Enzymatic Crosslinked Silk Fibroin Hydrogel for Biodegradable Electronic Skin and Pulse Waveform Measurements.

The development of a portable, controllable, and environmentally friendly electronic skin (e-skin) is highly desirable; however, it presents a major challenge. Herein, a biocompatible, biodegradable, and easily usable hydrogel was designed and fabricated as e-skin to enable the transmission of information regarding the spatial pressure distribution. Silk fibroin (SF) was used as the hydrogel skeleton, which endowed the hydrogel with intelligent mechanical sensitivity. During its conditioning in weakly acidic media, the density of the enzymatic crosslink increased and a dense network was formed due to the formation of covalent/hydrogen bonds. Additionally, a conductive SF/polyvinyl alcohol (PVA) hybrid film was molded as a flexible electrode after graphite deposition. The above SF sensing unit based on SF hydrogels and SF/PVA hybrid films showed high strain sensitivity (4.78), fast responsiveness (<0.1 s), good cycling stability (≥10,000), excellent biocompatibility, and biodegradability. Importantly, a coplanar 8 × 8 pixel SF-based e-skin array was successfully fabricated and applied for 3D signal transmission of the object. The SF-based e-skin was capable of precisely tracking the changes in the pulse pressure, the movement of the finger joint, and the vibrations of the vocal cord. Therefore, the current findings provide a solid foundation for future studies exploring the next generation of electronic devices.

Stretchable, Stable, and Degradable Silk Fibroin Enabled by Mesoscopic Doping for Finger Motion Triggered Color/Transmittance Adjustment.

As a kind of biocompatible material with long history, silk fibroin is one of the ideal platforms for on-skin and implantable electronic devices, especially for self-powered systems. In this work, to solve the intrinsic brittleness as well as poor chemical stability of pure silk fibroin film, mesoscopic doping of regenerated silk fibroin is introduced to promote the secondary structure transformation, resulting in huge improvement in mechanical flexibility (∼250% stretchable and 1000 bending cycles) and chemical stability (endure 100 °C and 3-11 pH). Based on such doped silk film (SF), a flexible, stretchable and fully bioabsorbable triboelectric nanogenerator (TENG) is developed to harvest biomechanical energy in vitro or in vivo for intelligent wireless communication, for example, such TENG can be attached on the fingers to intelligently control the electrochromic function of rearview mirrors, in which the transmittance can be easily adjusted by changing contact force or area. This robust TENG shows great potential application in intelligent vehicle, smart home and health care systems.

A capacitive humidity sensor based on all-protein embedded with gold nanoparticles @ carbon composite for human respiration detection.

Wool and silk fiber are the most extensive resources of protein fibers and have been used in the textile field for many years. The extracted biocompatible proteins are more and more widely used in flexible devices, sensors, tissue engineering, etc. Here, a fully biomaterial based flexible humidity sensor has been successfully fabricated for the first time. Interdigital electrodes of humidity sensor are printed on a transparent sensor substrate made of silk protein by inkjet printing. The humidity sensitive material is gold nanoparticles hosted nitrogen doped carbon (AuNPs@NC), which is fabricated by in situ dispersion of gold nanoparticles in a wool keratin assisted porous carbon precursor. The best treatment condition of the sensitive materials is obtained by comparing the sensitivity of humidity response. Moreover, the as-prepared biocompatible flexible sensor was successfully used to detect human respiration.

Tailoring NiCoAl layered double hydroxide nanosheets for assembly of high-performance asymmetric supercapacitors.

NiCoAl layered double hydroxide nanosheets (NiCoAl-LDHNs) were prepared by a one-step solvothermal method. The shape and size of the obtained nanosheets are optimized by adjusting the solvothermal time and the molar concentration ratio of Ni2+/Co2+ to obtain the electrode material with the best performance. When the solvothermal time is 9 h and the molar concentration ratio of Ni2+/Co2+ is 1:1, NiCoAl-LDHNs has the best morphology and electrochemical performance. When assembled into a supercapacitor, NiCoAl-LDHN-9 has a high specific capacitance of 1228.5 F g-1 at 1 A g-1. As the current density is increased to 20 A g-1, the specific capacitance is 1001.8 F g-1, which still has a high capacitance retention of 81.6%. When NiCoAl-LDHN-9 was assembled into an asymmetric supercapacitor, NiCoAl-LDHN-9//AC has a specific capacitance of 102.1 F g-1 at 0.5 A g-1. The asymmetric supercapacitor devices also show excellent electrochemical performance in terms of energy density (35.9 Wh kg-1 at 225.8 W kg-1), power density (4.8 kW kg-1 at 22.2 Wh kg-1) and cycle life (capacitance retention rate after 10,000 cycles is 87.1%). Those results indicate that NiCoAl-LDHN have the potential to be promising electrode materials for high performance supercapacitors.

Flexible and disposable gold nanoparticles-N-doped carbon-modified electrochemical sensor for simultaneous detection of dopamine and uric acid.

Catalytic and electrocatalytic applications of supported metal nanoparticles are hindered due to an aggregation of metal nanoparticles and catalytic leaching under harsh operations. Hence, stable and leaching free catalysts with high surface area are extremely desirable but also challenging. Here we report a gold nanoparticles-hosted mesoporous nitrogen doped carbon matrix, which is prepared using bovine serum albumin (BSA) through calcination. BSA plays three roles in this process as a reducing agent, capping agent and carbon precursor, hence the protocol exhibits economic and sustainable. Gold nanoparticles at N-doped BSA carbon (AuNPs@NBSAC)-modified three-electrode strip-based flexible sensor system has been developed, which displayed effective, sensitive and selective for simultaneous detection of uric acid (UA) and dopamine (DA). The AuNPs@NBSAC-modified sensor showed an excellent response toward DA with a linear response throughout the concentration range from 1 to 50 µM and a detection limit of 0.05 µM. It also exhibited an excellent response toward UA, with a wide detection range from 5 to 200 µM as well as a detection limit of 0.1 µM. The findings suggest that the AuNPs@NBSAC nanohybrid reveals promising applications and can be considered as potential electrode materials for development of electrochemical biosensors.

Programing Performance of Silk Fibroin Superstrong Scaffolds by Mesoscopic Regulation among Hierarchical Structures.

To design higher-strength natural scaffold materials, wool keratin (WK) rich in α-helix structures is used as a well-defined foreign substrate, which induces the formation of ß-crystallites in silk fibroin (SF). Consequently, the macroscopic properties of silk materials (such as the rheological properties of SF hydrogels and the mechanical properties of stents) can be manipulated by governing the change in the hierarchical mesoscopic structure of silk materials. In this work, by monitoring the structure and morphology in the SF gel process, the mechanism of the effect of keratin on SF network formation was speculated, which was further used to design ultra-high-strength protein scaffolds. It has been confirmed that WK accelerates the gelation of SF by reducing the multistep nucleation barrier and increasing the primary nucleation sites, and then establishing a high-density SF domain network. The modulus of the protein composite scaffold prepared by this facile strategy can reach 11.55 MPa, and the MC-3T3 cells can grow well on the scaffold surface. The results suggest that freeze-dried biocompatible SF-based scaffolds are potential candidates for bone tissue engineering.

A Machine-Fabricated 3D Honeycomb-Structured Flame-Retardant Triboelectric Fabric for Fire Escape and Rescue.

Fire disaster is one of the most common hazards that threaten public safety and social development: how to improve the fire escape and rescue capacity remains a huge challenge. Here, a 3D honeycomb-structured woven fabric triboelectric nanogenerator (F-TENG) based on a flame-retardant wrapping yarn is developed. The wrapping yarn is fabricated through a continuous hollow spindle fancy twister technology, which is compatible with traditional textile production processes. The resulting 3D F-TENG can be used in smart carpets as a self-powered escape and rescue system that can precisely locate the survivor position and point out the escape route to timely assist victim search and rescuing. As interior decoration, the unique design of the honeycomb weaving structure endows the F-TENG fabric with an excellent noise-reduction ability. In addition, combining with its good machine washability, air permeability, flame-retardency, durability, and repeatability features, the 3D F-TENG may have great potential applications in fire rescue and wearable sensors as well as smart home decoration.

From Molecular Reconstruction of Mesoscopic Functional Conductive Silk Fibrous Materials to Remote Respiration Monitoring.

Turning insulating silk fibroin materials into conductive ones turns out to be the essential step toward achieving active silk flexible electronics. This work aims to acquire electrically conductive biocompatible fibers of regenerated Bombyx mori silk fibroin (SF) materials based on carbon nanotubes (CNTs) templated nucleation reconstruction of silk fibroin networks. The electronical conductivity of the reconstructed mesoscopic functional fibers can be tuned by the density of the incorporated CNTs. It follows that the hybrid fibers experience an abrupt increase in conductivity when exceeding the percolation threshold of CNTs >35 wt%, which leads to the highest conductivity of 638.9 S m-1 among organic-carbon-based hybrid fibers, and 8 times higher than the best available materials of the similar types. In addition, the silk-CNT mesoscopic hybrid materials achieve some new functionalities, i.e., humidity-responsive conductivity, which is attributed to the coupling of the humidity inducing cyclic contraction of SFs and the conductivity of CNTs. The silk-CNT materials, as a type of biocompatible electronic functional fibrous material for pressure and electric response humidity sensing, are further fabricated into a smart facial mask to implement respiration condition monitoring for remote diagnosis and medication.

Continuous and Scalable Manufacture of Hybridized Nano-Micro Triboelectric Yarns for Energy Harvesting and Signal Sensing.

Textile-based triboelectric nanogenerators (TENG) that can effectively harvest biomechanical energy and sense multifunctional posture and movement have a wide range of applications in next-generation wearable and portable electronic devices. Hence, bulk production of fine yarns with high triboelectric output through a continuous manufacturing process is an urgent task. Here, an ultralight single-electrode triboelectric yarn (SETY) with helical hybridized nano-micro core-shell fiber bundles is fabricated by a facile and continuous electrospinning technology. The obtained SETY device exhibits ultralightness (0.33 mg cm-1), extra softness, and smaller size (350.66 µm in diameter) compared to those fabricated by conventional fabrication techniques. Based on such a textile-based TENG, high energy-harvesting performance (40.8 V, 0.705 µA cm-2, and 9.513 nC cm-2) was achieved by applying a 2.5 Hz mechanical drive of 5 N. Importantly, the triboelectric yarns can identify textile materials according to their different electron affinity energies. In addition, the triboelectric yarns are compatible with traditional textile technology and can be woven into a high-density plain fabric for harvesting biomechanical energy and are also competent for monitoring tiny signals from humans or insects.

Layer-by-layer immobilizing of polydopamine-assisted ε-polylysine and gum Arabic on titanium: Tailoring of antibacterial and osteogenic properties.

Bacterial infection has become a crucial reason that give rise to failure of medical implants in clinical applications. In this regard, various antibacterial surface modifications of implants have been developed in recent years. However, it remains a challenge to enable the implant surfaces with both suitable antibacterial and osteogenic properties. In this work, ε-polylysine and gum Arabic multilayer composite films were immobilized layer by layer (LBL) on anodized titanium with the assistance of polydopamine for the first time. In vitro antibacterial results showed that the bacteria numbers decreased with an increase in the loading amount of ε-polylysine. Furthermore, long-term antibacterial property up to 3 weeks against both gram-positive Staphylococcus aureus (S. aureus) and gram-negative Escherichia coli (E. coli) was obtained combined with the merits of covalent binding and LBL methods. Meanwhile, the cell proliferation and osteogenic differentiation of BMSCs on titanium dioxide nanotubes (TNTs) modified with composite films was significantly improved. Remarkably, a facile method to optimize anti-infective and osteogenic properties of medical titanium has been developed, and it was demonstrated that the ε-polylysine and gum Arabic multilayer composite films with assistance of polydopamine were able to endow the orthopedic implant materials both improved antibacterial property and excellent biocompatibility, which is of profound significance for practical application of titanium-based implants.

Tailoring the Meso-Structure of Gold Nanoparticles in Keratin-Based Activated Carbon Toward High-Performance Flexible Sensor.

Flexible biosensors with high accuracy and reliable operation in detecting pH and uric acid levels in body fluids are fabricated using well-engineered metal-doped porous carbon as electrode material. The gold nanoparticles@N-doped carbon in situ are prepared using wool keratin as both a novel carbon precursor and a stabilizer. The conducting electrode material is fabricated at 500 °C under customized parameters, which mimics A-B type (two different repeating units) polymeric material and displays excellent deprotonation performance (pH sensitivity). The obtained pH sensor exhibits high pH sensitivity of 57 mV/pH unit and insignificant relative standard deviation of 0.088%. Conversely, the composite carbon material with sp2 structure prepared at 700 °C is doped with nitrogen and gold nanoparticles, which exhibits good conductivity and electrocatalytic activity for uric acid oxidation. The uric acid sensor has linear response over a range of 1-150 µM and a limit of detection 0.1 µM. These results will provide new avenues where biological material will be the best start, which can be useful to target contradictory applications through molecular engineering at mesoscale.

Hierarchical Structure of Silk Materials Versus Mechanical Performance and Mesoscopic Engineering Principles.

A comprehensive review on the five levels of hierarchical structures of silk materials and the correlation with macroscopic properties/performance of the silk materials, that is, the toughness, strain-stiffening, etc., is presented. It follows that the crystalline binding force turns out to be very important in the stabilization of silk materials, while the ß-crystallite networks or nanofibrils and the interactions among helical nanofibrils are two of the most essential structural elements, which to a large extent determine the macroscopic performance of various forms of silk materials. In this context, the characteristic structural factors such as the orientation, size, and density of ß-crystallites are very crucial. It is revealed that the formation of these structural elements is mainly controlled by the intermolecular nucleation of ß-crystallites. Consequently, the rational design and reconstruction of silk materials can be implemented by controlling the molecular nucleation via applying sheering force and seeding (i.e., with carbon nanotubes). In general, the knowledge of the correlation between hierarchical structures and performance provides an understanding of the structural reasons behind the fascinating behaviors of silk materials.

An efficient disposable and flexible electrochemical sensor based on a novel and stable metal carbon composite derived from cocoon silk.

The present work reports cocoon silk fibroin (SF)as a unique precursor for the in-situ fabrication of well-engineered, stable and leach free gold nanoparticle doped carbonaceous materials (AuNPs@NSC). In principle, at the molecular level, SF has a singular structure that can be converted to a N-doped aromatic carbon structure by heat treatment. The electrochemical properties of the prepared nanocomposite were examined by cyclic voltammetry and differential pulse voltammetry. A flexible three electrode sensor system with AuNPs@NSC-modified working electrodes has been developed, to achieve easy operation and quick and accurate responses. The electrochemical results showed that the sensor made by the AuNPs@NSC-modified working electrode demonstrated high sensitivity for the detection of rutin, which is attributed to the good distribution of the AuNPs on the carbon matrix. Using differential pulse voltammetry (DPV), the AuNPs@NSC electrode was found to have a linear response in the range of 0.11-250 µM and a comparably low limit of detection of 0.02 µM (S/N = 3). To ensure the accuracy and applicability of the sensors, the concentration of rutin in the commodity (rutin capsule, 10 mg/capsule) was examined, and the sensor provided high precision with a minimum relative error (RE) of 3.3%. These findings suggest that AuNPs@NSC can be considered to be a potential electrode material for the development of electrochemical devices and has great potential in extending their application to the flexible sensor field.

All-Textile Electronic Skin Enabled by Highly Elastic Spacer Fabric and Conductive Fibers.

Electronic fabrics that combine traditional fabric with intelligent functionalities have attracted increasing attention. Here an all-fabric pressure sensor with a wireless battery-free monitoring system was successfully fabricated, where a 3D penetrated fabric sandwiched between two highly conductive fabric electrodes acts as a dielectric layer. Thanks to the good elastic recovery of the spacer fabric, the capacitance pressure sensor exhibits a high sensitivity of 0.283 KPa-1 with a fast response time and good cycling stability (≥20 000). Water-soluble poly(vinyl alcohol) template-assisted silver nanofibers were constructed on the high-roughness fabric surface to achieve high conductivity (0.33 Ω/sq), remarkable mechanical robustness, and good biocompatibility with human skin. In addition, the coplanar fabric sensor arrays were successfully designed and fabricated to spatially map resolved pressure information. More importantly, the gas-permeable fabrics can be stuck on the skin for wireless real-time pressure detection through a fiber inductor coil with a resonant frequency shift sensitivity of 6.8 MHz/kPa. Our all-fabric sensor is more suitable for textile technology compared with traditional pressure sensors and exhibited wide potential applications in the field of intelligent fabric for electronic skin.

Primary and Secondary Mesoscopic Hybrid Materials of Au Nanoparticles@Silk Fibroin and Applications.

In this work, we demonstrate the principle of mesoscopic construction of silk fibroin (SF) hybrid materials, which endows the materials with new performance. In implementing this strategy, mediating molecules, wool keratin (WK) molecules, were adopted to in-line synthesize Au nanoparticles (WK@AuNPs), which further create the stable linkage of AuNPs with SF nanofibril networks via templated ß-crystallization. Fourier transform infrared spectroscopy, X-ray diffraction, and atomic force microscopy demonstrate that the mesoscopic hybrid network structure of the hybrid materials is different from neat SF materials, which gives rise to various new performances, that is, long-stable fluorescence emission. As the fluorescence emission can be characteristically annealed by Cu ions, therefore be adopted as the highly selective ion probes. Moreover, as WK@AuNPs are homogeneously connected to SF nanofibril networks, the carbonization of the materials leads to secondary hybrid materials of carbon-Au, where nano-sized Au particles are well distributed in carbonized mesoscopic conductive carbon networks. Such hybrid materials of carbon-Au can be further fabricated into electrochemical (i.e., dopamine) sensors, which are demonstrated to have excellent sensing performance.

Solar energy assisted starch-stabilized palladium nanoparticles and their application in C-C coupling reactions.

Present work reports a novel one step, greener protocol for the synthesis of starch-stabilized palladium nanoparticles (PdNPs) with an average particle diameter of 30-40 nm. These particles were stable and uniform in size. In present protocol, the concentrated solar energy mediated reduction of palladium chloride was achieved by using citric acid as a reducing agent and starch as a capping agent. UV-Visible spectroscopy, Transmission Electron Microscopy, Field Emission Gun-Scanning Electron Microscopy, Selected Area Electron Diffraction and Electron dispersive X-ray Spectral analysis techniques were used to characterize this starch capped PdNPs. Herein; we are reporting such combination of starch and citric acid in the synthesis of PdNPs for the first time. The catalytic activity of synthesized nanoparticles has been checked for Suzuki and Heck cross coupling reactions. The product yield was confirmed by GC. The products were confirmed using GC-MS analysis and also using GC with the help of authentic standards. Solar energy assisted starch stabilized PdNPs showed excellent activity in the C-C bond formation between aryl halides (I, Br) with phenyl boronic acid and its derivatives. In addition, the catalyst showed good activity in the Heck coupling reaction of C-C bond formation of aryl halides with aromatic alkene. The use of starch, citric acid, water and solar energy makes present protocol greener.