In this study, nascent silk nanoribbons (SNRs) with an average thickness of 0.4 nm were extracted from natural silkworm silk by partially dissolving degummed silk (DS) in sodium hydroxide (NaOH)/urea solution at -12 °C. In this gentle treatment, the solvent could not destroy the nanofibrillar structure completely, but the chosen conditions would influence the dimensions of resulting SNRs. Molecular dynamics simulations of silk models indicated that the potential of mean force required to break hydrogen bonds between silk fibroin chains was 40% larger than that of van der Waals interactions between β-sheet layers, allowing the exfoliating treatment. It was found that the resulting SNRs contained a single β-sheet layer and amorphous silk fibroin molecules, which could be considered as the basic building block of DS consisting of hierarchical structures. The demonstrated technique for extracting ultrathin SNRs having the height of a single β-sheet layer may provide a useful pathway for creating stronger and tougher silk-based materials and/or adding functionality and durability in materials for various applications. The hierarchical structure model based on SNRs may afford more insight into the structure and property relationship of fabricating silk-based materials.
Keywords: NaOH/urea solution; hierarchical structure; low temperature; silk nanoribbons; single β-sheet layer.