Structural Origins of Silk Piezoelectricity

Uniaxially oriented, piezoelectric silk films are prepared by a two‐step method that involves first air drying aqueous, regenerated silk fibroin solutions into films, and then drawing the silk films to a desired draw ratio. The utility of two different drawing techniques—zone drawing and water‐immersion drawing—is investigated for processing the silk for piezoelectric studies. Silk films zone drawn to a ratio of λ 5 2.7 display relatively high dynamic shear piezoelectric coefficients of d 14 5 –1.5 pC N 21 , corresponding to an increase in d 14 of over two orders of magnitude due to film drawing. A strong correlation is observed between the increase in silk II, β ‐sheet content with increasing draw ratio as measured by FTIR spectroscopy ( C b $ \propto $ e 2.5 λ ), the concomitant increasing degree of orientation of β ‐sheet crystals detected via wide‐angle X‐ray diffraction (full width half maximum (FWHM) = 0.22° for λ = 2.7), and the improvement in silk piezoelectricity ( d 14 $ \propto $ e 2.4 λ ). Water‐immersion drawing leads to a predominantly silk I structure with a low degree of orientation (FWHM 5 75°) and a much weaker piezoelectric response compared to zone drawing. Similarly, increasing the β ‐sheet crystallinity without inducing crystal alignment, e.g., by methanol treatment, does not result in a significant enhancement of silk piezoelectricity. Overall, a combination of a high degree of silk II, β ‐sheet crystallinity and crystalline orientation are prerequisites for a strong piezoelectric effect in silk. Further understanding of the structural origins of silk piezoelectricity provides important options for future biotechnological and biomedical applications of this protein.