Dynamics in Controllable Stimuli-Responsive Self-Assembly of Polymer Vesicles with Stable Radical Functionality

Self-assembled polymer vesicles have emerged as exciting and promising materials for their potential application in drug delivery, but the dynamics of stimuli-responsive polymers in these areas with pendant functionality in order to understand the structure–property relationship under different physicochemical conditions is still open to discussion. In this work, nitroxide radical-containing copolymers were synthesized and utilized to investigate local dynamics in their vesicular assemblies. Herein, electron paramagnetic resonance (EPR) spectroscopy was applied to reveal the smart supramolecular vesicular structure and polymer chain dynamics in stimuli-responsive controlled assemblies by considering molecular-level interactions. These interactions and dynamics were dependent on the microenvironment of the assemblies, which might be affected by physicochemical parameters such as radical concentration, pH, redox agent, polarity, and viscosity. These observations help to accomplish quantitative insights into the stimuli-responsive colloidal vesicular assemblies. The vesicles were used as an anticancer drug carrier, which showed high drug loading efficiency (63.65%). The reduction-responsive prompt disassembly accelerated the release. Furthermore, the biocompatibility and anticancer activity were examined by cellular experiments against normal fibroblasts (L929) and human cervical cancer (HeLa) cell lines, respectively. The results demonstrate that this effort provides an easy strategy for designing controllable stimuli-responsive polymer nanosystems which promotes their promising application in cancer treatment.