Pathway-dependent Shape Transformation of Polymeric Vesicles under UV Light and the Assembly of UV-irradiated Polymer

Shape transformation of polymer particles is generally a nonequilibrium dynamics process. Controlling the shape transformation of polymers is increasingly attractive and challenging for scientists due to their extensive use in drug delivery and cancer therapy. Herein, we investigated the UV-triggered shape transformation pathway of polymeric vesicles assembled from Polystyrene-block-poly(4-vinylpyridine) and 4-hydroxyazobenzene (PS-b-P4VP(Azo-OH)) and the direct assembly pathway of UV-irradiated PS-b-P4VP(Azo-OH) homogeneous solution. In the shape transformation process, well-assembled vesicles can be transformed into toroid, cylindrical, rod-like, and spherical micelles. In the direct assembly pathway, rod-like and spherical micelles can be obtained. Interestingly, the toroid micelles can be obtained only from the UV-triggered shape transformation pathway. Contrasting the two pathways reveals the pathway dependence of PS-b-P4VP(Azo-OH) assembly, suggesting that the final assembly morphology is determined by the initial state and dynamic process. The speed of UV-triggered shape transformation and the final morphology of assemblies can be tuned easily by adjusting the UV illuminance, time, and content of Azo-OH addition. Moreover, the light-responsive polymeric vesicles can be used as drug carriers and have the potential to release drugs precisely.