Redox-Active Ultrathin Template of Silk Fibroin: Effect of Secondary Structure on Gold Nanoparticle Reduction

We report on an application of silk as an ultrathin redox-active template for controllable, one-step synthesis of gold nanoparticles via control over silk secondary structure. We found that both silk I and silk II molecular layers can facilitate gold nanoparticle formation at ambient conditions, indicating that tyrosine groups are available for metal ion reduction in both forms of silk. We suggest that the presence of β-sheets in silk II facilitates tyrosine ordering thereby resulting in well-dispersed, uniform nanoparticles with diameters of less than 6 nm. In addition, the mineralization does not result in transformation of the silk I secondary structure to silk II. In fact, the silk I structure is stabilized from further transformation into silk II even upon drying. These results are critical for developing a better understanding of silk interfacial behavior and offer an opportunity to design a new class of nanocomposites that combine the beneficial features of silk with those of the nanoparticles.