Enzymatically-mineralized double-network hydrogels with ultrahigh mechanical strength, toughness, and stiffness

Background: Synthetic hydrogels are commonly mechanically weak which limits the scope of their applications. Methods: In this study, we synthesized an organic-inorganic hybrid hydrogel with ultrahigh strength, stiffness, and toughness via enzyme-induced mineralization of calcium phosphate in a double network of bacterial cellulose nanofibers and alginate-Ca²⁺. Results: Cellulose nanofibers formed the first rigid network via hydrogen binding and templated the deposition of calcium phosphate, while alginate-Ca²⁺ formed the second energy-dissipating network via ionic interaction. The two networks created a brick-mortar-like structure, in which the “tortuous fracture path” mechanism by breaking the interlaced calcium phosphate-coated bacterial cellulose nanofibers and the hysteresis by unzipping the ionic alginate-Ca²⁺ network made a great contribution to the mechanical properties of the hydrogels. Conclusion: The optimized hydrogel exhibited ultrahigh fracture stress of 48 MPa, Young's modulus of 1329 MPa, and fracture energy of 3013 J/m², which are barely possessed by the reported synthetic hydrogels. Finally, the hydrogel represented potential use in subchondral bone defect repair in an ex vivo model.