Strategies for constructing polymeric micelles and hollow spheres in solution via specific intermolecular interactions.

We succeeded recently in developing a series of new pathways to polymeric micelles and hollow spheres via intermolecular specific interactions. A new micellization mechanism of block copolymers was realized by using the specific interaction between a low molecular weight compound and one of the blocks in low-polarity solvents. Many more successes have been achieved by our "block copolymer-free" strategies. We are now able to use homopolymers, random copolymers, oligomers, etc. as building blocks to construct noncovalently connected micelles (NCCM), in which the core and shell are connected by hydrogen bonding. Some of such NCCMs are readily converted further into hollow spheres by cross-linking the shell and then switching the medium to one that dissolves the core. Rigid polymer chains and their complementary homopolymers can directly assemble into large hollow spheres thanks to the propensity to parallel packing of the rigid chains. In addition, some of the NCCMs show perfect stimuli-responsive properties. pH-dependent micellization and pH-dependent micelle-hollow-sphere transition are realized in water-soluble graft copolymers driven by complexation and decomplexation between the main chain and grafts.