Silk fibroin (SF) is a natural protein polymer and promising biomaterial. Chemical modifications have attracted growing interest in expanding SF applications. However, the majority of amino acid residues in SF are non-reactive and most of the reactive ones are in the crystalline region. Herein, a modification was conducted to investigate the possibility of direct modification on the surface of natural SF by a reagent with a mild reactivity, the type and quantity of the residues involved in the reactions, and the structural changes upon modification. Infrared spectrum, ¹H NMR, titration and amino acid analyses, X-ray diffraction, and hemolysis test were used to analyze the materials. The results showed that sulfonic acid groups were grafted onto SF and the reaction occurred mainly at serine residues through hydroxyl groups. In total, 0.0958 mmol/g of residues participated in the modification with a modification efficiency of 7.6%. Moreover, the crystallinity and the content of β-sheet structure in SF increased upon modification. The modified material had good blood-compatibility. In conclusion, surface modification on native SF through serine residues was practicable and had the advantage of increased β-sheet structure. This will provide an alternative way for the modification of fibroin for the desired application in the biomedical field.

Poly (ε-caprolactone) (PCL) and chitosan (CS) are widely used as biodegradable and biocompatible polymers with desirable properties for tissue engineering applications. Composite membranes (CS–PCL) with various blend ratios (CS:PCL, w/w) of 0:100, 5:95, 10:90, 15:85, 20:80, and 100:0 were successfully prepared by lyophilization. The thermal stabilities of the CS–PCL membranes were systematically characterized by thermogravimetric analysis (TG), dynamic thermogravimetry (DTG), and differential scanning calorimetry (DSC). It was shown that the blend ratio of PCL and CS had a significant effect on the thermal stability, hydrophilicity, and dynamic mechanical viscoelasticity of the CS–PCL membranes. All the samples in the experimental range exhibited high elasticity at low temperature and high viscosity at high temperatures by dynamic mechanical thermal analysis (DMTA). The performances of the CS–PCL membranes were at optimum levels when the blend ratio (w/w) was 10:90. The glass transition temperature of the CS–PCL membranes increased from 64.8 °C to 76.6 °C compared to that of the pure PCL, and the initial thermal decomposition temperature reached 86.7 °C. The crystallinity and porosity went up to 29.97% and 85.61%, respectively, while the tensile strength and elongation at the breakage were 20.036 MPa and 198.72%, respectively. Therefore, the 10:90 (w/w) blend ratio of CS/PCL is recommended to prepare CS–PCL membranes for tissue engineering applications.