A Protein‐Like Nanogel for Spinning Hierarchically Structured Artificial Spider Silk

Spider dragline silk is draw-spun from soluble, β-sheet-crosslinked spidroin in aqueous solution. This spider silk has an excellent combination of strength and toughness, which originates from the hierarchical structure containing β-sheet crosslinking points, spiral nanoassemblies, a rigid sheath, and a soft core. Inspired by the spidroin structure and spider spinning process, a soluble and crosslinked nanogel is prepared and crosslinked fibers are drew spun with spider-silk-like hierarchical structures containing cross-links, aligned nanoassemblies, and sheath-core structures. Introducing nucleation seeds in the nanogel solution, and applying prestretch and a spiral architecture in the nanogel fiber, further tunes the alignment and assembly of the polymer chains, and enhances the breaking strength (1.27 GPa) and toughness (383 MJ m-3 ) to approach those of the best dragline silk. Theoretical modeling provides understanding for the dependence of the fiber's spinning capacity on the nanogel size. This work provides a new strategy for the direct spinning of tough fiber materials.