Structural characterization of nanofiber silk produced by embiopterans (webspinners).
Embiopterans produce silken galleries and sheets using exceptionally fine silk fibers in which they live and breed. In this study, we use electron microscopy (EM), Fourier-transform infrared (FT-IR) spectroscopy, wide angle X-ray diffraction (WAXD) and solid-state nuclear magnetic resonance (ssNMR) techniques to elucidate the molecular level protein structure of webspinner (embiid) silks. Silks from two speciesAntipaluria urichiandAposthonia ceylonicaare studied in this work. Electron microscopy images show that the fibers are about 90-100 nm in diameter, making webspinner silks among the finest of all known animal silks. Structural studies reveal that the silk protein core is dominated by β-sheet structures, and that the protein core is coated with a hydrophobic alkane-rich surface coating. FTIR spectra of native embiid silk shows characteristic alkane CH2stretchings near 2800-2900 cm-1, which decrease approximately 50% after washing the silk with 2 : 1 CHCl3: MeOH. Furthermore,13C ssNMR data shows a significant CH2resonance that is strongly affected by the presence of water, supporting the idea that the silk fibers are coated with a hydrocarbon-rich layer. Such a layer is likely used to protect the colonies from rain. FTIR data also suggests that embiid silks are dominated by β-sheet secondary structures similar to spider and silkworm silk fibers. NMR data confirms the presence of β-sheet nanostructures dominated by serine-rich repetitive regions. A deconvolution of the serine Cβ NMR resonance reveals that approximately 70% of all seryl residues exist in a β-sheet structure. This is consistent with WAXD results that suggest webspinner silks are 70% crystalline, which is the highest crystalline fraction reported for any animal silks. The work presented here provides a molecular level structural picture of silk fibers produced by webspinners.
Department of Chemistry and Biochemistry, Arizona State University, Tempe, Arizona 85287-1604, USA.
J Bennett
JB
Addison
Department of Chemistry and Biochemistry, Arizona State University, Tempe, Arizona 85287-1604, USA.
Thomas M Osborn
TM
Popp
Department of Chemistry and Biochemistry, Arizona State University, Tempe, Arizona 85287-1604, USA.
Warner S
WS
Weber
Department of Biology, Santa Clara University, Santa Clara, CA, USA.
Janice S
JS
Edgerly
Department of Chemistry and Biochemistry, Arizona State University, Tempe, Arizona 85287-1604, USA.
Gregory P
GP
Holland
Department of Chemistry and Biochemistry, Arizona State University, Tempe, Arizona 85287-1604, USA.
Jeffery L
JL
Yarger