Mussel-Inspired Self-Healing Double-Cross-Linked Hydrogels by Controlled Combination of Metal Coordination and Covalent Cross-Linking

Mussel-inspired hydrogels held together by reversible catecholato-metal coordination bonds have recently drawn great attention owing to their attractive self-healing, viscoelastic and adhesive properties together with their pH-responsive nature. A major challenge in these systems is to orchestrate the degree of catechol oxidation that occurs under alkaline conditions in air and has a great impact on the aforementioned properties because it introduces irreversible covalent cross-links to the system, which stiffens the hydrogels but consume catechols needed for self-healing. Herein, we present a catechol-based hydrogel design that allows for the degree of oxidative covalent cross-linking to be controlled. Double cross-linked hydrogels with tunable stiffness are constructed by adding the oxidizable catechol analogue, tannic acid, to an oxidation-resistant hydrogel construct held together by coordination of the dihydroxy functionality of 1-(2'-carboxyethyl)-2-methyl-3-hydroxy-4-pyridinone to trivalent metal ions. By varying the amount of tannic acid, the hydrogel stiffness can be customized to a given application while retaining the self-healing capabilities of the hydrogel's coordination chemical component.