Spider Silk‐Inspired Hyaluronic Acid‐Based Hydrogels with Superior Self‐Healing Capability and Enhanced Strength

Abstract Hyaluronic acid hydrogels are promising materials for diverse applications, yet their potential is hampered by limitations such as low self‐healing efficiency and insufficient mechanical strength. Inspired by the heterogeneous structures of spider silk, we introduce a novel dual dynamically crosslinked network hydrogel. This hydrogel comprises an acylhydrazone‐crosslinked network, utilizing aldehyde hyaluronic acid (AHA) and 3,3′‐dithiobis (propionohydrazide) (DTP) as a first network, and a secondary network formed by hydrogen bonds‐crosslinked network between tannic acid (TA) and silk fibroin (SF) with β‐sheet formation. The hydrogel exhibits exceptional self‐healing ability due to the dynamic and reversible nature of Schiff base bonds, disulfide bonds, and hydrogen bonds, achieving complete healing within 5 minutes. Additionally, the spider silk‐inspired heterogeneous structures enhance mechanical properties. Furthermore, the incorporation of TA provides enhances adhesion, as well as remarkable antibacterial and antioxidant properties. This innovative hyaluronic acid‐based hydrogel, inspired by spider silk, offers a promising avenue to fortify both the mechanical strength and self‐healing capabilities of hydrogels, thus expanding opportunities for applications in tissue engineering and biomedicine.