A dual-responsive supra-amphiphilic polypseudorotaxane constructed from a water-soluble pillar[7]arene and an azobenzene-containing random copolymer.

Macromolecular supra-amphiphiles refer to a kind of macromolecular amphiphiles whose hydrophlic and hydrophobic parts are connected by noncovalent forces. They have applications in various fields, such as drug delivery, sensor systems, and biomedical materials. Here we report a novel molecular recognition motif between a new thermoresponsive water-soluble pillar[7]arene (WP7) and an azobenzene derivative. Furthermore, we utilized this recognition motif to construct the first pillararene-based supra-amphiphilic polypseudorotaxane which can self-assemble to form vesicles in water. Due to the dual-responsiveness of the molecular recognition motif (the thermoresponsiveness of WP7 and photoresponsiveness of azobenzene), the reversible transformations between solid nanospheres based on the self-assembly of the polymer backbone and vesicles based on the self-assembly of the supra-amphiphilic polypseudorotaxane were achieved by adjusting the solution temperature or UV-visible light irradiation. These dual-responsive aggregation behaviors were further used in the controlled release of water-soluble dye calcein molecules.