PH- and Ionic-Strength-Induced Contraction of Polybasic Micelles in Buffered Aqueous Solutions

Abstract

We report the synthesis and characterization of poly(dimethylaminoethyl methacrylate)-block-poly(styrene) (PDMAEMA-b-PS) diblock copolymers by RAFT polymerization. These polymers form uniform spherical micelles with dispersities less than 0.05 upon addition of aqueous buffer to polymer solutions in DMF. Potentiometric titrations under constant ionic strength conditions yield the first rigorous ionic-strength-effective pKa correspondence for PDMAEMA homopolymers and micelles. We demonstrate that the effective polymer pKa increases monotonically toward the monomer pKa with increasing ionic strength, but decreases slightly upon association of polymer chains into micelles. We further characterize the pH- and ionic-strength-induced contraction of the micelle coronas in buffered aqueous solutions. In monoprotic buffers, the micelle corona behaves as a salted osmotic brush, as has been observed for other block polyelectrolyte micelle systems in unbuffered solutions. In polyprotic buffers, however, we observe an ...