Bone‐Adhesive Anisotropic Tough Hydrogel Mimicking Tendon Enthesis

Tendon consists of soft collagen, yet it is mechanically strong and firmly adhered to the bone owing to its hierarchically anisotropic structure and unique tendon‐to‐bone integration (enthesis), respectively. Despite the recent advances in biomaterials, hydrogels simultaneously providing tendon‐like high mechanical properties and strong adhesion to bone‐mimicking enthesis is still challenging. Here, a strong, stiff, and adhesive triple‐network (TN) anisotropic hydrogel that mimics a bone‐adhering tendon is shown. The tough adhesive TN hydrogel is developed by combining imidazole‐containing polyaspartamide (providing multiple hydrogen bonds to the bone surface) and energy‐dissipative alginate–polyacrylamide double‐network. To mimic the anisotropic structure and high mechanical properties of tendons, the bone‐adhered TN hydrogel is linearly stretched and subsequently fixed via secondary cross‐linking. The resulting hydrogel exhibits high tensile modulus and strength while maintaining a high bone adhesion without chemical modification of the bone surface. Furthermore, a bone–ligament–bone structure with strong bone adhesion reminiscent of the natural ligament is realized. A strong adhesive triple‐network hydrogel consisting of ionically cross‐linked alginate, polyacrylamide, and adhesive imidazole‐containing polyaspartamide derivatives subjected to stretching‐mediated linear remodeling followed by cross‐linking exhibits strong mechanical properties and high adhesiveness. The hydrogel exhibits an anisotropic structure similar to that of tendons. The proposed hydrogel is promising for the development of artificial tendons and clinical applications.