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Thermodynamic Analysis of Silk Fibroin–Graphite Hybrid Materials and Their Morphology

Silk fibroin (SF) is a β-sheet-rich protein that is responsible for the remarkable tensile strength of silk. In addition to its mechanical properties, SF is biocompatible and biodegradable, making it an attractive candidate for use in biotic/abiotic hybrid materials. A pairing of particular interest is the use of SF with graphene-based nanomaterials (GBNs). The properties of this interface drive the formation of well-ordered nanostructures and can improve the electronic properties of the resulting hybrid. It was previously demonstrated that SF can form lamellar nanostructures in the presence of graphite; however, the equilibrium morphology and associated driving interactions are not fully understood. Here, in this study, we characterize these interactions between SF and SF lamellar with graphite using molecular dynamics (MD) simulations and umbrella sampling (US). We find that SF lamellar nanostructures have strong orientational and spatial preferences on graphite that are driven by the hydrophobic effect, destabilizing solvent–protein interactions and stabilizing protein–protein and protein–graphite interactions. Finally, we show how careful consideration of these underlying interactions can be applied to rationally modify the nanostructure morphology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Multifunctional Silk Fibroin Hydrogels with Strong Adhesion for Tissue Sealing and Wearable Electronic Sensors

Multifunctional hydrogels with excellent adhesion, biodegradability, and conductivity are essential for overcoming the obstacles of postoperative secondary injury, flexible sensing instability, and so on. Herein, we develop a multifunctional silk fibroin (SF) hydrogel modified with poly(acrylic acid). Owing to the stable chemical cross-linking network and the abundant carboxylic acid groups of the SF network, the SF hydrogel exhibits a high tensile strength of 74.34 kPa due to sufficient cohesion and interfacial interactions. Additionally, the tensile strain reaches a maximum of 414.6%, the compressive strength is 0.9 MPa, and the shear adhesive strength for pig skin tissues is as high as 64 kPa. Compared with most hydrogels, our multifunctional SF hydrogel with a low swelling ratio provides excellent adhesion, biodegradation, and conductivity, which shows advantages in terms of invasive tissue sealing. Furthermore, the use of self-adhesive SF hydrogels as conductive hydrogels in flexible sensors also benefits the collection of physiological electricity and human motion signals in the field of wearable and implantable electronic devices.

adhesive↗

Boost of the Bio-memristor Performance for Artificial Electronic Synapses by Surface Reconstruction

Biomaterial-based memristors (bio-memristors) are often adopted to emulate biological synapse functions and applied to construct neural computing networks in brain-inspired chip systems. However, the randomness of conductive filament formation in bio-memristors inhibits their switching performance by causing the dispersion of the device-switching parameters. In this case, a facile porous silk fibroin (p-SF) memristor was obtained through a protein surface reconstruction strategy, in which the size of the hole can be adjusted by the density of hybrid nanoseeds. Here, the porous SF memristors exhibit greatly enhanced electrical characteristics, including uniform I-V cycles, centralized distribution of the switching voltages, and both high and low resistances, compared to devices without pores. The results of three-dimensional (3D) simulations based on classical density functional theory (cDFT) suggest that the reconstructed pores in the SF layers guide the formation and fracture of Ag filaments under an electric field and enhance the overall conductivity by separating Ag + ion and electron diffusion pathways. Ag + ions are predicted to preferentially diffuse through pores, whereas electrons diffuse through the SF network. Interestingly, the device conductance can be bidirectionally modulated gradually by positive and negative voltages, can faithfully simulate short-term and long-term plasticity, and can even realize the triplet-spike-timing-dependent plasticity (triplet-STDP) rule, which can be used for pattern recognition in biological systems. The simulation results reveal that a memristor network of this type has an accuracy of ~95.78% in memory learning and the capability of pattern learning. This work provides a facile technology route to improve the performance of bionic-material memristors.

36 MATERIALS SCIENCE↗

Preparation of Highly Crystalline Silk Nanofibrils and Their Use in the Improvement of the Mechanical Properties of Silk Films

Due to their commendable biocompatibility, regenerated silk fibroin (RSF) films have attracted considerable research interest. However, the poor mechanical properties of RSF films have limited their use in various biomedical applications. In this study, a novel, highly crystalline silk fibril was successfully extracted from silk by combining degumming with ultrasonication. Ultrasonication accelerated the development of silk nanofibrils measuring 130–200 nm on the surface of the over-degummed silk fibers, which was confirmed via scanning electron microscopy. Additionally, the crystallinity index of silk fibril was found to be significantly higher (~68%) than that of conventionally degummed silk (~54%), as confirmed by the Fourier-transform infrared (FTIR) spectroscopy results. Furthermore, the breaking strength and elongation of the RSF film were increased 1.6 fold and 3.4 fold, respectively, following the addition of 15% silk nanofibrils. Thus, the mechanical properties of the RSF film were remarkably improved by the addition of the silk nanofibrils, implying that it can be used as an excellent reinforcing material for RSF films.

36 MATERIALS SCIENCE↗

Two-dimensional silk

Despite the promise of silk-based devices, the inherent disorder of native silk limits performance. Here, we report highly ordered two-dimensional silk fibroin (SF) films grown epitaxially on van der Waals (vdW) substrates. Using atomic force microscopy, nano–Fourier transform infrared spectroscopy, and molecular dynamics, we show that the films consist of lamellae of SF molecules that exhibit the same secondary structure as the nanocrystallites of native silk. Increasing the SF concentration results in multilayers that grow either by direct assembly of SF molecules into the lamellae or, at high concentrations, along a two-step pathway beginning with a disordered monolayer that then crystallizes. Scanning Kelvin probe measurements show that these films substantially alter the surface potential; thus, they provide a platform for silk-based electronics on vdW solids.

36 MATERIALS SCIENCE↗

Two-Dimensional Silk Crystal Films as Matrix Layer for High-Performance Microelectronics

This study explores a bio-inspired approach for memristive devices by combining Keggin-type polyoxometalates (POMs)-[SiW 12 O 40 ] 4 (POM-T) and [PW 12 O 40 ] 3 (POM-P), with silk fibroin (SF) to create 2D SF–POM layers on highly ordered pyrolytic graphite (HOPG) as resistive switching layers for memristors. We propose that the ordered SF layer template 0D POMs facilitate the formation of conductive filaments, thereby enhancing the variability of the manufactured memristors. AFM analysis revealed that both SF and SF–POM layers shared similar morphologies, while SF–POM–T formed larger aggregates, likely due to the stronger acidity of POM-T, which probably caused SF to aggregate and alter its secondary structure. Scanning Kelvin probe microscopy (SKPM) revealed that POMs reduced the contact potential difference of HOPG, resulting in lower work functions. Compared to an SF device, the SF–POM–P device showed improved memristive behavior, with a larger current gap and good repeatability over multiple sweeps; whereas the SF–POM–T device did not exhibit memristor activity, likely due to acidity-induced disruption of the SF template’s order and CF formation. More importantly, SF–POM–P devices also demonstrated programmable memristive states. Finally, combining simulation-driven memristor modeling, we showcase a co-design workflow for advancing bioinspired memristors through new materials design, synthesis, and device modeling and development.

36 MATERIALS SCIENCE↗

Transgenic silkworms expressing spider silk

Transgenic silkworms stably expressing synthetic spider silk genes or composite silkworm/spider silk genes are disclosed. The exogenous spider silk genes are stably intergrated into a defined site of the fibroin heavy chain intron or a fibroin light chain intron of silkworms. Synthetic spider silk proteins and composite spider silk-silkworm genes and proteins are provided. The expression of exogenous spider silk genes is driven by the endogenous fibroin heavy chain promoter, improving the genetic stability of transgenic silkworms. The composite silkworm/spider silk fibers exhibit exceptional mechanical performance, compared to normal silkworm silk fibers and other transgenic silkworm fibers.

Lewis, Randolph V.↗