Nano-TiO2 induced secondary structural transition of silk fibroin studied by two-dimensional Fourier-transform infrared correlation spectroscopy and Raman spectroscopy

By sol-gel processing, regenerated nano-TiO2/SF (silk fibroin) composite films were synthesized. The experimental results revealed that the nano-TiO2 particles were well dispersed in the regenerated silk fibroin. Using FT-IR and Raman spectroscopy, the secondary structures of these composite films with concentrations of 0, 0.2, 0.4, 0.8 and 1.6 wt% were characterized. Concentration-perturbed two-dimensional (2D) correlation spectra were calculated for the spectra in the 1800-1600 cm(-1) region. To investigate nano-TiO2 particles induced changes in the secondary structure and hydration, the slice spectra were calculated from the synchronous and asynchronous spectra, respectively. The transmittance IR and Raman spectra measurement indicated that the secondary structure of the pure silk film was mostly random coil and alpha-helix, while the composite films were beta-sheet. With increasing nano-TiO2 content, the secondary structure of composite films was changed from typical Silk I to typical Silk II. However, it was found that the transition of the SF's secondary structures would be restrained by excessive nano-TiO2 (over 0.8%) introduced into the composite SF films. Through the FT-IR absorbance and 2D correlation spectra, it was demonstrated that the formation of nano-TiO2 particles could induce the partial transformation of SF conformation from Silk I to Silk II.