Photo-Cross-linking-Induced Morphology Change of Nonspherical Poly(trimethylene carbonate)-Based Polymer Self-Assemblies

Nonspherical polymer self-assembled nanoparticles represent a versatile class of nanocompartments, and their anisotropic morphological features endow them with tailored functionalities, rendering them highly promising for applications in nanomedicine. However, precise control over the structure and functionality of nonspherical assemblies remains a critical challenge. In this work, we synthesized amphiphilic block copolymers composed of a hydrophilic poly(ethylene glycol) (PEG) block and a hydrophobic coumarin-functionalized poly(trimethylene carbonate) (PTMC) segment. In the presence of salts, the formulation of nonspherical assemblies (e.g., tubular polymersomes and wormlike micelles) via osmotic pressure was obtained. Upon UV light irradiation, [2+2] cycloaddition of coumarin moieties was triggered, driving a morphological transformation from tubular polymersomes to wormlike micelles. More importantly, this photoinduced structural rearrangement was exploited to construct a light-responsive cargo release system, where the morphological transition directly modulates cargo release behavior. This study not only establishes an effective strategy for the photomediated reshaping of polymer nanocompartments but also highlights the potential of photoresponsive anisotropic particles as advanced smart delivery vehicles.