Development of Self-Healing Double-Network Hydrogels: Enhancement of the Strength of Wheat Gluten Hydrogels by In Situ Metal–Catechol Coordination

Wheat gluten, a byproduct of the wheat starch industry, is widely used as a dough strengthener and gelling agent. In this research, we developed novel double-network hydrogels by gelation of gluten using in situ metal-catechol coordination. The first network consisted of physically associated gluten molecules, while the second network consisted of Fe³⁺-cross-linked proanthocyanidins (PACs). Dynamic shear rheology experiments suggested that coordination of Fe³⁺ and PACs greatly enhanced the mechanical properties of the gluten hydrogels. The double-network hydrogels exhibited a 3-fold higher shear modulus than pure gluten hydrogels. The formation of bis- and tris-catechol-Fe³⁺ complexes between Fe³⁺ and PACs in the hydrogels was confirmed by ultraviolet-visible spectrometry and isothermal titration calorimetry (ITC). The ITC measurements of Fe³⁺ binding to PACs indicated a molar stoichiometry of 1:4 and a dissociation constant ( K_D) of 24.9 × 10^-9. When subject to repeated shear deformation-compression cycles, the hydrogels exhibited strong and rapid recovery of their rheological properties. The strong, self-healing characteristics of the double-network gluten hydrogels produced in this study may be useful for certain applications in the food, agriculture, biomedicine, and tissue-engineering industries.