Nanosilk Template-Guided/Induced Construction of Brush-/Flower-like 3D Nanostructures

Biomaterials with natural hierarchical structures typically exhibit extraordinary properties because of their multilevel structural designs. They offer many templates and models as well as inspiration for material design, particularly for fabricating structure-regulated, performance-enhanced, and function-enriched materials. Biopolymer-based nanocomposites with ingenious nanostructures constructed through ecofriendly and sustainable approaches are highly desirable to meet the multifunctional requirements of developing bioinspired materials. Herein, an all-silk fibroin-based nanocomposite with a brush-like nanostructure was constructed for the first time using a nanotemplate-guided assembly approach in which dissolved silk assembled directly on a silk nanowhisker (SNW) backbone to form peculiar nanobrushes based on the classical micelle model. Three-dimensional spider-like or centipede-like silk nanobrushes (SNBs) were fabricated by varying the SNW backbone length from 0.16 to 6 μm. The branches with average lengths of 32-290 nm were also adjustable. SNBs were further designed to regulate and induce biomineralization of hydroxyapatite (HAP) to form interesting flower-like nanostructures, in which the HAP nanosphere (diameters ∼16 nm) "core" was covered by SNBs with branches extending to form a "shell" (∼101 nm in length). Based on such protein nanotemplate-guided formation of nanoscale structures, practical hollow conduits with remarkable mechanical properties, biocompatibility, shape memory behavior, and bone engineering potential were fabricated. This study inspires the design of polymorphous biopolymer-based nanostructures with enhanced performance at multiple length scales where the weaknesses of individual building blocks are offset.