Phenylboronic acid as a sugar- and pH-responsive trigger to tune the multiple micellization of thermo-responsive block copolymer

Phenylboronic acid-containing thermo-responsive block copolymer, poly(ethylene oxide)-b-poly(methoxydi(ethylene glycol) methacrylate-co- aminophenylboronic acid ethyl methacrylate) (PEO-b-P(DEGMMA-co-PBAMA)), was employed to investigate the multiple micellization and dissociation transitions. The unique sugar- and pH-responsive properties of phenylboronic acid were interesting to provide two parallel approaches to tune the critical micellization temperature (CMT) and multiple micellization of thermo-responsive block copolymer. The block copolymers were molecularly soluble below 21 °C and underwent micellization above 21 °C at pH 8.7. After glucose was added at 24 °C, hydrophobic phenylboronic acid was changed to hydrophilic boronate–glucose complex and the CMT of the thermo-sensitive block was increased which caused the dissociation of micelles. In parallel, if the solution pH was increased from 8.7 to 11 at 25 °C, micelles were disrupted because of the formation of hydrophilic phenylboronate anion, which elevated the CMT of the thermo-sensitive block polymer. The introduction of phenylboronic acid groups into the thermo-responsive block copolymers provides a novel approach to tune the multiple micellization and dissociation transitions that might have great potentials in biomedical applications.