Enhancing Mechanical Properties of Silk Fibroin Hydrogel through Restricting the Growth of β-Sheet Domains

Usually, regenerated silk fibroin (RSF) hydrogels cross-linked by chemical agents such as horseradish peroxide (HRP)/H2O2 perform elastic properties, while display unsatisfactory strength for practical applications especially as load-bearing materials, and inadequate stability when incubated in a simulated in vivo environment. Here, the RSF hydrogel with both excellent strength and elasticity was prepared by inducing the conformation transition from random coil to β-sheet in a restricted RSF network precross-linked by HRP/H2O2. Such “dual-networked” hydrogels, regarding the one with 10 wt % RSF (Mw: 220 kDa) as a representative, show around 100% elongation, as well as the compressive modulus and tensile modulus up to 3.0 and 2.5 MPa respectively, which are much higher than those of physically cross-linked natural polymer hydrogels (commonly within 0.01–0.1 MPa at the similar solid content). It has been shown that the enhanced comprehensive mechanical properties of RSF hydrogels derive from the formation of small-sized and uniformly distributed β-sheet domains in the hydrogel during the conformation transition of RSF whose size is limited by the first network formed by cross-linkers with HRP/H2O2. Importantly, the tough RSF hydrogel changes the normally weak recognition of various RSF hydrogels and holds a great potential to be the material in biomedical field because it seems to be very promising regarding its biocompatibility, biodegradability, etc.