Crystallization-Driven Self-Assembly of Rod–Coil–Rod Pseudopolyrotaxanes into Spherical Micelles, Nanorods, and Nanorings in Aqueous Solutions

A novel rod-containing block copolymer is constructed by supramacromolecular self-assembly of α-cyclodextrin and a triblock copolymer with methoxy polyethylene glycol as the flanking chains and the midterm block alternately connected by 2,2-dimethylolbutyric acid and isophorone diisocyanate. The assembled rod-containing block copolymer shows an exciting phenomenon of concentration- and pH-dependent morphological switching of well-defined nanostructures. In the solutions at pH 9.2, spherical micelles, rod-like micelles, and hydrogel are observed successively with an increase of the concentration. Notably, the rod-like micelles are composed of spherical segments due to the combination of the crystalline cores of the spherical micelles. In addition, 1D nanostructures with different curvatures from linear rod-like micelles (pH 9.2) to ring-shaped micelles (pH 7.5) can be obtained by controlling the pH values of the assembled systems.