Molecular Chain Rearrangement-Induced In Situ Formation of Nanofibers for Improving the Strength and Toughness of Hydrogels

Although poly(vinyl alcohol) (PVA) hydrogel has high elasticity and is suitable for cartilage tissue engineering, it is difficult to have both high strength and toughness. In this study, a simple and universal strategy is proposed to prepare strong and tough PVA hydrogels by in situ forming nanofibers on the original network structure induced by a molecular chain rearrangement. Quenching-tempering alteratively in ethanol and water several times is carried out to strengthen PVA hydrogels (PVA-Et<i>_n</i> hydrogels) due to the advantages of noncovalent bonds in adjustability and reversibility. The results show that, after three quenching-tempering cycles, PVA-Et₃ hydrogel with water content up to 79 wt % shows comprehensive improved mechanical properties. The compression modulus, tensile modulus, fracture strength, tensile strain, and tear energy of the PVA-Et₃ hydrogel are 270, 250, 260, 130, and 180% of the initial PVA hydrogel, respectively. The improved mechanical properties of the PVA-Et₃ hydrogel are attributed to the strong cross-linked PVA chains and hydrogen bond-reinforced nanofibers. This study not only provides a simple and efficient solution for the preparation of strong and tough polymer scaffolds in tissue engineering but also provides new insights for understanding the mechanism of improving the mechanical properties of polymer hydrogels by adjusting the molecular structure.