Selective Coupling and Polymerization of Folded Polymer Micelles to Nanodomain Self-Assemblies.

Abstract

Herein, we developed selective coupling and polymerization systems of folded polymer micelles via physical interaction in water. The polymer micelles serve as nanodomains to provide double core micelles, alternating necklace micelles, and micelle-connected hydrogels. For this, cation- or anion-tail unimer micelles and amine- or carboxy-tail unimer micelles were designed; the unimer micelles consist of folded amphiphilic random copolymers carrying hydrophilic poly(ethylene glycol) and hydrophobic or hydrogen-bonding pendants. Mixing a cation-tail micelle and an anion-tail micelle, and even the combination of a double cation-tail micelle and a double anion-tail micelle, selectively provided double-core micelles in water without forming large aggregates. Double core micelles afforded structural transformation into linear or cyclic polymers and dynamic exchange of the micelle domains. In contrast, mixing amine-tail micelles and carboxy-tail micelles gave an alternating necklace micelle or a hydrogel. The controlled connection of polymer micelles was achieved by designing suitable physical interaction. This technique opened new ways to create various nanodomain self-assemblies with controlled higher-order structure.