pH- and Thermoresponsive Self-Assembly of Cationic Triblock Copolymers with Controlled Dynamics

Transient hydrogels formed by cationic BAB triblock copolymers consisting of a hydrophilic poly(dimethylaminoethyl methacrylate) (P(DMAEMA)) A block and amphiphilic B blocks composed of randomly distributed DMAEMA and n-butyl methacrylate (nBMA) units were investigated. Oscillatory shear measurements revealed formation of dynamic networks with terminal relaxation times that can be controlled by tuning the ionization degree (a) of the DMAEMA units or the temperature up until 50 degrees C. A sol-gel transition could be induced by increasing the pH. Above 50 degrees C irreversible aggregation was observed. The behavior of these pH-sensitive cationic copolymers is compared with that of pH-sensitive anionic copolymers, revealing that incorporating stimuli-responsive hydrophilic units within the hydrophobic blocks of amphiphilic block copolymers may be a general way to control the exchange dynamics of the latter.