Exploring the effects of glyco-copolymer architectures on the solution self-assembly of amphiphilic thermoresponsive linear, star, and cyclic polymers†

Polymer architecture can influence the morphology of polymer self-assemblies. However, although the ability to control the nanostructure of self-assemblies is crucial for optimizing their potential applications, the ways in which changes in macromolecular architecture affect the structures of self-assemblies and the conformation of polymer chains in self-assemblies remain virtually unknown. Herein, we investigate the self-assembly behavior of four amphiphilic copolymers with different chain configurations, namely, AB, ABA, 3-arm block copolymers, and cyclic graft copolymers. We demonstrate that changes in the macromolecular architecture can result in the formation of different nanostructures, including unilamellar vesicles, cylindrical micelles, spherical micelles, and multilamellar vesicles. X-ray and light-scattering measurements also reveal that the conformations of the polymer chains in the self-assemblies are different, which contributes to the differences in their nanostructures. Our findings provide insights into the ways in which changes in polymer architecture affect self-assembly behavior and suggest that the macromolecular architecture should be considered an important factor for controlling the structure of molecular assemblies.