Synthesis of silk fibroin-g-PAA composite using H2O2-HRP and characterization of the in situ biomimetic mineralization behavior

- Vinyl monomer was successfully graft copolymerized with SF during H2O2-HRP treatment.
- Mineral phases were detected on SF-g-PAA membranes after biomimetic mineralization.
- SF-g-PAA/HAp composite exhibited acceptable biocompatibility and outstanding adhesion property.
- A novel method for preparation of the fibroin-based biomaterial for bone tissue engineering was provided.

Silk fibroin (SF) as a bioactive protein can offer growth substrates for hydroxyapatite (HAp) deposition. In the current work, graft copolymerization of acrylic acid (AA) onto fibroin chains was carried out using hydrogen peroxide-horseradish peroxidase (H2O2-HRP) catalytic system, SF-g-polyacrylic acid (PAA) membranes was prepared subsequently, followed by in situ biomimetic mineralization in the Ca/P solutions, aiming at promoting the deposition of HAp and endowing the fibroin-based biocomposite with enhanced bioactivity. Meanwhile, p-hydroxyphenylacetamide (PHAD) and methyl acrylate (MA), as the model compounds of tyrosine residues in SF and vinyl monomer were used to disclose the mechanism of graft copolymerization. The data from FTIR and SEC chromatograms indicated that vinyl monomer was successfully graft copolymerized with SF during H2O2-HRP treatment. According to the results of XRD, SEM patterns and EDS-Mapping, mineral phases on the surfaces of SF-g-PAA membranes were detected after different cycles of biomimetic mineralization, and the mechanical property of SF-g-PAA/HAp membrane was noticeably improved. Cell viability and adhesion assays revealed that the composite of SF-g-PAA/HAp exhibited acceptable biocompatibility and outstanding adhesion property. The present work provides a novel method for preparation of the fibroin-based biomaterial for bone tissue engineering.