Thermo-Driven Dynamic Reversible Self-Assembly of Crystalline Polymersomes and Worms for Active Polymerization Safety Sensors

Stimuli-responsive nanoparticles capable of reversible morphological transformations is a challenge in the field of intelligent polymers. This work presents a novel strategy termed “thermo-driven dynamic reversible self-assembly”, which enables efficient and reversible interconversion between polymersomes and worms, with over 95.0% structural retention after three cycles. This was achieved by grafting crystalline polycaprolactone (PCL) side chains onto the backbone of poly(4-vinylpyridine)-b-polystyrene via polymerization-induced self-assembly. Multiscale mechanistic analysis reveals that the crystallization and melting behavior of brush PCL side chains dynamically modulates the hydrophilic–hydrophobic balance. At low temperatures, the crystalline domains function as physical cross-linking points that stabilize the vesicles. Upon heating, the melting of these domains enhances chain segment mobility, thereby promoting a transition to low-curvature worms. Leveraging this temperature responsiveness, a radical inhibitor was encapsulated within the vesicle cavity, achieving a loading capacity of 13.4%, and constructed an active safety protection system. When applied to an acrylic acid polymerization system, the abrupt temperature increase caused by a runaway reaction triggered the vesicle-to-worm transition, resulting in the rapid release of 98.0% of the inhibitor and effectively preventing gelation. This work demonstrates thermo-driven reversible self-assembly of micelles, and integrates this capability with chemical safety protocols, offering a self-triggered, energy-free protective mechanism.