The present review article highlights a specific class of responsive polymer-based hydrogels which are formed through association of oppositely charged polyion segments. The underpinning temporary three-dimensional network is constituted of hydrophilic chains (either ionic or neutral) physically crosslinked by ion pair formation arising from intermolecular polyionic complexation of oppositely charged repeating units (polyacid/polybase ionic interactions). Two types of hydrogels are presented: (i) hydrogels formed by triblock copolymers bearing oppositely charged blocks (block copolyampholytes), forming self-assembled networks; and (ii) hydrogels formed by co-assembly of oppositely charged polyelectrolyte segments belonging to different macromolecules (either block copolymers or homopolyelectrolytes). Due to the weak nature of the involved polyions, these hydrogels respond to pH and are sensitive to the presence of salts. Discussing and evaluating their solution, rheological and structural properties in dependence on pH and ionic strength, it comes out that the hydrogel properties are tunable towards potential applications.
Keywords: block polyampholyte; ionic interactions; pH-responsive; physical hydrogel; polyelectrolyte; polyion association; three-dimensional (3D) network.