water to form block copolymer nano-objects. However, almost all RAFT-mediated emulsion polymerizations are limited to AB diblock copolymers by using monofunctional macro-RAFT agents with non-reactive end groups. In this study, the first investigation on how the reactive end group of macro-RAFT agent affects RAFT-mediated emulsion polymerization is reported. Three macro-RAFT agents with different end groups are synthesized and employed in RAFT-mediated emulsion polymerization. Effects of end groups on morphologies of block copolymer nano-objects and polymerization process are studied. Block copolymer nano-objects prepared by using an asymmetric difunctional macro-RAFT agent can be functionalized by further chain extension on the surface. It is expected that the current study will not only expand the scope of RAFT-mediated emulsion polymerization, but also provide a novel strategy to prepare functional polymer nanoparticles.