Tuning the microstructure and mechanical properties of lyophilized silk scaffolds by pre-freezing treatment of silk hydrogel and silk solution.

This work aims to understand how pre-freezing treatments (-20 °C, -80 °C or -196 °C (liquid nitrogen)) affect the microstructure, mechanical properties and secondary structure of silk scaffolds prepared from lyophilization of silk hydrogels and silk solutions. It is found that in comparison with silk solutions, silk hydrogels at the same silk fibroin concentrations produce scaffolds with more nanofibrous structures when they are pre-frozen at the different temperatures. Although pre-freezing with liquid nitrogen can produce nanofibrous scaffolds from either a silk solution (low concentration of 2%) or silk hydrogel (produced from 2 to 6% silk fibroin solutions), aligned macro-channels can be produced only from silk hydrogels. In addition, scaffolds obtained from silk hydrogels are dominated by ß-sheets due to the crystallization process for gel network formation, while scaffolds prepared from silk solutions are largely amorphous. The findings of this work are important to tune the microstructure and mechanical properties of silk scaffolds.

Enhanced formation of bioactive and strong silk-bioglass hybrid materials through organic-inorganic mutual molecular nucleation induction and templating.

Materials based on silk fibroin (SF) are important for many biomedical applications due to their excellent biocompatibility and tunable biodegradability. However, the insufficient mechanical strength and low bioactivity of these materials have limited their applications. For silk hydrogels, slow gelation is also a crucial problem. In this work, a simple approach is developed to address these challenging problems all at once. By mixing SF solution with bioglass (BG) sol, instant gelation of silk is induced, the storage modulus of the hydrogel and the compressive modulus of the aerogel are significantly enhanced. The formation of a complex of SF and tetraethyl orthosilicate (TEOS), either through hydrogen bonding or TEOS condensation on SF, facilitated the aggregation of SF and, on the other hand, created active sites for the condensation of TEOS and BG formation on the surface of silk nanofibrils. The resultant hybrid gels have much higher capacity for biomineralization, indicating their higher bioactivity, compared with the pristine silk gels. This organic (SF)-inorganic (BG) mutual nucleation induction and templating can be used for a general approach to produce bioactive silk materials of various formats not limited to gels and may also inspire the formation of other functional protein-BG hybrid materials.