In Situ Cross-Linking of Vesicles in Polymerization-Induced Self-Assembly.

In situ cross-linking of nano-objects with controllable morphologies in polymerization-induced self-assembly (PISA) has been a challenge because cross-linking lowers chain mobility and hence inhibits morphology transition. Herein, we propose a novel strategy that allows in situ cross-linking of vesicles in PISA in an aqueous dispersion polymerization formulation. This is realized by utilizing an asymmetric cross-linker bearing two vinyl groups of differing reactivities such that cross-linking is delayed to the late stage of polymerization when morphology transition has completed. Cross-linked vesicles with varying degrees (1-5 mol %) of cross-links were prepared, and their resistance to solvent dissolution and surfactant disruption was investigated. It was found that vesicles with ≥2 mol % cross-links were able to retain their structural integrity and colloidal stability when dispersed in DMF or in the presence of 1% of an anionic surfactant sodium dodecyl sulfate.