Spider silk is a striking and robust natural material that has an unrivaled combination of strength and elasticity. There are two major problems in creating materials from recombinant spider silk proteins (rSSps): expressing sufficient quantities of the large, highly repetitive proteins and solvating the naturally self-assembling proteins once produced. To address the second problem, we have developed a method to rapidly dissolve rSSps in water in lieu of traditional organic solvents and accomplish nearly 100% solvation and recovery of the protein. Our method involves generating pressure and temperature in a sealed vial by using short, repetitive bursts from a conventional microwave. The method is scalable and has been successful with all rSSps used to date. From these easily generated aqueous solutions of rSSps, a wide variety of materials have been produced. Production of fibers, films, hydrogels, lyogels, sponges, and adhesives and studies of their mechanical and structural properties are reported. To our knowledge, ours is the only method that is cost-effective and scalable for mass production. This solvation method allows a choice of the physical form of product to take advantage of spider silks' mechanical properties without using costly and problematic organic solvents.
The mechanical properties and biocompatibility of spider silks have made them one of the most sought after and studied natural biomaterials. A biomimetic process has been developed that uses water to solvate purified recombinant spider silk proteins (rSSps) prior to material formation. The absence of harsh organic solvents increases cost effectiveness, safety, and decreases the environmental impact of these materials. This development allows for the investigation of aqueous-based rSSps as coatings and adhesives and their potential applications. In these studies it was determined that fiber-based rSSps in nonfiber formations have the capability to coat and adhere numerous substrates, whether rough, smooth, hydrophobic, or hydrophilic. Further, these materials can be functionalized for a variety of processes. Drug-eluting coatings have been made with the capacity to release a variety of compounds in addition to their inherent ability to prevent blood clotting and biofouling. Additionally, spider silk protein adhesives are strong enough to outperform some conventional glues and still display favorable tissue implantation properties. The physical properties, corresponding capabilities, and potential applications of these nonfibrous materials were characterized in this study. Mechanical properties, ease of manufacturing, biodegradability, biocompatibility, and functionality are the hallmarks of these revolutionary spider silk protein materials.
Using transgenic silkworms with their natural spinning apparatus has proven to be a promising way to spin spider silk-like fibers. The challenges are incorporating nativesize spider silk proteins and achieving an inheritable transgenic silkworm strain. In this study, a CRISPR/Cas9 initiated fixed-point strategy was used to successfully incorporate spider silk protein genes into the Bombyx mori genome. Native-size spider silk genes (up to 10 kb) were inserted into an intron of the fibroin heavy or light chain (FibH or FibL) ensuring that any sequence changes induced by the CRISPR/Cas9 would not impact protein production. The resulting fibers are as strong as native spider silks (1.2 GPa tensile strength). The transgenic silkworms have been tracked for several generations with normal inheritance of the transgenes. This strategy demonstrates the feasibility of using silkworms as a natural spider silk spinner for industrial production of high-performance fibers.
Silkworm silk has become increasingly relevant for material applications. However, the industry as a whole is retracting because of problems with mass production. One of the key problems is the inconsistent properties of the silk. A means by which to improve the silk material properties is through enhanced sericulture techniques. One possible technique is altering the feed of the silkworms to include single-wall carbon nanotubes (SWNTs) or graphene (GR). Recently published results have demonstrated substantial improvement in fiber mechanical properties. However, the effect of the surfactant used to incorporate those materials into the feed on the fiber mechanical properties in comparison to normal silkworm silk has not been studied or reported. Thus, the total effect of feeding the SWNT and GR in the presence of surfactants on silkworms is not understood. Our study focuses on the surfactant [calcium lignosulfonate (LGS)] and demonstrates that it alone results in appreciable improvement of mechanical properties in comparison to nontreated silkworm silk. Furthermore, our study demonstrates that mixing the LGS, SWNT, and GR directly into the artificial diet of silkworms yields improved mechanical properties without decline below the control silk at high doses of SWNT or GR. Combined, we present evidence that mixing surfactants, in this case LGS, directly with the diet of silkworms creates a high-quality fiber product that can exceed 1 GPa in tensile strength. With the addition of nanocarbons, either SWNT or GR, the improvement is even greater and consistently surpasses control fibers. However, feeding LGS alone is a more economical and practical choice to consistently improve the mechanical properties of silkworm fiber.
The ability of the rapid-capacitive discharge approach to access optimal viscosity ranges in metallic glasses for thermoplastic processing is explored. Using high-speed thermal imaging, the heating uniformity and stability against crystallization of Zr35Ti30Cu7.5Be27.5 metallic glass heated deeply into the supercooled region is investigated. The method enables homogeneous volumetric heating of bulk samples throughout the entire supercooled liquid region at high rates (~105 K/s) sufficient to bypass crystallization throughout. The crystallization onsets at temperatures in the vicinity of the “crystallization nose” were identified and a Time-Temperature-Transformation diagram is constructed, revealing a “critical heating rate” for the metallic glass of ~1000 K/s. Thermoplastic process windows in the optimal viscosity range of 100–104 Pa·s are identified, being confined between the glass relaxation and the eutectic crystallization transition. Within this process window, near-net forging of a fine precision metallic glass part is demonstrated.
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