Functionalization and Reinforcement of Recombinant Spider Dragline Silk Fibers by Confined Nanoparticle Formation

Spider dragline silk is a remarkable protein fiber that is mechanically superior to almost any other natural or synthetic material. As a sustainable supply of natural dragline silk is not feasible, recombinant production of silk fibers with native-like mechanical properties and non-native physiochemical functions is highly desirable for various applications. Here, we report a new strategy for simultaneous functionalization and reinforcement of recombinant spider silk fibers by confined nanoparticle formation. First, a mimic silk protein (N16C) of spider Trichonephila clavipes was recombinantly produced and wet-spun into fibers. Drawing the as-spun fibers in water led to post-drawn fibers more suitable for the templated synthesis of nanoparticles (NPs) with uniform distribution throughout the synthetic fibers. This was exemplified using a chemical precipitation reaction to generate copper sulfide nanoparticle-incorporated fibers. These fibers and the derived fabric displayed a significant photothermal effect as their temperatures could increase to over 40 °C from room temperature within 3 min under near-infrared laser irradiation or simulated sunlight. In addition, the tensile strength and toughness of the nanofunctionalized fibers were greatly enhanced, and the toughness of these synthetic fibers could reach 160.1 ± 21.4 MJ m^-3, which even exceeds that of natural spider dragline silk (111.19 ± 30.54 MJ m^-3). Furthermore, the confined synthesis of gold NPs via a redox reaction was shown to improve the ultraviolet-protective effect and tensile mechanical properties of synthetic silk fibers. These results suggest that our strategy may have great potential for creating functional and high-performance spider silk fibers and fabrics for wide applications.