Self-Healing Mussel-Inspired Multi-pH-Responsive Hydrogels

Self-healing hydrogels can be made using either reversible covalent cross-links or coordination chemistry bonds. Here we present a multi-pH-responsive system inspired by the chemistry of blue mussel adhesive proteins. By attaching DOPA to an amine-functionalized polymer, a multiresponsive system is formed upon reaction with iron. The degree of polymer cross-linking is pH controlled through the pH-dependent DOPA/iron coordination chemistry. This leads to the formation of rapidly self-healing high-strength hydrogels when pH is raised from acidic toward basic values. Close to the p<i>K</i>_a value, or more precisely the pI value, of the polymer, the gel collapses due to reduced repulsion between polymer chains. Thereby a bistable gel-system is obtained. The present polymer system more closely resembles mussel adhesive proteins than those previously reported and thus also serves as a model system for mussel adhesive chemistry