Sequence structure controllable polymerization-induced self-assembly

Polymerization-induced self-assembly (PISA) combines synthesis and self-assembly of artificial polymers in one-pot, which brings us one step closer to emulating biosynthesis. However, the reported PISA formulations primarily focus on developing nano-objects with new chemical compositions and rarely on structural regulation of polymers with specific components. Herein, sequence structure controllable polymerization-induced self-assembly (SCPISA) is reported by using 7-(2-methacryloyloxyethoxy)-4-methylcoumarin (CMA) as a monomer. During the copolymerization of 2-hydroxyethyl methacrylate (HEMA) and CMA, controlled incorporation of CMA units into the polymer chains can be realized by programmable light/heat changes. SCPISA-based P(HEMA-co-CMA) copolymers with the same composition but different sequence structures generate a range of assemblies. Moreover, the morphologies of the resultant nano-objects can also be controlled by regulating the feed molar ratio of CMA and HEMA, which is similar to the conventional PISA, but the synthesis procedure is obviously simplified in SCPISA. The versatility of the methodology is further demonstrated by the fabrication of different functional nano-objects with sequence structure-dependent morphologies in SCPISA systems with different functional monomers.