Chaotropic‐Anion‐Induced Supramolecular Self‐Assembly of Ionic Polymeric Micelles

Traditional micelle self-assembly is driven by the association of hydrophobic segments of amphiphilic molecules forming distinctive core-shell nanostructures in water. Here we report a surprising chaotropic-anion-induced micellization of cationic ammonium-containing block copolymers. The resulting micelle nanoparticle consists of a large number of ion pairs (≈60,000) in each hydrophobic core. Unlike chaotropic anions (e.g. ClO4(-)), kosmotropic anions (e.g. SO4(2-)) were not able to induce micelle formation. A positive cooperativity was observed during micellization, for which only a three-fold increase in ClO4(-) concentration was necessary for micelle formation, similar to our previously reported ultra-pH-responsive behavior. This unique ion-pair-containing micelle provides a useful model system to study the complex interplay of noncovalent interactions (e.g. electrostatic, van der Waals, and hydrophobic forces) during micelle self-assembly.