Silk fibroin scaffolds with stable silk I crystal and tunable properties

It is crucial to develop a three-dimensional scaffold with tunable physical properties for the biomedical application of silk fibroin (SF). The crystallization of polymers dictates their bulk properties. The presence of two unique crystal types, silk I and silk II, provides a mechanism for controlling the properties of SF biomaterials. However, it remains challenging to manipulate silk I crystallization. In this study, we demonstrate the stability and tunability of SF scaffolds with silk I structure prepared by a freezing-annealing processing. The porous structure and mechanical properties of the scaffolds can be readily regulated by SF concentration. XRD results show that the typical peaks representing silk I do not shift when subjected to various post-treatments, such as ethanol soaking, heating, water vapor annealing, UV irradiation, and high-temperature/high-pressure, indicating the stability of silk I crystal type. Moreover, the crystallization kinetics can be regulated by changing annealing time. This physical process can regulate the transition from non-crystalline to silk I, in turn controlling the mechanical properties and degradation rate of the SF scaffolds. Our result show that this green, all-aqueous strategy provides new directions for the design of SF-based biomaterials with controllable properties.