Silica nanoparticle-loaded thermoresponsive block copolymer vesicles: a new post-polymerization encapsulation strategy and thermally triggered release.

A thermoresponsive amphiphilic diblock copolymer that can form spheres, worms or vesicles in aqueous media at neutral pH by simply raising the dispersion temperature from 1 °C (spheres) to 25 °C (worms) to 50 °C (vesicles) is prepared polymerization-induced self-assembly (PISA). Heating such an aqueous copolymer dispersion from 1 °C up to 50 °C in the presence of 19 nm glycerol-functionalized silica nanoparticles enables this remarkable 'shape-shifting' behavior to be exploited as a new post-polymerization encapsulation strategy. The silica-loaded vesicles formed at 50 °C are then crosslinked using a disulfide-based dihydrazide reagent. Such covalent stabilization enables the dispersion to be cooled to room temperature without loss of the vesicle morphology, thus aiding characterization and enabling the loading efficiency to be determined as a function of both copolymer and silica concentration. Small-angle X-ray scattering (SAXS) analysis indicated a mean vesicle membrane thickness of approximately 20 ± 2 nm for the linear vesicles and TEM studies confirmed encapsulation of the silica nanoparticles within these nano-objects. After removal of the non-encapsulated silica nanoparticles multiple centrifugation-redispersion cycles, thermogravimetric analysis indicated that vesicle loading efficiencies of up to 86% can be achieved under optimized conditions. Thermally-triggered release of the silica nanoparticles is achieved by cleaving the disulfide bonds at 50 °C using tris(2-carboxyethyl)phosphine (TCEP), followed by cooling to 20 °C to induce vesicle dissociation. SAXS is also used to confirm the release of silica nanoparticles by monitoring the disappearance of the structure factor peak arising from silica-silica interactions.