Synthesis and pH-responsive dissociation of framboidal ABC triblock copolymer vesicles in aqueous solution

A series of pH-responsive all-methacrylic ABC triblock copolymer vesicles were prepared from precursor diblock copolymer vesicles via RAFT seeded emulsion polymerisation. Microphase separation between the two hydrophobic membrane-forming B and C blocks produced a distinctive framboidal morphology, for which the mean globule size can be tuned by adjusting the triblock copolymer composition. These vesicles remain intact at neutral pH, but undergo irreversible dissociation on addition of acid as a result of protonation of the tertiary amine groups located within the third block. Small-angle X-ray scattering (SAXS) was utilised to characterise the morphologies formed at pH 8 and pH 3. According to time-resolved SAXS studies, the acid-induced dissociation of these pH-responsive framboidal vesicles involves appreciable membrane swelling within 50 ms and is complete.