Self-assembling fibrous supramolecular assemblies with sophisticated hierarchical structures at the mesoscale are of interest from both fundamental and applied engineering. In this paper, the relatively hydrophilic domains of silk fibroin (HSF) were extracted and used in studies of self-assembly. The HSF fraction spontaneously self-assembled into nanofibers, 10 to 100 μm long and 50 to 250 nm in diameter, within 2 to 8 h in aqueous conditions. Interestingly, these HSF nanofibers consisted of dozens of nanofibrils arranged in a parallel organization with assembled diameters of ∼30 nm, similar to the sophisticated hierarchical structure observed in native silk fibers. Dynamic morphology and conformation studies were carried out to determine the mechanisms underlying the HSF self-assembly process at both the nanoscale and mesoscale. The HSF self-assembled into nanofibers in a bottom-to-up manner, from "sticky" colloid particles to cylindrical globules, to form nanofibrous networks. Because of the enhanced HSF self-assembling kinetics and the hierarchical structure of HSF nanofibers, this hydrophilicity-driven approach provides further insight into silk fibroin (SF) self-assembly in vivo and also offers new tools for the recapitulation of high-performance materials for engineering applications.
Keywords: hierarchical; hydrophilicity; nanofiber; self-assembly; silk fibroin.