Engineering Programmable Synthetic Vesicles with Permeability Regulated by a Single Molecular Bridge

Self-assembly of biomimetic vesicles has broad impacts in the development of functional materials and applications to a variety of fields. Although promising, facile construction of function programmable synthetic vesicles to meet special requirements is still in its infancy and highly desirable. We developed novel polymeric vesicles with photo/chemo-programmable permeability through an aqueous-based one-pot polymerization-induced self-assembly (PISA) strategy. This is realized by using a newly designed macro-chain transfer agent and installing a single azobenzene moiety to bridge the hydrophilic and hydrophobic blocks of the amphiphiles. These polymeric vesicles can realize either release of small molecules only by light-induced selective permeability or burst release of all contents from the lumen by chemo-induced degradation of the amphiphiles and disassembly of the vesicular structure. The proof-of-concept principles are demonstrated and supported by monitoring the structural evolution of these biomimetic vesicles. This work offers new inspiration for the design of “smart” systems in nanoreactors, drug delivery, and molecular storage.