Access to Photoreactive Core-Shell Nanomaterials by Photoinitiated Polymerization-Induced Self-Assembly

We report the straightforward synthesis of photoreactive nanoobjects exhibiting various colloidal morphologies by photoinitiated polymerization-induced self-assembly (PISA). Poly(oligoethylene glycol methyl ether methacrylate) copolymers with pendent UV-activatable diaryl tetrazole moieties were employed as macromolecular chain-transfer agents in water for the dispersion photopolymerization of 2-hydroxypropyl methacrylate under visible light. This led to the in situ formation of amphiphilic block copolymers, driving the self-assembly into core-shell nanoparticles, nanofibers, and nano/microvesicles. The tetrazole group present in the shell of the nanoobjects permitted functionalization with various functional molecules and polymers via UV-triggered nitrile imine-mediated tetrazole-ene cycloaddition (NITEC), enabling the alteration of surface properties of the nanomaterials (fluorescence, charge, hydrophilicity).