Preparation of a Series of Photoresponsive Polymersomes Bearing Photocleavable a 2-nitrobenzyl Group at the Hydrophobic/Hydrophilic Interfaces and Their Payload Releasing Behaviors

In this study, the structure-function relationships of a series of polymersomes composed of well-defined amphiphilic diblock copolymers were investigated. The building blocks were synthesized by clicking hydrophobic polymers, synthesized beforehand, and commercially available poly(ethylene glycol) with photocleavable 2-nitrobenzyl compounds bearing alkyne and maleimide functionalities. All of the tested polymersomes preserved their hollow structures even after sufficient photoirradiation. Nevertheless, the release rate of an entrapped anionic fluorophore was highly dependent on the molecular weight and the type of hydrophobic polymer, as well as on the presence or absence of the charged end groups. Moreover, the polymersomes with a 2-nitrosobenzyl photolysis residue within the hydrophobic shells exhibited photo-induced payload release after complete photolysis. It was concluded that the payload release was mediated by photo-induced permeability changes of the hydrophobic shells rather than the decomposition of their overall structures.