Fast-setting multi-stimuli responsive silk hydrogels tailored with dual network interface

Abstract

Silk fibroin, a naturally occurring and versatile polymer with broad range of material forms and applications, presents numerous advantages. Notably, hydrogels are noteworthy among these advantages due to their inherent hydrophilicity, biocompatibility, and flexibility. Nevertheless, their practical utility has been hindered by intricate preparation procedures and limited mechanical strength. In this investigation, we introduce a straightforward and cost-effective method for producing a novel silk hydrogel. Subsequent to the hydrogel synthesis, an ethanol treatment was employed to induce the preferential formation of β-sheet conformations. The developed system exhibits rapid gelation (gelation time: 3 min) and non-swelling behavior (swelling ratio = 0.47). This suggests its potential suitability for biomedical devices without imposing strain on adjacent tissues. Conformational rearrangement of polymeric chains induced by ethanol treatment contributed to heightened material crystallinity, resulting in a remarkable 55.9% increase in Young's modulus and a substantial 91.2% enhancement in ultimate tensile strength for the ethanol-treated hydrogels (SF/AG/Gly/Eth) when compared to their non-ethanol-treated counterparts (SF/AG/Gly). Additionally, in-situ biodegradation studies on silk hydrogels confirmed the material's degradability, with a notable 94.75% weight loss within 3 days, following pseudo-second-order kinetics (R2 = 0.991). This degradation is attributed to action of proteolytic enzymes on the amino acid units of silk fibroin, alleviating concerns regarding waste generation. Moreover, these pH and water-responsive hydrogels can be harnessed in the fabrication of intelligent biomedical devices. Further, drug release studies on silk hydrogels showed that both ethanol-treated and non-treated samples displayed sustained drug release following the Korsmeyer−Peppas model, with an entrapment efficiency of 65.6% and 48.2%, respectively.