Thermoresponsive Polysaccharide Graft Polymer Vesicles with Tunable Size and Structural Memory

Controlling polymer vesicle size is difficult and a major obstacle for their potential use in biomedical applications, such as drug-delivery carriers and nanoreactors. Herein, we report size-tunable polymer vesicles based on self-assembly of a thermoresponsive amphiphilic graft copolymer. Unilamellar polymer vesicles form upon heating chilled polymer solutions, and vesicle size can be tuned in the range of 40-70 nm by adjusting the initial polymer concentration. Notably, the polymer can reversibly switch between a monomer state and a vesicle state in accordance with a cooling/heating cycle, which changes neither the size nor the size distribution of the vesicles. This lack of change suggests that the polymer memorizes a particular vesicle conformation. Given our vesicles' size tunability and structural memory, our research considerably expands the fundamental and practical scope of thermoresponsive amphiphilic graft copolymers and renders amphiphilic graft copolymers useful tools for synthesizing functional self-assembled materials.