Natural Spider Silk Research Articles

The Cribellate Nanofibrils of the Southern House Spider: Extremely Thin Natural Silks with Outstanding Extensibility

AbstractCribellate silks, produced by ancient spiders, are fascinating because they feature a highly sophisticated, 3D hierarchical structure consisting of filaments with different diameters and shapes. Here, the smallest and thinnest constituents of the cribellate silk are investigated: nanofibrils that form a dense mesh that is supported by larger fibers. Analysis of their structure via atomic force and transmission electron microscopies shows that they are flattened fibrils, only ≈5 nm thick — thinner than any other natural spider silk fibrils previously reported. In this work, the first mechanical tensile testing experiments on these fibrils are carried out, which reveals that the fibrils show an outstanding extensibility of at least 1100%, almost twice as much as the most stretchable spider silk previously reported. Based on these extraordinary findings, this work significantly expands the parameter space of materials properties attainable by spider silks and provides further insights into their nanomechanics.

Artificial Spider Silk Materials: From Molecular Design, Mesoscopic Assembly, to Macroscopic Performances

AbstractSpider silk is one of the strongest and toughest fibrous materials available in nature. Its superior properties make it a good candidate for applications in various fields ranging from protective body armor to scaffolds for medical implants. However, harvesting a substantial amount of natural spider silk remains challenging because spiders cannot be easily bred. With the development of synthetic biology and its integration with materials science, considerable research has been directed toward engineering and production of synthetic spider silk materials. Here the study overviews general strategies on molecular design, mesoscopic assembly, and macroscopic regulation of artificial spider silk materials. The insights into the correlation between silk protein sequences, mesoscopic assemblies, and macroscopic material properties are provided for guiding de novo design and engineering of next‐generation spider silk materials. This review also emphasizes the challenges and future perspectives for advancing the translational research on these designer functional materials for diverse applications.

Superior strength, highly stretchable, bionic self-healing polyurethane and its composites for flexible conductivity and self-cleaning applications

Balancing the exceptional mechanical strength and repair efficiency of self-healing materials presents a significant challenge to unlocking their full potential in practical applications. Inspired by natural spider silk and cartilage, multiple dynamic hydrogen bonds were introduced into the pre-prepared polyurethane (PU). Then modifided graphene oxide (GO) nanosheets with dynamic hydrogen bonds were added into the prepared PU to form composites (AU-PU/GDU) to establish a dense hydrogen bond network structure, providing strong interfacial interactions. The AU-PU/GDU film exhibits excellent tensile strength (39.6 MPa), high elongation at break (1155.6 %), and outstanding repair efficiency (90.3 %). Using AU-PU/GDU as the flexible base, a superhydrophobic conductive composite coating (F-AU-PU/GDU) with a contact angle greater than 150° was prepared by incorporating superhydrophobic nanomaterials. This work lays the foundation for the development of multifunctional materials through the creation of self-healing superhydrophobic conductive composite coatings, which have a wide range of potential applications.

Super-Toughness Carbon Nanotube Yarns by Bio-Inspired Nano-Coiling Engineering.

Lightweight structural materials are commonly used as effective fillers for advanced composites with high toughness. This study focused on enhancing the toughness of direct-spun carbon nanotube yarns (CNTYs) by controlling the micro-textural structure using a water-gap-based direct spinning. Drawing inspiration from the structural features of natural spider silk fibroin, characterized by an α-helix in the amorphous region and β-sheet in the crystalline region, multiscale bundles within CNTYs are reorganized into a unique nano-coil-like structure. This nano-coiled structure facilitated the efficient dissipation of external mechanical loads through densification with the rearrangement of multiscale bundles, improving specific strength and strain. The resulting CNTYs exhibited exceptional mechanical properties with toughness reaching 250Jg-1, making them promising alternatives to commercially available fibers in lightweight, high-toughness applications. These findings highlight the significance of nano-coiling engineering for emulating bio-inspired micro-textural structures, achieving remarkable enhancement in the toughness of CNTYs.

Biomimetic Design of Hydration‐Responsive Silk Fibers and their Role in Actuators and Self‐Modulated Textiles

AbstractHydration‐induced shape‐morphing behavior has been discovered in many natural fiber‐based materials, yet this smart behavior in regenerated fibers from biopolymers lacks investigation. Here, hierarchically structured silk fibers are developed with anisotropic long‐range molecular organization and water‐responsive effects resembling natural spider silk. The regenerated silk fibers exhibit the water‐triggered shape‐memory effect and a water‐driven cyclic response. The reversible hydrogen bonds and transformation in the metastable secondary structure from α‐helices/random coils to β‐sheets are explored as the mechanisms responsible for the water‐responsiveness. The silk fibers obtained possess a tensile strength higher than 104 MPa at a fracture strain of ≈100%, showing noticeable toughness. The water‐responsive silk fibers exhibit a shape recovery rate of ∼83% and generate a maximum actuation stress of up to 18 MPa during the water‐driven cyclic contraction that outperforms most traditional natural textile fibers. The regenerated silk fibers show potential for use in water‐driven actuators, artificial muscle, and smart fabrics based on the integration of suitable mechanical properties and water responsiveness.

Review of Spider Silk Applications in Biomedical and Tissue Engineering.

This review will present the latest research related to the production and application of spider silk and silk-based materials in reconstructive and regenerative medicine and tissue engineering, with a focus on musculoskeletal tissues, and including skin regeneration and tissue repair of bone and cartilage, ligaments, muscle tissue, peripheral nerves, and artificial blood vessels. Natural spider silk synthesis is reviewed, and the further recombinant production of spider silk proteins. Research insights into possible spider silk structures, like fibers (1D), coatings (2D), and 3D constructs, including porous structures, hydrogels, and organ-on-chip designs, have been reviewed considering a design of bioactive materials for smart medical implants and drug delivery systems. Silk is one of the toughest natural materials, with high strain at failure and mechanical strength. Novel biomaterials with silk fibroin can mimic the tissue structure and promote regeneration and new tissue growth. Silk proteins are important in designing tissue-on-chip or organ-on-chip technologies and micro devices for the precise engineering of artificial tissues and organs, disease modeling, and the further selection of adequate medical treatments. Recent research indicates that silk (films, hydrogels, capsules, or liposomes coated with silk proteins) has the potential to provide controlled drug release at the target destination. However, even with clear advantages, there are still challenges that need further research, including clinical trials.

Silica-bridged inorganic-organic hybrid membrane for efficient daytime radiative cooling

Passive daytime radiative cooling (PDRC) has been considered as a cost-effective technology for efficient energy consumption and utilization, in which the heat is directly delivered into the outer space (3 K) through reflection and radiation. To achieve the high-performance PDRC, textile-based porous membranes are widely employed as radiators, however, the PDRC efficiency affected by the mechanical robustness. Herein, inspired by natural spider silks, a micro-/nano-sized hierarchical membrane-based radiator, which is rationally constructed with the interconnected polyethylene oxide (PEO) nanofibers bridged by the robust silica (SiO2) microspheres, was fabricated with the assistance of electrospinning. This as-prepared membrane features a hierarchically porous structure and a strong interfacial binding, resulting in the optimal optical and mechanical properties. For example, in the presence of a silane coupling agent, the tensile strength and the toughness of the resultant organic–inorganic hybrid membrane are enhanced by 7.1 and 7.2 times, respectively, compared to the organic PEO-based membrane. Furthermore, the assembled radiator demonstrates a temperature difference between 16.1 and 27.4 °C, accompanied by an average solar reflectance of 95.6 % and an average atmospheric window emittance of 89.9 %. This work provides a promising solution for achieving daytime radiative cooling at a reasonable cost and this technology could be extended into a wide range of application fields, such as smart buildings and aerospace industries.

Spidroin-mimetic Engineered Protein Fibers with High Toughness and Minimized Batch-to-batch Variations through β-sheets Co-assembly.

Synthetic spidroin fibers have not yet attained the same level of toughness and stability as natural spider silks due to the complexity of composition and hierarchical structure. Particularly, understanding the intricate interactions between spidroin components in spider fiber is still elusive. Herein, we report modular design and preparation of spidroin-mimetic fibers composed of a conservative C-terminus spidroin module, two different natural β-sheets modules, and a non-spidroin random-coil module. The resulting fibers exhibit a toughness of ~200 MJ/m3, reaching the highest value among the reported artificial spider silks. The interactions between two components of recombinant spidroins facilitate the intermolecular co-assembly of β-sheets, thereby enhancing the mechanical strength and reducing batch-to-batch variability in the dual-component spidroin fibers. Additionally, the dual-component spidroin fibers offer potential applications in implantable or even edible devices. Therefore, our work presents a generic strategy to develop high-performance protein fibers for diverse translations in different scenarios.

Durability improvement strategies for wettable fog harvesting devices inspired by spider silk fibers: a review.

Water scarcity is a persistent challenge, and in this case, the freshwater content in the air and water collection phenomena observed in nature provide ideas for fog harvesting. The fog-harvesting capabilities of natural spider silk have long attracted attention. Thus, researchers have undertaken significant efforts for the preparation of wettable biomimetic knotted fibers. However, the fragility of their chemical coating and the susceptibility of spun fibers to damage often present substantial challenges in the durability of fog harvesting equipment. Herein, from a bioengineering perspective, we review the improvement strategies for enhancing the mechanical properties of wettable biomimetic spider silk fibers based on the dense nanoconfined hydrogen-bond array crystalline regions and uniformly embedded amorphous regions of natural wettable spider silk fibers. These strategies aim to achieve high tensile strength, good fracture toughness, and corrosion resistance. Additionally, by incorporating UV inhibitors during spinning, the effects of sunlight can be mitigated or shielded, thereby greatly enhancing the mechanical durability of fog-harvesting devices under harsh realistic conditions.

Comparative Analysis of Various Spider Silks in Regard to Nerve Regeneration: Material Properties and Schwann Cell Response.

Peripheral nerve reconstruction through the employment of nerve guidance conduits with Trichonephila dragline silk as a luminal filling has emerged as an outstanding preclinical alternative to avoid nerve autografts. Yet, it remains unknown whether the outcome is similar for silk fibers harvested from other spider species. This study compares the regenerative potential of dragline silk from two orb-weaving spiders, Trichonephila inaurata and Nuctenea umbratica, as well as the silk of the jumping spider Phidippus regius. Proliferation, migration, and transcriptomic state of Schwann cells seeded on these silks are investigated. In addition, fiber morphology, primary protein structure, and mechanical properties are studied. The results demonstrate that the increased velocity of Schwann cells on Phidippus regius fibers can be primarily attributed to the interplay between the silk's primary protein structure and its mechanical properties. Furthermore, the capacity of silk fibers to trigger cells toward a gene expression profile of a myelinating Schwann cell phenotype is shown. The findings for the first time allow an in-depth comparison of the specific cellular response to various native spider silks and a correlation with the fibers' material properties. This knowledge is essential to open up possibilities for targeted manufacturing of synthetic nervous tissue replacement.

Regionalization of cell types in silk glands of Larinioides sclopetarius suggest that spider silk fibers are complex layered structures

In order to produce artificial silk fibers with properties that match the native spider silk we likely need to closely mimic the spinning process as well as fiber architecture and composition. To increase our understanding of the structure and function of the different silk glands of the orb weaver Larinioides sclopetarius, we used resin sections for detailed morphology, paraffin embedded sections for a variety of different histological stainings, and a histochemical method for localization of carbonic anhydrase activity. Our results show that all silk glands, except the tubuliform glands, are composed of two or more columnar epithelial cell types, some of which have not been described previously. We observed distinct regionalization of the cell types indicating sequential addition of secretory products during silk formation. This means that the major ampullate, minor ampullate, aciniform type II, and piriform silk fibers most likely are layered and that each layer has a specific composition. Furthermore, a substance that stains positive for polysaccharides may be added to the silk in all glands except in the type I aciniform glands. Active carbonic anhydrase was found in all silk glands and/or ducts except in the type I aciniform and tubuliform glands, with the strongest staining in aggregate glands and their ductal nodules. Carbonic anhydrase plays an important role in the generation of a pH gradient in the major ampullate glands, and our results suggest that some other glands may also harbor pH gradients.

Research Progress on Spider‐Inspired Tough Fibers†

Comprehensive SummarySpider silk has attracted increasing attention due to its fascinating combination of ultra‐high tenacity high strength, and excellent elasticity. Based on the fundamental biological studies on spider silk, significant research efforts have been devoted to biotechnology and chemical synthesis to mimic or even exceed the properties of natural spider silk fibers. Moreover, the natural spider silk fiber has been simulated with the burgeoning development of numerous spinning technologies, including wet spinning, dry spinning, electrostatic spinning, and microfluidic spinning, which continuously help to optimize the properties of synthetic spider silk. The unique characteristics of natural spider silk include high refraction transmission, heat resistance, antimicrobial properties, biocompatibility, and super shrinking. Biconical recreation of spider silk with special features and extraordinary capabilities demonstrates potential applications in biomedicine, smart wearables, artificial muscles and sensors, aerospace and other domains.

Natural spider silk nanofibrils produced by assembling molecules or disassembling fibers.

Spider silk is biocompatible, biodegradable, and rivals some of the best synthetic materials in terms of strength and toughness. Despite extensive research, comprehensive experimental evidence of the formation and morphology of its internal structure is still limited and controversially discussed. Here, we report the complete mechanical decomposition of natural silk fibers from the golden silk orb-weaver Trichonephila clavipes into ≈10 nm-diameter nanofibrils, the material's apparent fundamental building blocks. Furthermore, we produced nanofibrils of virtually identical morphology by triggering an intrinsic self-assembly mechanism of the silk proteins. Independent physico-chemical fibrillation triggers were revealed, enabling fiber assembly from stored precursors "at-will". This knowledge furthers the understanding of this exceptional material's fundamentals, and ultimately, leads toward the realization of silk-based high-performance materials. STATEMENT OF SIGNIFICANCE: Spider silk is one of the strongest and toughest biomaterials, rivaling the best man-made materials. The origins of these traits are still under debate but are mostly attributed to the material's intriguing hierarchical structure. Here we fully disassembled spider silk into 10 nm-diameter nanofibrils for the first time and showed that nanofibrils of the same appearance can be produced via molecular self-assembly of spider silk proteins under certain conditions. This shows that nanofibrils are the key structural elements in silk and leads toward the production of high-performance future materials inspired by spider silk.

Special fog harvesting mode on bioinspired hydrophilic dual-thread spider silk fiber

Normal bioinspired spider silk fibers (BSSFs) show effective fog collection abilities but are weak in the rapid transport of captured droplets, which could potentially hinder the further improvement of fog harvesting efficiency. Factually, previous works have shown that the main axis of natural spider silk consists of two separate, parallel threads, similar to the microchannel structure of Sarracenia trichome. This structural feature may be an important factor contributing to the highly efficient fog harvesting ability of spider silks. However, to the best of our knowledge, previous studies on BSSFs have ignored this feature. In this work, inspired by spider silk and Sarracenia trichome, a novel bioinspired hydrophilic dual-thread spider silk fiber (HDSSF) is obtained via a simple dipping coating method to introduce capillary force. On the HDSSF, compared to previous works, a totally different fog harvesting mode was observed, i.e., captured droplets could be rapidly transported to spindle knots under the effect of capillary force and internal Laplace pressure difference via the connectivity of liquid film and no obvious droplets could be observed on the threads. The experimental observations and underlying mechanism analyses have verified that this special fog harvesting mode allows rapid transport and directional collection of droplets to accelerate the surface reconstruction rate, coupled with the high droplet capture ability of fiber, resulting in a significant improvement of fog harvesting efficiency (9.03 g cm−2·h−1, a 590% increase compared with normal BSSF). Such HDSSF is potentially applicable in high-efficiency fog harvesting systems, droplet transport devices and other engineering applications related to fog harvesting.

Wet spinning is employed to produce spider silk with high elasticity

Spider silk exhibits exceptional strength and elasticity in its natural form. Over the course of several decades, researchers have been working on artificially spinning recombinant spider silk proteins (spidroin) in order to replicate the remarkable mechanical properties of natural spider silk. In this study, we utilized the wet spinning method to investigate the relationship between the concentration of the coagulation bath and fiber performance. We discovered that the concentration of methanol plays a crucial role in determining the continuity, diameter, and mechanical properties of the fibers. Lower concentrations of methanol favor the production of continuous, thinner fibers with higher strain. Additionally, secondary stretching during the spinning process contributes to the production of silk fibers with stable mechanical properties and thermal stability. By employing different concentrations of methanol and applying additional stretching, we successfully produced silk fibers with a high strain of 2.1652 ± 0.3871 mm/mm. Furthermore, these wet-spun fibers demonstrated the ability to promote the growth of Schwann cells, indicating their potential application in the field of biomedical engineering. Hence, the exceptional mechanical properties and the ability to promote cellular growth make the obtained spider silk fibers highly promising for various biomedical applications.

Spider dragline silk fibres maintain rectangular columnar liquid crystalline phase

ABSTRACT The liquid crystalline phase of spider silk is thought to enable for the silk protein to be stored at high concentration in the gland without gelation, facilitating the instant fibre formation at the spinning duct. Nevertheless, it has never been revealed whether the liquid crystalline state of the silk protein maintains after the fibre formation. In this study, we conducted the X-ray liquid crystal structure analysis to reveal the details of molecular assemblies of the native spider silk proteins. Based on the wide- and small angle X-ray scattering data using the uniaxial bundle of spider draglines, the spider dragline silk fibres maintain a rectangular columnar liquid crystalline phase with a P21/a (p2gg) symmetry. The liquid crystalline state of the spider silk fibre is not nematic, cholesteric, nor hexagonal columnar, as previously proposed, but rectangularly packed columnar liquid crystal. The movable silk molecular chains along the long fibre axis in the rectangular columnar liquid crystalline structure help to explain the mechanical strength of the native spider dragline silk fibres. The results obtained in this study will contribute to understanding the biological basis underlying the silk fibre formation and will be useful to the biomimicry of spider silk fibres.

Microstructure similarity analysis between synthetic phase-separated block copolymers and natural spider silk

This papers primary purpose is to explore why the microstructure of synthetic block copolymers and natural spider silk is similar at the nanoscale. This paper analyses the main chain segments and secondary structures of natural spider silk, clarifies the aggregation order, and introduces the contribution of secondary systems to the properties of natural block copolymers. Secondly, combined with the synthesis mechanism of natural spider silk, this paper summarizes and analyzes the general process of the synthesized block copolymer. Finally, the conditions of self-assembly of artificial fragments to form the structure are analyzed by employing mean-field theory and a phase diagram. Natural and ideal synthetic spider silk block copolymers have high similarity in performance. To achieve this, scientists can only start from the primary segment to understand their arrangement order in the secondary structure. Then the influence of each block on the properties of the silk fiber is analyzed. At the same time, the size and shape of self-assembled block copolymers are controlled at the micro-scale, thereby changing their properties. The mechanism above shows that the synthesized spider silk block copolymer is similar to natural spider silk in microscopic morphology.

Bioinspired Robust Helical‐Groove Spindle‐Knot Microfibers for Large‐Scale Water Collection

AbstractHelical structure is ubiquitous in nature with high‐order configuration, specific paths, large superficial areas, providing an approach to bioinspired wettability control. Owing to its special hydrophilic rough surfaces and periodic knot and joint structure, natural spider silk can catch tiny droplets in fog and transport them directionally, sparking scientific interest in bioinspired knotted microfibers to address the risk of water scarcity. To further enhance the water collection ability, a bioinspired helical‐groove‐modified spindle‐knot (HSK) microfiber is continuously fabricated in this work by a simple coating method combined with crack regulation. The formation and morphology can be precisely manipulated by adjusting the drawing velocity and concentration of the coating solution. Compared with smooth spindle‐knot microfibers, HSK exhibits greater performances of wetting speed, droplets growth rate, and hanging ability, which can be attributed to the unique helical paths that bring capillary force difference and offer extra three‐phase contact line lengths for water collection behavior. The maximum droplet volume is almost 2114 times that of the microfiber knots, which is the highest compared with previous reports. Moreover, HSK microfibers are endowed with repairable wettability, long‐term durability, excellent mechanical properties, and flexibility, showing great potential in the realm of applications for large‐scale water collection.

Spider Silk Protein Forms Amyloid-Like Nanofibrils through a Non-Nucleation-Dependent Polymerization Mechanism.

Amyloid fibrils-nanoscale fibrillar aggregates with high levels of order-are pathogenic in some today incurable human diseases; however, there are also many physiologically functioning amyloids in nature. The process of amyloid formation is typically nucleation-elongation-dependent, as exemplified by the pathogenic amyloid-β peptide (Aβ) that is associated with Alzheimer's disease. Spider silk, one of the toughest biomaterials, shares characteristics with amyloid. In this study, it is shown that forming amyloid-like nanofibrils is an inherent property preserved by various spider silk proteins (spidroins). Both spidroins and Aβ capped by spidroin N- and C-terminal domains, can assemble into macroscopic spider silk-like fibers that consist of straight nanofibrils parallel to the fiber axis as observed in native spider silk. While Aβ forms amyloid nanofibrils through a nucleation-dependent pathway and exhibits strong cytotoxicity and seeding effects, spidroins spontaneously and rapidly form amyloid-like nanofibrils via a non-nucleation-dependent polymerization pathway that involves lateral packing of fibrils. Spidroin nanofibrils share amyloid-like properties but lack strong cytotoxicity and the ability to self-seed or cross-seed human amyloidogenic peptides. These results suggest that spidroins´ unique primary structures have evolved to allow functional properties of amyloid, and at the same time direct their fibrillization pathways to avoid formation of cytotoxic intermediates.

Ambient-conditions spinning of functional soft fibers via engineering molecular chain networks and phase separation

Producing functional soft fibers via existing spinning methods is environmentally and economically costly due to the complexity of spinning equipment, involvement of copious solvents, intensive consumption of energy, and multi-step pre-/post-spinning treatments. We report a nonsolvent vapor-induced phase separation spinning approach under ambient conditions, which resembles the native spider silk fibrillation. It is enabled by the optimal rheological properties of dopes via engineering silver-coordinated molecular chain interactions and autonomous phase transition due to the nonsolvent vapor-induced phase separation effect. Fiber fibrillation under ambient conditions using a polyacrylonitrile-silver ion dope is demonstrated, along with detailed elucidations on tuning dope spinnability through rheological analysis. The obtained fibers are mechanically soft, stretchable, and electrically conductive, benefiting from elastic molecular chain networks via silver-based coordination complexes and in-situ reduced silver nanoparticles. Particularly, these fibers can be configured as wearable electronics for self-sensing and self-powering applications. Our ambient-conditions spinning approach provides a platform to create functional soft fibers with unified mechanical and electrical properties at a two-to-three order of magnitude less energy cost under ambient conditions.