We report on a novel assembly approach to fabricate ultrathin robust freely standing nanocomposite membranes. The materials are composed of a pre-cross-linked silk fibroin matrix with incorporated silica nanoparticles with silsesquioxane cores (POSS) or clay nanoplatelets. These reinforced silk membranes have enhanced mechanical properties as compared to traditional silk-based nanocomposites reported previously. Up to 6-fold and 8-fold increase in elastic modulus and toughness, respectively, were found for these nanocomposites. In contrast, traditional LbL-assembled nanocomposites showed only a 3-fold increase in mechanical strength. The silk nanocomposites obtained also revealed excellent optical transparency in the visible region especially if reinforced with POSS nanoparticles, which suggests their utility as low cost, nontoxic, and easily scalable reinforced biomaterials for mechanically demanding applications.
Neutron reflectivity (NR) measurements of ultrathin surface films (below 30 nm) composed of Bombyx mori silk fibroin protein in combination with atomic force microscopy and ellipsometry were used to reveal the internal structural organization in both dry and swollen states. Reconstituted aqueous silk solution deposited on a silicon substrate using the spin-assisted layer-by-layer (SA-LbL) technique resulted in a monolayer silk film composed of random nanofibrils with constant scattering length density (SLD). However, a vertically segregated ordering with two different regions has been observed in dry, thicker, seven-layer SA-LbL silk films. The vertical segregation of silk multilayer films indicates the presence of a different secondary structure of silk in direct contact with the silicon oxide surface (first 6 nm). The layered structure can be attributed to interfacial β-sheet crystallization and the formation of well-developed nanofibrillar nanoporous morphology for the initially deposited silk surface layers with the preservation of less dense, random coil secondary structure for the layers that follow. This segregated structure of solid silk films defines their complex nonuniform behavior in the D(2)O environment with thicker silk films undergoing delamination during swelling. For a silk monolayer with an initial thickness of 6 nm, we observed the increase in the effective thickness by 60% combined with surprising decrease in density. Considering the nanoporous morphology of the hydrophobic silk layer, we suggested that the apparent increase in its thickness in liquid environment is caused by the air nanobubble trapping phenomenon at the liquid-solid interface.
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