Green syntheses of silk fibroin/wool keratin-protected Au-Ag nanoclusters with enhanced fluorescence for multicolor and patterned anti-counterfeiting

Counterfeiting is a serious worldwide issue that threatens human health and economic security. How to apply anti-counterfeiting techniques to textile materials remains a great challenge. Herein, we report bimetallic Au-Ag nanoclusters (NCs) synthesized by one-step reduction of chloroauric acid (HAuCl4) and silver nitrate (AgNO3) with wool keratin (WK) as reducer and silk fibroin (SF) as stabilizer. The strongest orange-red fluorescence under ultraviolet light as well as the highest zeta potential absolute values of -27.97 mV were simultaneously realized in the optimal proportion Au-AgNCs2 (WK/SF is 3/2), which was further processed to a series of anticounterfeiting films by blending with SF, silk sericin (SS), and polyvinyl alcohol (PVA). After successfully being numbered into fifteen colors, a dark blue-orange-dark red-dark blue cyclic fluorescent anti-counterfeiting color chart was designed. In addition, a two-Maxwell-unit model was constructed to assist with the microstructure analysis, which found that the formation of hydrogen bonds and the secondary structure transition from alpha-helices to beta-sheets during stretching were responsible for improving the mechanical properties and the twostaged fracture curves of films, respectively. Finally, a patterned and multicolor fluorescence anticounterfeiting fabric application was demonstrated by combining the color chart and screen printing, indicating the great potential in textile anti-counterfeiting.

Automated summary

Counterfeiting is a global issue that poses threats to human health and economic security. This study presents a novel approach to apply bimetallic nanoclusters to textile materials for anti-counterfeiting purposes. The optimized Au-Ag nanoclusters exhibited strong orange-red fluorescence and high zeta potential values, which were then used to create anti-counterfeiting films. A cyclic fluorescent color chart and a microstructure model were developed to demonstrate the potential of this method in textile anti-counterfeiting.