Using Host-Guest Chemistry to Tune the Kinetics of Morphological Transitions Undertaken by Block Copolymer Vesicles

Hostguest chemistry is exploited to tune the rate at which block copolymer vesicles undergo morphological transitions. More specifically, a concentrated aqueous dispersion of poly(glycerol monomethacrylate-co-glycidyl methacrylate)poly(2-hydroxypropyl methacrylate) [P(GMA-co-GlyMA)-PHPMA] diblock copolymer vesicles was prepared via polymerization-induced self-assembly (PISA). The epoxy groups in the GlyMA residues were ring-opened using a primary amine-functionalized beta-cyclodextrin (NH2-beta-CD) in order to prepare beta-CD-decorated vesicles. Addition of azobenzene-methoxypoly(ethylene glycol) (azo-mPEG) to such vesicles results in specific binding of this water-soluble macromolecular reagent to the beta-CD groups on the hydrophilic P(GMA-co-GlyMA) stabilizer chains. Such hostguest chemistry induces a morphological transition from vesicles to worms and/or spheres. Furthermore, the rate of this morphological transition can be tuned by UV/visible-light irradiation and/or guest molecule competition. This novel molecular recognition strategy offers considerable scope for the design of new stimulus-responsive diblock copolymer vesicles for targeted delivery and controlled release of cargoes.