Spider Silk Research Articles

High-performance magnetic artificial silk fibers produced by a scalable and eco-friendly production method

Flexible magnetic materials have great potential for biomedical and soft robotics applications, but they need to be mechanically robust. An extraordinary material from a mechanical point of view is spider silk. Recently, methods for producing artificial spider silk fibers in a scalable and all-aqueous-based process have been developed. If endowed with magnetic properties, such biomimetic artificial spider silk fibers would be excellent candidates for making magnetic actuators. In this study, we introduce magnetic artificial spider silk fibers, comprising magnetite nanoparticles coated with meso-2,3-dimercaptosuccinic acid. The composite fibers can be produced in large quantities, employing an environmentally friendly wet-spinning process. The nanoparticles were found to be uniformly dispersed in the protein matrix even at high concentrations (up to 20% w/w magnetite), and the fibers were superparamagnetic at room temperature. This enabled external magnetic field control of fiber movement, rendering the material suitable for actuation applications. Notably, the fibers exhibited superior mechanical properties and actuation stresses compared to conventional fiber-based magnetic actuators. Moreover, the fibers developed herein could be used to create macroscopic systems with self-recovery shapes, underscoring their potential in soft robotics applications.

Mechanical and structural features of three AcSp proteins underlie the diverse material properties of aciniform silks of Neoscona spiders

Spider silks are desirable multicomponent biomaterials characterized by great tensile strength, extensibility, and biocompatibility. Of all spider silk types, aciniform silk has highest toughness due to its combination of high tensile strength and elsticity. Here, we identify three major spidroin components (AcSp1A, AcSp1B, and AcSp2) from aciniform silk of orbweb weaving spider, Neoscona scylloides, and present their full-length coding gene sequences. Comparative sequence and expression level analysis show that AcSp1B has highest expression level and higher serine content than other two AcSp proteins, while the AcSp2 shows very low mRNA level. Furthermore, three recombinant minimalist AcSp proteins are produced and could be induced to form fibers by shear forces in a physiological buffer. The manual-drawn AcSp1B fiber shows strongest tensile strength among three AcSp fibers because of its higher β-sheet formed by abundant serine content. We also compare mechanical properties of aciniform silks between two Neoscona species (N. theisi and N. scylloides) and found that aciniform silks from N. theisi exhibit higher tensile strength than those of N. scylloides, which may result from altering expression levels of two AcSp1 proteins. Collectively, our results provide insights into the mechanical features of each component in aciniform silk from N. scylloides and reveal the molecular mechanism of diverse material properties of aciniform silk among species.

Accelerated Reversible Conversion of Li2S2 to Li2S by Spidroin Regulated Li+ Flux for High-performance Li-Sulfur Batteries.

Regulating the transformation of sulfur species is the key to improving the electrochemical performance of lithium-sulfur (Li-S) batteries, in particular, to accelerate the reversible conversion between solid phase Li2S2 and Li2S. Herein, we introduced Spidroin, which is a main protein in spider silk, as a dual functional separator coating in Li-S batteries to effectively adsorb polysulfides via the sequence of amino acids in its primary structure and regulate Li+ flux through the β-sheet of its secondary structure, thus accelerating the reversible transformation between Li2S2 and Li2S. Spidroin-based Li-S cells exhibited an exceptional electrochemical performance with a high specific capacity of 744.1 mAh g-1 at 5 C and a high areal capacity of 7.5 mAh cm-2 at a low electrolyte-to-sulfur (E/S) ratio of 6 μL mgs -1 and a sulfur loading of 8.6 mgs cm-2.

Accelerated Reversible Conversion of Li2S2 to Li2S by Spidroin Regulated Li+ Flux for High‐performance Li‐Sulfur Batteries

Regulating the transformation of sulfur species is the key to improving the electrochemical performance of lithium‐sulfur (Li‐S) batteries, in particular, to accelerate the reversible conversion between solid phase Li2S2 and Li2S. Herein, we introduced Spidroin, which is a main protein in spider silk, as a dual functional separator coating in Li‐S batteries to effectively adsorb polysulfides via the sequence of amino acids in its primary structure and regulate Li+ flux through the β‐sheet of its secondary structure, thus accelerating the reversible transformation between Li2S2 and Li2S. Spidroin‐based Li‐S cells exhibited an exceptional electrochemical performance with a high specific capacity of 744.1 mAh g‐1 at 5C and a high areal capacity of 7.5 mAh cm‐2 at a low electrolyte‐to‐sulfur (E/S) ratio of 6 μL mgs‐1 and a sulfur loading of 8.6 mgs cm‐2.

Spider web-reinforced chitosan/starch biopolymer for active biodegradable food packaging

In this study, starch (ST), chitosan (CH), spider silk (SW), and their hybrid composite bioplastics were fabricated and examined for physicochemical and mechanical properties. The essential oils (EOs) of Rosmarinus officinalis were encapsulated to enhance their biological application. The prepared composite films were characterized using various spectroscopic techniques such as XRD, SEM, GCMS–, UV–VIS, TGA, and FTIR spectroscopy. The antimicrobial activity of the prepared film was tested against S. aureus bacterial and C. albican fungal strains which showed a greater zone of inhibition for the composite film encapsulated with EOs. The biodegradability of the synthesized film was evaluated for 60 days in soil under laboratory conditions. The composite film containing spider web and essential oil significantly improved mechanical properties. The physicochemical results, such as moisture, solubility, swelling, transmittance, opacity, and water vapor permeability, of the prepared bioplastic were comparable with those of the control plastic. The EO-based film had greater antioxidant activity against DPPH, hydrogen peroxide, and phosphomolybdenum assays, with an inhibition range of 60–70 %. The addition of spider web and essential oil to the chitosan/ starch film significantly increased the shelf life of injera and tomatoes for 7 and 10 days, respectively for the EO-based film. The biodegradability of the synthesized film has shown a great reduction in the weight and growth of microorganisms. In general, the CH/ST/SW and CH/ST/SW/EOs composite films have greater mechanical, biological, physicochemical, and potential improvement of food shelf life applied as either coating or packaging material.

Super‐Strong, Super‐Stiff, and Super‐Tough Fluorescent Alginate Fibers with Outstanding Tolerance to Extreme Conditions

AbstractThe combination of multiple physical properties is of great importance for widening the application scenarios of biomaterials. It remains a great challenge to fabricate biomolecules‐based fibers gaining both mechanical strength and toughness which are comparable to natural spider dragline silks. Here, by mimicking the structure of dragline silks, a high‐performance fluorescent fiber Alg‐TPEA‐PEG is designed by non‐covalently cross‐linking the polysaccharide chains of alginate with AIEgen‐based surfactant molecules as the flexible contact points. The non‐covalent cross‐linking network provides sufficient energy‐dissipating slippage between polysaccharide chains, leading to Alg‐TPEA‐PEG with highly improved mechanical performances from the plastic strain stage. By successfully transferring the extraordinary mechanical performances of polysaccharide chains to macroscopic fibers, Alg‐TPEA‐PEG exhibits an outstanding breaking strength of 1.27 GPa, Young's modulus of 34.13 GPa, and toughness of 150.48 MJ m−3, which are comparable to those of dragline silk and outperforming other artificial materials. More importantly, both fluorescent and mechanical properties of Alg‐TPEA‐PEG can be well preserved under various harsh conditions, and the fluorescence and biocompatibility facilitate its biological and biomedical applications. This study affords a new biomimetic designing strategy for gaining super‐strong, super‐stiff, and super‐tough fluorescent biomaterials.

Machine Learning-Assisted Gesture Sensor Made with Graphene/Carbon Nanotubes for Sign Language Recognition.

Gesture sensors are essential to collect human movements for human-computer interfaces, but their application is normally hampered by the difficulties in achieving high sensitivity and an ultrawide response range simultaneously. In this article, inspired by the spider silk structure in nature, a novel gesture sensor with a core-shell structure is proposed. The sensor offers a high gauge factor of up to 340 and a wide response range of 60%. Moreover, the sensor combining with a deep learning technique creates a system for precise gesture recognition. The system demonstrated an impressive 99% accuracy in single gesture recognition tests. Meanwhile, by using the sliding window technology and large language model, a high performance of 97% accuracy is achieved in continuous sentence recognition. In summary, the proposed high-performance sensor significantly improves the sensitivity and response range of the gesture recognition sensor. Meanwhile, the neural network technology is combined to further improve the way of daily communication by sign language users.

Fluorescent alginate fiber with super-strong and super-tough mechanical performances for biomedical applications

Emerging research attentions are focused on the development of fluorescent biomaterials for various biomedical applications, including fluorescence-guided surgery. However, it is still challenging to prepare biomolecules-based fluorescent fibers with both satisfactory biocompatibility and optimal mechanical properties. Here, we develop a fluorescent robust biofiber through using a tetraphenylethene-containing surfactant as the contact points between polysaccharide chains of alginate. This newly developed contact points not only strengthen the cross-linking network of polysaccharide chains, but also afford enough energy-dissipating slippage for polysaccharide chains. Consequently, the generated fluorescent fiber is endowed with highly improved mechanical performances from plastic strain stage. The experimental results indicate that the fluorescent fiber shows good mechanical properties of breaking strength of 1.10 GPa (12.09 cN/dtex), Young's modulus of 39.81 GPa and toughness of 137.26 MJ/m3, which are comparable to those of dragline silk and outperforming spider silk proteins and other artificial materials. More importantly, its satisfactory biosafety and wound healing-promoting ability as a fluorescent suture are solidly proved by both in vitro and in vivo assays, which opens an opportunity for its biological and biomedical applications. This study provides a novel strategy for the development of robust fluorescent biomaterials.

Influence of Initial Secondary Structure on Conformation and Mechanical Properties of Spider Silk Protein Gels.

Recombinant spider silk protein (RSP) is a promising biomaterial for developing high-performance materials independent of fossil fuels. In this study, we investigated the influence of the initial secondary structure of RSPs on the properties of RSP-based hydrogels. By altering the initial structure of RSP to β-sheets (β-RSP), α-helices (α-RSP), and random coils (rc-RSP) through solvent treatment, we compared the structures and mechanical properties of the resulting gels. Solid-state NMR revealed a β-sheet-rich structure in all gels, with the α-RSP gel exhibiting significantly higher strength and Young's modulus compared to the rc-RSP gel. X-ray diffraction revealed that the α-RSP gel had a unique crystalline structure, distinguishing it from the β-RSP and rc-RSP gels. The different initial secondary structures possibly lead to variations in the crystalline and network structures of the molecular chains within the gels, explaining the superior mechanical properties observed in the α-RSP gels.

Spider silk tensile performance does not correlate with web use.

Spider silk is amongst the toughest materials produced by living systems, but its tensile performance varies considerably between species. Despite the extensive sampling of the material properties and composition of dragline silk, the understanding why some silks perform better than others is still limited. Here, I adopted a phylogenetic comparative approach to re-analyse structural and mechanical data from the Silkome database and the literature across 164 species to (a) provide an extended model of silk property evolution, (b) test for correlations between structural and mechanical properties, and (c) to test if silk tensile performance differs between web-building and non-web-building species. Unlike the common notion that orb-weavers have evolved the best performing silks, outstanding tensile properties were found both in and outside the araneoid clade. Phylogenetic linear models indicated that the mechanical and structural properties of spider draglines poorly correlate, but silk strength and toughness correlated better with birefringence (an indicator of the material anisotropy) than crystallinity. Furthermore, in contrast to previous ideas, silk tensile performance did not differ between ecological guilds. These findings indicate multiple unknown pathways towards the evolution of spider silk tensile super-performance, calling for a better integration of non-orb-weaving spiders in spider silk studies.

Enhancing demulsification efficiency and sustaining constant separation flux in oil/water emulsions via Janus membrane inspired by spider silk

Conventional special wettable membranes for the separation of the surfactant-stabilized oil/water emulsions primarily rely on the “size-sieving” mechanism, which enhances efficiency by reducing the pore size, leading to a trade-off between separation flux and efficiency. Inspired by spider silk, we developed a novel Janus membrane (JPSPP) capable of high demulsification capacity and constant separation flux. This membrane combines a superhydrophobic PS@PDMS membrane (PPM) with spindle-knotted structures on a negatively charged superhydrophilic PAN@SAS membrane (PSM) through electrospinning. The synergy of electrostatic force generated by charged surfaces, the Laplace pressure created by spindle-knotted geometry, and the wettability gradient resulting from asymmetric wettability enhance the demulsification capacity. The high and constant separation flux was achieved as Laplace pressure drives rapid coalescence of demulsified oil droplets towards the top of the spindle-knotted structures, facilitating oil detachment and efficient water permeation downward. As a result, the JPSPP membrane achieved a separation efficiency exceeding 99.9 %, with a constant separation flux of up to 1952.27 L m−2 h−1, representing a 3–4 folds improvement compared to the pure PAN membranes (PM). The separation performance of the JPSPP still maintains excellent separation performance with efficiency above 98.3 % and a slight attenuation in flux after twenty filtration cycles. The research proposes groundbreaking solutions that significantly enhance the demulsification efficiency and maintain a constant separation flux for oil/water emulsions, with the potential to profoundly impact multiple industries including food processing, energy production, and the petroleum industry, etc.

A phenomenological theory for hydration-induced supercontraction and twist of spider dragline silk

Spider dragline silk is one promising material for producing artificial muscles, owing to its remarkable capacity for supercontraction and twist when exposed to high humidity. Based on the hydration absorption equation and the standard reinforcing model, we develop a phenomenological theory for elucidating the hydration-induced supercontraction and twist of spider dragline silk. The theory can reasonably predict the responses of softening, anisotropy, hydration-supercontraction, and twist of spider dragline silk. The theoretical predictions align with the experimental results. This study provides valuable insight into the underlying mechanisms of the hydration-induced deformation of spider dragline silk.

Ion‐Specific Interactions Engender Dynamic and Tailorable Properties in Biomimetic Cationic Polyelectrolytes

AbstractBiomaterials such as spider silk and mussel byssi are fabricated by the dynamic manipulation of intra‐ and intermolecular biopolymer interactions. Organisms modulate solution parameters, such as pH and ion co‐solute concentration, to effect these processes. These biofabrication schemes provide a conceptual framework to develop new dynamic and responsive abiotic soft material systems. Towards these ends, the chemical diversity of readily available ionic compounds offers a broad palette to manipulate the physicochemical properties of polyelectrolytes via ion‐specific interactions. In this study, we show for the first time that the ion‐specific interactions of biomimetic polyelectrolytes engenders a variety of phase separation behaviors, creating dynamic thermal‐ and ion‐responsive soft matter that exhibits a spectrum of physical properties, spanning viscous fluids to viscoelastic and viscoplastic solids. These ion‐dependent characteristics are further rendered general by the merger of lysine and phenylalanine into a single, amphiphilic vinyl monomer. The unprecedented breadth, precision, and dynamicity in the reported ion‐dependent phase behaviors thus introduce a broad array of opportunities for the future development of responsive soft matter; properties that are poised to drive developments in critical areas such as chemical sensing, soft robotics, and additive manufacturing.

Porous Spindle-Knot Fiber by Fiber-Microfluidic Phase Separation for Water Collection and Nanopatterning.

Porous spindle-knot structures have been found in many creatures, such as spider silk and the root of the soybean plant, which show interesting functions such as droplet collection or biotransformation. However, continuous fabrication of precisely controlled porous spindle-knots presents a big challenge, particularly in striking a balance among good structural controllability, low-cost, and functions. Here, we propose a concept of a fiber-microfluidics phase separation (FMF-PS) strategy to address the above challenge. This FMF-PS combines the advantages of a microchannel regulated Rayleigh instability of polymer solution coated onto a fiber with the nonsolvent-induced phase separation of the polymer solution, which enables continuous and cost-effective production of porous spindle-knot fiber (PSKF) with well-controlled size and porous structures. The critical factors controlling the geometry and the porous structures of the spindle-knot by FMF-PS have been systematically investigated. For applications, the PSKF exhibited faster water droplet nucleation, growth, and maximum water collection capability, compared to the control samples, as revealed by in situ water collection growth curves. Furthermore, high-level fabrics of the PSKFs, including a two-dimensional network and three-dimensional architecture, have been demonstrated for both large-scale water collection and art performance. Finally, the PSKF is demonstrated as a programmable building block for surface nanopatterning.

Overexpressed Artificial Spidroin Based Microneedle Spinneret for 3D Air Spinning of Hybrid Spider Silk.

Efforts have been devoted to developing strategies for converting spider silk proteins (spidroins) into functional silk materials. However, studies mimicking the exact natural spinning process of spiders encounter arduous challenges. In this paper, consistent with the natural spinning process of spiders, we report a high-efficient spinning strategy that enables the mass preparation of multifunctional artificial spider silk at different scales. By simulating the structural stability mechanism of the cross-β-spine of the amyloid polypeptide by computer dynamics, we designed and obtained an artificial amyloid spidroin with a significantly increased yield (13.5 g/L). Using the obtained artificial amyloid spidroin, we fabricated artificial spiders with artificial spinning glands (hollow MNs). Notably, by combining artificial spiders with 3D printing, we perform patterned air spinning at the macro- and microscales, and the resulting patterned artificial spider silk has excellent pump-free liquid flow and conductive and frictional electrical properties. Based on these findings, we used macroscale artificial spider silk to treat rheumatoid arthritis in mice and micro artificial spider silk to prepare wound dressings for diabetic mice. We believe that artificial spider silk based on an exact spinning strategy will provide a high-efficient way to construct and modulate the next generation of smart materials.

The evolution of silk production in Crustacea

ABSTRACT Spun silk is found only in arthropods, where it plays critical roles in feeding, protection, and reproduction. It has evolved repeatedly within the arthropods, providing an opportunity for comparative analyses to reveal the mechanisms driving convergent evolution within this taxon. Silk in crustaceans has received much less attention than silk in arachnids and insects but may have unique and useful properties. We combine data on the morphology of silk and silk systems with ancestral state reconstruction and find that silk has likely evolved convergently at least six times within Crustacea. We also break down the components of crustacean silk as a composite trait by discussing the silk properties, the silk production systems, and the silk genes. We find that amphipod and tanaid silks are similar to silkworm and spider silks but have their own unique silk system morphology. Much remains unknown about the origins and diversification of silk in crustaceans; we propose that the molecular investigation of silk genes and systems will provide a path forward. By investigating the evolution of silk production in crustaceans, we may discover insights into predispositions for silk production in arthropods and valuable substrates for biomaterial research.

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.

Spider Silk: Rapid, Bottom‐Up Self‐Assembly of MaSp1 into Hierarchically Structured Fibers Through Biomimetic Processing

AbstractSpider dragline silk's exceptional mechanical performance, coupled with its benign production pathway, have inspired the design of diverse smart materials. Remarkably, relatively little is known about the self‐assembly process of major ampullate spidroin 1 (MaSp1) – the main protein constituent of dragline fiber – during its rapid conversion from soluble precursor protein into hierarchically structured mature silk fibers. Herein, the biomimetic potential of MaSp1 is explored using a new recombinant platform with full domain representation. MaSp1 is found to undergo efficient liquid‐liquid phase separation (LLPS) in response to kosmotropic ions, with notably higher propensity compared to MaSp2, and with MaSp1 exhibiting a more complex solubility profile relative to levels of sodium chloride. To further the understanding of silk spinning, the rapid assembly of mesoscale structures is monitored in real‐time in response to ion and pH gradients, revealing a progression from LLPS droplets toward aligned hierarchical fibers. Furthermore, using this biomimetic system, insoluble macroscopic MaSp1 fibers can be readily generated, wherein the application of mechanical deformation triggers the emergence of β‐sheet secondary structures. The insights gained from this study can have broader application in efforts to mimic the formation of biomaterials with spatially organized features across multiple length scales.

Current Progress on Scale‐Up and Commercialization of Microbially‐Produced Silk

AbstractOver the past two decades, significant advancements have been made in the scalable production and commercialization of microbially‐produced recombinant protein polymers. This perspective presents the evolution from early research efforts to the development of market‐ready products, with a focus on recombinant silk‐like proteins. Initial attempts to synthesize spider silk proteins in microbial hosts faced challenges with solubility, stability, and yield. Recent advancements in synthetic biology, protein engineering, and bioprocess development have enabled the substantial progress on these challenges. Early commercial efforts highlight the complexities and high costs involved in silk production and more recent strategies have shifted toward processes with better scalability, techno‐economics, and product properties. Significant commercial progress has been made, with products launched in textiles and personal care. Although market penetration is limited so far, substantial groundwork is laid for future success. Key challenges remain, such as continued high production costs and the need for cost‐effective purification and fiber spinning techniques. However, the convergence of scientific, technological, and market developments –including a growing number of product launches – suggests that recombinant silk and protein polymers can soon become widespread sustainable materials across various industries.

1H, 15N and 13C resonance assignments of eggcase silk protein 3.

Spider silk is a high-performance biomaterial known for its outstanding combination of strength and flexibility. Among the six distinct types of spider silk, eggcase silk stands out as it is exclusively produced from the tubuliform gland, playing a specialized role in offspring protection. In the spider species Latrodectus hesperus, eggcase silk is spun from a large spidroin complex, including the major silk component tubuliform spidroin 1 (TuSp1) and at least six different minor silk components. One of these minor components is eggcase protein 3 (ECP3), a small silk protein of 11.8kDa that lacks the typical spidroin architecture. ECP3 shows very limited homology to all known spidroins. In this study, we report nearly complete backbone and side-chain resonance assignments of ECP3 as a basis for studying the structural mechanisms involved in eggcase silk formation.