RESUMEN

Silk is one of the toughest fibrous materials known despite spun at ambient temperature and pressure with water as a solvent. It is a great challenge to reproduce high-performance artificial fibers comparable to natural silk by bionic for the incomplete understanding of silkworm spinning in vivo. Here, we found that amphipol and digitonin stabilized the structure of natural silk fibroin (NSF) by a large-scale screening in vitro, and then studied the close-to-native ultrastructure and hierarchical assembly of NSF in the silk gland lumen. Our study showed that NSF formed reversible flexible nanofibrils mainly composed of random coils with a sedimentation coefficient of 5.8 S and a diameter of about 4 nm, rather than a micellar or rod-like structure assembled by the aggregation of globular NSF molecules. Metal ions were required for NSF nanofibril formation. The successive pH decrease from posterior silk gland (PSG) to anterior silk gland (ASG) resulted in a gradual increase in NSF hydrophobicity, thus inducing the sol-gelation transition of NSF nanofibrils. NSF nanofibrils were randomly dispersed from PSG to ASG-1, and self-assembled into anisotropic herringbone patterns at ASG-2 near the spinneret ready for silkworm spinning. Our findings reveal the controlled self-assembly mechanism of the multi-scale hierarchical architecture of NSF from nanofibrils to herringbone patterns programmed by metal ions and pH gradient, which provides novel insights into the spinning mechanism of silk-secreting animals and bioinspired design of high-performance fibers.

Asunto(s)

RESUMEN

Optical biosensors based on micro/nanofibers are highly valuable for probing and monitoring liquid environments and bioactivity. Most current optical biosensors, however, are still based on glass, semiconductors, or metallic materials, which might not be fully suitable for biologically relevant environments. Here, we introduce biocompatible and flexible microfibers from lotus silk as microenvironmental monitors that exhibit waveguiding of intrinsic fluorescence as well as of coupled light. These features make single-filament monitors excellent building blocks for a variety of sensing functions, including pH probing and detection of bacterial activity. These results pave the way for the development of new and entirely eco-friendly, potentially multiplexed biosensing platforms.

Asunto(s)

RESUMEN

Wound repair is challenging for traditional wound dressings. New bioactive dressings need to be developed urgently. Herein, we reported a highly bioactive silk protein wound dressing (SPD) with natural silk fiber-sericin hydrogel interpenetrating double network structure, which combines the dual characteristics of natural silk and sericin hydrogel. Silk fiber scaffolds were secreted directly from silkworms bred by regulating their spinning behaviors. Sericin in SPD is obtained by dissolving silkworm cocoons at high temperature and high pressure, while it remains intact activities to self-assemble a hydrogel. To explore the effect of SPD, we first systematically evaluated its physicochemical properties and biological activitiesin vitro. The SPD exhibits high porosity, prominent mechanical strength, pH-responsive degradability, and excellent anti-oxidation and cell compatibility. Besides, SPD can load and maintain long-term drug release. Based on the satisfactory performance of SPDin vitro, effectivein vivotreatment was achieved in a mouse full-thickness wound model, as demonstrated by a significantly accelerated wound healing process, promote the regeneration of hair follicles and sebaceous glands, increased expression of vascular endothelial growth factor, and reduced inflammation. Further, resveratrol was loaded into SPD to enhance the effects of anti-oxidation and anti-inflammation for wound healing. Our investigation shows that SPD with excellent physicochemical and biological properties applied in a murine full-thickness skin wound model resulted in remarkable and efficient acceleration of healing process, which may inspire the design of new, effective, and safer medical materials for tissue regeneration.

Asunto(s)

RESUMEN

As a natural high-performance material with a unique hierarchical structure, silk is endowed with superior mechanical properties. However, the current approaches towards producing regenerated silk fibroin (SF) for the preparation of biomedical devices fail to fully exploit the mechanical potential of native silk materials. In this study, using a top-down approach, we exfoliated natural silk fibers into silk nanofibrils (SNFs), through the disintegration of interfibrillar binding forces. The as-prepared SNFs were employed to reinforce the regenerated SF solution to fabricate orthopedic screws with outstanding mechanical properties (compression modulus > 1.1 GPa in a hydrated state). Remarkably, these screws exhibited tunable biodegradation and high cytocompatibility. After 28 days of degradation in protease XIV solution, the weight loss of the screw was ~20% of the original weight. The screws offered a favorable microenvironment to human bone marrow mesenchymal stem cell growth and spread as determined by live/dead staining, F-action staining, and Alamar blue staining. The synergy between native structural components (SNFs) and regenerated SF solutions to form bionanocomposites provides a promising design strategy for the fabrication of biomedical devices with improved performance.

RESUMEN

Silk nanofibrils (SNFs) extracted from natural silkworm silk represent a class of high-potential protein nanofiber material with unexplored biomedical applications. In this study, a SNF-assembled microsphere with extracellular matrix (ECM)-mimicking architecture and high specific surface area was developed. The SNFs were exfoliated from silkworm silks through an all-aqueous process and used as the building blocks for constructing the microspheres. Inspired by the structure and bioactive composition of ECM, hyaluronic acid (HA) was used as a bio-glue to regulate SNF assembly. With the assistance of HA, the SNF microspheres with stable fluffy nanofibrous structures were synthesized through electrospray. The biomimetic structure and nature derived composition endow the microspheres with excellent biocompatibility and enhanced osteogenic differentiation-inducing ability to mesenchymal stem cells. As proof of versatility, the SNF microspheres were further functionalized with other molecules and nanomaterials. Taking the advantages of the excellent blood compatibility and modifiability from the molecular level to the nanoscale of SNF microspheres, we demonstrated their versatile applications in protease detection and blood purification. On the basis of these results, we foresee that this natural silk-based nanofibrous microsphere may serve as a superior biomedical material for tissue engineering, early disease diagnosis, and therapeutic devices.

Asunto(s)

RESUMEN

BACKGROUND: Though there are many patents on silk, patents on sea silk are rare. Sea silk is one of the most coveted materials in the world, and the technology to make sea silk is at an extremely high risk of extinction. Unlike spider dragline silk and silkworm silk, this natural silk has been forgotten in the academic commune for millennia, though it has many fascinating properties: high strength, remarkable adhesion, extreme lightweight, and others. METHODS: Here we report that mussel-derived silk fibers can be fabricated by electrospinning. Instead of extracting proteins from byssus, we directly use the protein solution from alive blue mussels, which are intensely commercially used. The protein solution and the polyvinyl alcohol solution are mixed together to produce mussel-based silk fibers. RESULTS: The mussel-based silk fibers have many special properties like high mechanical strength, remarkable super-contraction and good wetting properties. CONCLUSION: The electrospinning mussel-based silk fibers have the potential for use as a replacement for the rarest sea silk and as a new bio-inspired material with multi-functions.

Asunto(s)

RESUMEN

Recently, ternary cobalt nickel sulfide, performing as the promising electrode material for supercapacitors has obtained great interests. Herein, the hollow and spinous NiCo2S4 nanotubes are designed and prepared through a simple hydrothermal reaction using the natural silk as the template. The spinous Ni-Co precursors are grown on the natural silk through a facile hydrothermal strategy and the hollow structure is obtained by decomposing the silk via hydrothermal sulfurization. After the calcination treatment, the hollow and spinous NiCo2S4 nanotubes are applied as the electrode material and exhibit better electrochemical performance than the solely vulcanized samples. In addition, owing to the unique hollow and spinous structure of NiCo2S4 nanotubes, the supercapacitor electrode material shows good specific capacitance (630 F g-1 at 1 A g-1), low internal resistance Rs (0.68 Ω) and high capacitance retention (91% after 3000 cycles) at 10 A g-1. Furthermore, an all-solid-state asymmetric supercapacitor is self-assembled with the SC400 composite and exhibits an energy density of 52.34 Wh kg-1 at the power density of 2206.37 W kg-1. Additionally, a blue LED indicator can be powered by connecting two ASCs in series. The prepared hollow and spinous NiCo2S4 nanotubes with excellent electrochemical properties can envision promising applications in energy storage devices and nanotechnology.