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

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.