Effects of pH on the Stimuli-Responsive Characteristics of Double Betaine Hydrophilic Block Copolymer PGLBT--PSPE.

We investigated the pH-responsive behavior of the carboxybetaine-sulfobetaine diblock copolymer poly(2-(2-(methacryloyloxy)ethyl)dimethylammonio)acetate--3-((2-(methacryloyloxy)ethyl)dimethylammonio)propane-1-sulfonate (PGLBT--PSPE) in aqueous solution under varying temperatures. Alongside the temperature-responsive PSPE block which induces self-assembly of polymer micelles under the upper critical solution temperature, the PGLBT motifs having protonation sites caused additional changes in the phase behaviors. In acidic conditions where the pH is lower than the p of PGLBT--PSPE, the transmittance of polymer solutions more abruptly dropped and became cloudy at higher temperatures compared to the case of salt-free solutions. There were two simultaneous diffusive modes in the turbid solutions equivalent to unimers or micelles and large aggregates over a few hundred nanometers. Unlike in neutral and basic conditions, those large aggregates did not disappear after the emergence of the polymer micelles. The trend of the temperature-responsive behavior hardly changed in the alkaline solutions; however, the critical temperature significantly decreased. The surface charge of the unimers and self-assembled objects determined by zeta potential measurement varied from neutral or negative to positive with proton addition and further positively increased below the micelle formation temperature. This indicates the cationization of PGLBT moieties and their arrangement in the outer layer of the polymer micelle surface. In spite of the positively charged outer surface, two fast and slow diffusive modes representing micelles and large clusters were repeatedly observed in acidic solutions, and to some extent, size-grown particles eventually precipitated.