Spiders achieve superior silk fibres by controlling the molecular assembly of silk proteins and the hierarchical structure of fibres. However, current wet-spinning process for recombinant spidroins oversimplifies the natural spinning process. Here, water-soluble recombinant spider dragline silk protein (with a low molecular weight of 47 kDa) was adopted to prepare aqueous spinning dope. Artificial spider silks were spun via microfluidic wet-spinning, using a continuous post-spin drawing process (WS-PSD). By mimicking the natural spinning apparatus, shearing and elongational sections were integrated in the microfluidic spinning chip to induce assembly, orientation of spidroins, and fibril structure formation. The additional post-spin drawing process following the wet-spinning section partially mimics the spinning process of natural spider silk and substantially contributes to the compact aggregation of microfibrils. Subsequent post-stretching further improves the hierarchical structure of the fibres, including the crystalline structure, orientation, and fibril melting. The tensile strength and elongation of post-treated fibres reached up to 510 MPa and 15%, respectively.

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In this study, nascent silk nanoribbons (SNRs) with an average thickness of 0.4 nm were extracted from natural silkworm silk by partially dissolving degummed silk (DS) in sodium hydroxide (NaOH)/urea solution at −12 °C. In this gentle treatment, the solvent could not destroy the nanofibrillar structure completely, but the chosen conditions would influence the dimensions of resulting SNRs. Molecular dynamics simulations of silk models indicated that the potential of mean force required to break hydrogen bonds between silk fibroin chains was 40% larger than that of van der Waals interactions between β-sheet layers, allowing the exfoliating treatment. It was found that the resulting SNRs contained a single β-sheet layer and amorphous silk fibroin molecules, which could be considered as the basic building block of DS consisting of hierarchical structures. The demonstrated technique for extracting ultrathin SNRs having the height of a single β-sheet layer may provide a useful pathway for creating stronger and tougher silk-based materials and/or adding functionality and durability in materials for various applications. The hierarchical structure model based on SNRs may afford more insight into the structure and property relationship of fabricating silk-based materials.

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As spider silks have extraordinary mechanical properties, the design of high-performance artificial silk fibers has been one of the focuses in the field of biomimetic fibers. Cellulose nanofibers (CNFs) have considerable potential being an effective reinforcing agent in biocompatible composites because of their high aspect ratio, good stiffness of the crystalline regions, and biocompatibility. In this study, regenerated silk fibroin (RSF)/CNF hybrid fibers were dry-spun through a microfluidic chip, which mimicked the shape of spider’s major ampullate gland. The results showed that the presence of CNF can substantially enhance the mechanical properties of RSF. In specific, the breaking strength of the RSF/CNF fibers with 0.1 wt % CNF was increased to 486 ± 106 MPa with a maximum value of 686 MPa, significantly higher than that of silk fibers from silkworm. The enhancement could be attributed to higher orientation of crystalline and mesophase contents, higher crystallinity, and hydrogen bonds linked between RSF and CNF. This study outlined a simple and environmentally friendly pathway to generate artificial silks with high-performance properties.

Spider dragline silk is a remarkable fiber made by spiders from an aqueous solution of spidroins, and this feat is largely attributed to the tripartite domain architecture of the silk proteins leading to the hierarchical assembly at the nano- and microscales. Although individual amino- and carboxy-terminal domains have been proposed to relate to silk protein assembly, their tentative synergizing roles in recombinant spidroin storage and spinning into synthetic fibers remain elusive. Here, we show biosynthesis and self-assembly of a mimic spidroin composed of amino- and carboxy-terminal domains bracketing 16 consensus repeats of the core region from spider Trichonephila clavipes. The presence of both termini was found essential for self-assembly of the mimic spidroin termed N16C into fibril-like (rather than canonical micellar) nanostructures in concentrated aqueous dope and ordered alignment of these nanofibrils upon extrusion into an acidic coagulation bath. This ultimately led to continuous, macroscopic fibers with a tensile fracture toughness of 100.9 ± 13.2 MJ m–3, which is comparable to that of their natural counterparts. We also found that the recombinant proteins lacking one or both termini were unable to similarly preassemble into fibrillar nanostructures in dopes and thus yielded inferior fiber properties. This work thereby highlights the synergizing role of terminal domains in the storage and processing of recombinant analogues into tough synthetic fibers.

The miniaturization of portable electronic devices has fueled the development of microsupercapacitors that hold great potential to complement or even replace microbatteries and electrolytic capacitors. In spite of recent developments taking advantage of printing and lithography, it remains a great challenge to attain a high energy density without sacrificing the power density. Herein, a new protocol mimicking the spider's spinning process is developed to create highly oriented microfibers from graphene-based composites via a purpose-designed microfluidic chip. The orientation provides the microfibers with an electrical conductivity of ∼3 × 10 S m, which leads to a high power density; the energy density is sustained by nanocarbons and high-purity metallic molybdenum disulfide. The microfibers are patterned in-plane to fabricate asymmetric microsupercapacitors for flexible and on-chip energy storage. The on-chip microsupercapacitor with a high pattern resolution of 100 μm delivers energy density up to the order of 10 W h cm and retains an ultrahigh power density exceeding 100 W cm in an aqueous electrolyte. This work provides new design of flexible and on-chip asymmetric microsupercapacitors based on microfibers. The unique biomimetic microfluidic fabrication of graphene microfibers for energy storage may also stimulate thinking of the bionic design in many other fields.

Spider and silkworm produce diverse silk fibers from spinning dopes through smart spinnerets. Spider's capture silk is composed of core thread and periodic spindle‐knots, while silkworm silk consists of fibroin core and sericin outer layer. To mimic the morphologies of natural heterostructured silks, artificial fibers are dry‐spun using a multichannel microfluidic chip, served with a highly viscous core solution of regenerated silk fibroin and low viscosity sheath solution of sericin. Silk fibers with core–sheath, groove, and spindle‐knot structures are obtained by controlling the flow rates and viscosities of the two microfluids depending on the laminar flow, Kelvin–Helmholtz instability, or Plateau–Rayleigh instability.