Autonomic Self-Healing Silk Fibroin Injectable Hydrogels Formed via Surfactant-Free Hydrophobic Association

Many natural materials, such as silk, animal bone, nacre, and plant fibers, achieve outstanding strength and toughness through the rupture of sacrificial bonds between chain segments in the organic phase. In this work, we present a bioinspired strategy to fabricate silk fibroin-based hydrophobic-association (HA) hydrogels by incorporating the hydrophobic interaction as a sacrificial bond into the alginate ionic network, which not only enhanced the mechanical extensibility, strength, and toughness of the hydrogels but also enabled self-recovery and self-healing properties via reversible hydrophobic interactions without external stimuli at room temperature. The hydrophobic interaction system consisted of the hydrophobic monomer stearyl methacrylate (C18M) and an amphiphilic regenerated silk fibroin (RSF) solution. The mechanical tests and rheometry indicated that the hydrophobic interaction served as the sacrificial bond that preferentially ruptures prior to the alginate ionic network under an external load...