Anisotropic architecture and electrical stimulation enhance neuron cell behaviour on a tough graphene embedded PVA: alginate fibrous scaffold

Tough scaffolds comprised of aligned and conductive fibers are promising for peripheral nerve regeneration due to their unique mechanical and electrical properties. Several studies have confirmed that electrical stimulation can control the axonal extension in vitro. However, the stimulatory effects of scaffold architecture and electrical stimulation have not yet been investigated in detail. Here, we assessed a comparison between aligned and random fibers made of graphene (Gr) embedded sodium alginate (SA) polyvinyl alcohol (PVA) (Gr-AP scaffolds) for peripheral nerve engineering. The effects of applied electrical stimulation and orientation of the fabricated fibers on the in vitro attachment, alignment, and proliferation of PC12 cells (a rat neuronal cell line) were investigated. The results revealed that the aligned fibrous Gr-AP scaffolds closely mimicked the anisotropic structure of the native sciatic nerve. Aligned fibrous Gr-AP scaffolds significantly improved mechanical properties as well as cell-scaffold integration compared to random fibrous scaffolds. In addition, electrical stimulation significantly improved PC12 cell proliferation. In summary, our findings revealed that aligned fibrous Gr-AP scaffolds offered superior mechanical characteristics and structural properties that enhanced neural cell–substrate interactions, resulting in a promising construct for nerve tissue regeneration.

Tough scaffolds comprised of aligned and conductive fibers are promising for peripheral nerve regeneration due to their unique mechanical and electrical properties.     

A conductive sodium alginate and carboxymethyl chitosan hydrogel doped with polypyrrole for peripheral nerve regeneration

Polymer materials with electrically conductive properties have good applications in their respective fields because of their special properties. However, they usually exhibited poor mechanical properties and biocompatibility. In this work, we present a simple approach to prepare conductive sodium alginate (SA) and carboxymethyl chitosan (CMCS) polymer hydrogels (SA/CMCS/PPy) that can provide sufficient help for peripheral nerve regeneration. SA/CMCS hydrogel was cross-linked by calcium ions provided by the sustained release system consisting of d-glucono-δ-lactone (GDL) and superfine calcium carbonate (CaCO₃), and the conductivity of the hydrogel was provided by doped with polypyrrole (PPy). Gelation time, swelling ratio, porosity and Young''s modulus of the conductive SA/CMCS/PPy hydrogel were adjusted by polypyrrole content, and the conductivity of it was within 2.41 × 10⁻⁵ to 8.03 × 10⁻³ S cm⁻¹. The advantages of conductive hydrogels in cell growth were verified by controlling electrical stimulation of cell experiments, and the hydrogels were also used as a filling material for the nerve conduit in animal experiments. The SA/CMCS/PPy conductive hydrogel showed good biocompatibility and repair features as a bioactive biomaterial, we expect this conductive hydrogel will have a good potential in the neural tissue engineering.

Polymer materials with electrically conductive properties have good applications in their respective fields because of their special properties.     

A study on graphene composites for peripheral nerve injury repair under electrical stimulation

Electrical stimulation (ES) provides an effective alternative to peripheral nerve repair via conductive scaffolds. The aim of the present study is to investigate a graphene (GR)/thermoplastic polyurethane (TPU) composite for the repair of peripheral nerve injury under ES. To this end, conductive composite membranes were fabricated by blending GR (2, 4 and 6 wt%) with TPU. GR maintains its own structure in the composite and enhances the mechanical and electrical properties of the composite. The composites with excellent biocompatibility had a hemolysis rate of less than 5%. As a result, the 4GR–TPU (4 wt% GR) sample with enhanced mechanical properties possessed the highest conductivity value of 33.45 ± 0.78 S m⁻¹. Compared with the non-conductive sample, 4GR–TPU was favorable for the viability of Schwann cells (SCs) under ES. When different voltages of ES were applied, a direct current of 10 mV was more suitable for the growth and proliferation of SCs. This study provides beneficial information for peripheral nerve repair via ES.

Electrical stimulation (ES) provides an effective alternative to peripheral nerve repair via conductive scaffolds.     

Designable core–shell graphite particles for thermally conductive and electrically insulating polymer composites

Electrically insulating graphite particles were prepared by coating graphite with electrically insulating materials via a two-step mechanical mixing process. Graphite particles were treated with a binder in the 1^st mixing process and coated with an electrically insulating particle in the 2^nd mixing process under high shear forces within a short processing time (below 1 min). Micron-sized graphite particles were successfully coated with various inorganic particles of appropriate particle diameter. Talc and boron nitride exhibited good affinities with graphite and formed effective coating layers to render reliable electrical insulation. Graphite coated with talc and boron nitride exhibited a high volume resistivity, greater than 10⁹ Ω cm. The insulating property was retained even after compounding and moulding the coated graphite particles with a polymer. The two-step coating process under high shear forces is a promising method for production of coated graphite particles.

Core–shell graphite particles were successfully prepared via a mechanical mixing process. The thermally conductive and electrically insulating properties were designable for injection mouldable polymer composites.     

Novel double anisotropic conductive flexible composite film endued with improved luminescence

Brand-new double anisotropic conductive flexible composite films (ACFs) were firstly put forward, devised and fabricated. The flexible array composite films were constructed via electrospinning using highly aligned Janus nanoribbons as conductive and constitutive units. The Janus nanoribbon consists of two parts, which are respectively conducting side and insulating-luminescent side. The Janus nanoribbons array composite film has two layers, and the two layers are combined tightly to form a top-to-bottom structure. In the composite film, the length direction of the Janus nanoribbons (namely conducting direction) in the two layers is perpendicular, so that a composite film with double electrically conductive anisotropy is achieved. In addition, by adjusting the content of PANI, conductive anisotropy of each layer of the composite film can be tuned, and the conductance in the conducting direction is about 10⁸ times stronger than that in the insulating direction. The Janus nanoribbon array composite films also have tunable and improved luminescent properties, achieving bi-functionality of double anisotropically electrical conduction and luminescence. The proposed design concept and preparation technology will provide theoretical and technical support for the design and fabrication of novel multifunctional ACFs.

Brand-new double anisotropic conductive flexible composite films endued with tuned electrically conductive anisotropy and improved luminescence were prepared by electrospinning.     

Carbon nanotubes as electrophysiological building blocks for a bioactive cell scaffold through biological assembly to induce osteogenesis

Bio-functional cell scaffolds have great potential in the field of tissue regenerative medicine. In this work, a carbon nanotube (CNT) gel scaffold via specific pairing of functionalized nucleobases was developed for specifically targeted drug delivery and in vitro osteogenesis. The CNT gel scaffold with nano-fibrous architectures was established by Watson–Crick base pairing between thymine and adenine of low molecular weight heparin, respectively. As scaffold precursors, adenine and thymine functionalized heparin derivatives could additionally bind cell growth factors by the affinity interaction. The resulting nano-fibrous gel scaffolds showed excellent mechanical integrity and advanced electro-physiological functions. Potential application of the electrophysiological CNT gel scaffold in bone tissue engineering was confirmed by encapsulation of human adipose-derived stem cells (ASCs). Our results indicate that the electrically conductive networks formed by CNTs within the nano-fibrous framework are the key characteristics of cell scaffolds leading to improved ASC organization and differentiation by an extra electrical stimulus (ES). Specifically, ASCs cultured in bio-electrical gel scaffolds showed ∼4 times higher spontaneous osteogenesis in combination with bone morphogenetic protein 2 (BMP-2), compared to those cultured on pristine hydrogels. This electrophysiological CNT gel scaffold containing BMP-2 exhibited beneficial effects on ASC activity and osteogenetic differentiation, which suggested a promising future for local treatment of bone regeneration.

Bio-functional cell scaffolds have great potential in the field of tissue regenerative medicine.     

Construction of a graphene/polypyrrole composite electrode as an electrochemically controlled release system

A new class of stimuli responsive drug delivery systems is emerging to establish new paradigms for enhancing therapeutic efficacy. To date, most electro-responsive systems rely on noble metal electrodes that likely cause the limitations for implantation applications. Herein, a graphene/polypyrrole composite electrode (GN–PPy–FL) was fabricated based on two-dimensional (2D) graphene (GN) film and conductive and biocompatible polypyrrole (PPy) nanoparticles loaded with a negative drug model of fluorescein sodium (FL) via chemical oxidation polymerization. The conductive composite electrode was utilized as a drug carrier to realize the electrically controlled release of the FL. The release rate from conductive nanoparticles can be controlled by the applied voltages. The study provides a multi-stimuli responsive drug release system, demonstrating the potential applications of the controlled release of various drugs, peptides or proteins.

A biocompatible conductive composite electrode GN–PPy–FL can realize controlled release of a drug model triggered by low voltages.     

Roll-to-roll continuous carbon nanotube sheets with high electrical conductivity

Large scale manufacturing of electrically conductive carbon nanotube (CNT) sheets with production capability, low cost, and long-term electrical performance stability is still a challenge. A new method to fabricate highly conductive continuous buckypaper (CBP) with roll-to-roll production capability and relatively low cost is reported. The electrical conductivity of CBP can be improved to 7.6 × 10⁴ S m⁻¹ by using an oxidant chemical (i.e. HNO₃ and I₂) doping method. To compensate for the conductivity degradation caused by the instability of the oxidant chemical doping, a polymer layer of poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) was coated on the chemically doped CBP. The fabricated highly conductive CBP showed stable electrical performance in air for more than a month. This CBP material with high electrical conductivity, relatively low cost, and roll-to-roll manufacturing capability could enable a wide range of engineering applications including flexible conductors, electromagnetic interference (EMI) shielding materials, and electrodes in energy devices.

Highly electrically conductive, roll-to-roll continuous buckypaper (CBP) with stable performance was achieved by chemical doping and polymer coating (PEDOT:PSS).     

A novel lamellar structural biomaterial and its effect on bone regeneration

To evaluate a novel lamellar structural biomaterial as a potential biomaterial for guided bone regeneration, we describe the preparation of a collagen membrane with high mechanical strength and anti-enzyme degradation ability by using the multi-level structure of Ctenopharyngodon idella scales. The physical and chemical properties, in vitro degradation, biocompatibility, and in vivo osteogenic activity were preliminarily evaluated. In conclusion, it was shown that the multi-layered collagen structure material had sufficient mechanical properties, biocompatibility, and osteogenic ability. Meanwhile, it is also shown that there is a gap in current clinical needs, between the guided tissue regeneration membrane and the one being used. Therefore, this study provides useful insights into the efforts being made to design and adjust the microstructure to balance its mechanical properties, degradation rate, and osteogenic activity.

To evaluate a novel lamellar structural biomaterial for guided bone regeneration, we describe the preparation of a collagen membrane with high mechanical strength and anti-enzyme degradation ability using Ctenopharyngodon idella scales.     

Hypercrosslinked phenothiazine-based polymers as high redox potential organic cathode materials for lithium-ion batteries

Organic cathode materials have been demonstrated to be highly promising sustainable cathode materials for rechargeable lithium-ion batteries. However, the low redox potentials, low electrical conductivity, and the undesirable dissolution in organic electrolytes greatly limit their applications. Herein, two insoluble hypercrosslinked porous conductive polymers with phenothiazine motifs, HPEPT and HPPT, were successfully accomplished with high and stable discharge potentials at 3.65 and 3.48 V versus Li/Li⁺. HPEPT and HPPT with good electrical conductivity exhibited outstanding rate capabilities (up to 800 mA g⁻¹) even at a high mass loading up to 70 wt%. This study shows that excellent organic cathode materials could be achieved readily through this prudent design.

Hypercrosslinked conductive polymers with phenothiazine motifs were achieved and studied as organic cathode materials, exhibiting excellent electrochemical performance.     

Solvent-free electrically conductive Ag/ethylene vinyl acetate (EVA) composites for paper-based printable electronics

Solvent-free electrically conductive composites have been applied to flexible electronics to obtain high electrical conductivity. However, some of the proposed composites have low electrical conductivities and are unable to meet the requirements of commercial printable electronics. In this study, solvent-free electrically conductive Ag/EVA (ethylene vinyl acetate) composites for paper-based printable electronics were prepared by a thermal melting method. The properties of these electrically conductive Ag/EVA composites, including particle sizes, morphologies and phase purities of the flake silver flake powders, were investigated using a particle size analyzer, scanning electron microscopy (SEM) and X-ray diffraction (XRD), respectively. The results showed that nanometer-thick flake silver flake powders with smooth and flat surfaces were made by the nanofilm transition technique. These obtained powders were able to form smooth face-to-face contacts, which facilitated the formation of an excellent conductive network in the conductive system. Dynamic mechanical analysis (DMA) was conducted to investigate the mechanical properties of EVA and Ag/EVA composites. A Fourier transformation infra-red (FTIR) spectrometer, laser micro-Raman spectrometer and thermogravimetric analyzer were used to analyze the organic functional groups, glass transition temperatures and thermal weight losses of the EVA resin and solvent-free electrically conductive composites. The solvent-free electrically conductive Ag/EVA composite, which contained 55 wt% of the as-prepared flake silver flake powders, was found to have an extremely low volume resistivity of 1.23 × 10⁻⁴ Ω cm as well as excellent bending performance and adhesion. These features indicate the great potential of these composites for application in printed electronics.

A novel type of solvent-free electrically conductive Ag/EVA composite for paper-based printable electronics was prepared through a thermal melting method.     

All-organic,conductive and biodegradable yarns from core–shell nanofibers through electrospinning

Electrically conductive and biodegradable materials are desired for a range of applications in wearable electronics to address the growing ecological problem of e-waste. Herein, we report on the design and fabrication of all-organic, conductive and biodegradable nanofibrous core–shell yarn produced by in situ polymerization of aniline on the surface of electrospun poly(ε-caprolactone) nanofibers. The effect of concentration of aniline monomer on the morphology and resistivity of deposited polyaniline layer was investigated. The electrical resistance changed almost instantaneously with the strain for multiple stretch and recovery cycles. This rapid and sensitive response to mechanical loading and unloading is promising to validate the possibility of using the conductive yarns as strain sensors for monitoring human motion. Increasing the number of plies of yarn to three resulted in a three-fold reduction of the resistance. The twisted plied yarns were incorporated into fabric by stitching to demonstrate their use as a wearable electrode for capacitive sensors. This approach presents an early step in realizing all-organic conductive biodegradable nanofibrous yarns for biodegradable smart textiles.

A nanofibrous yarn that changes the electrical resistance instantaneously with the strain for multiple stretch and recovery cycles.     

Diazonium-functionalized thin films from the spontaneous reaction of p-phenylenebis(diazonium) salts

Salts of the diazonium coupling agent p-phenylenebis(diazonium) form diazonium-terminated conjugated thin films on a variety of conductive and nonconductive surfaces by spontaneous reaction of the coupling agent with the surface. The resulting diazonium-bearing surface can be reacted with various organic and inorganic nucleophiles to form a functionalized surface. These surfaces have been characterized with voltammetry, XPS, infrared and Raman spectroscopy, and atomic force microscopy. Substrates that can be conveniently and quickly modified with this process include ordinary glass, gold, and an intact, fully assembled commercial screen-printed carbon electrode. The scope and convenience of this process make it promising for practical surface modification.

We present a surface functionalization procedure based on diazonium-functionalized thin films produced by spontaneous surface grafting of p-phenylene-bis(diazonium) cation.     

Flexible PEBAX/graphene electromagnetic shielding composite films with a negative pressure effect of resistance for pressure sensors applications

In the current work, we fabricated flexible poly(ether-block-amide) (PEBAX)/graphene composite films by a combination of facile melt blending and compression molding technique. The graphene content significantly affects the mechanical properties, electrical conductivity and electromagnetic interference (EMI) shielding performance. An electrically conductive percolation threshold of 1.75 vol% graphene was obtained in the PEBAX/graphene composites. With the introduction of 4.45 vol%, and 8.91 vol% graphene content, the average EMI SE of composite films could reach 16.6 and 30.7 dB, respectively. More interestingly, the PEBAX/graphene composite exhibited a nearly-linear negative pressure coefficient (NPC) effect of resistance with increasing outer pressure stimulation, which was attributed to the formation of more conductive pathways caused by the decreased distance between adjacent graphene. In addition, these composites demonstrated good sensing stability, recoverability and reproducibility after stabilization by cyclic pressure loading. The current study provides guidelines for the large-scale preparation of elastomer NPC sensors and smart EMI shielding devices.

Graphene/PEBAX composite films present high-efficiency EMI shielding properties and good sensitivity as well as sensing stability.     

Self-assembled functional components-doped conductive polypyrrole composite hydrogels with enhanced electrochemical performances

A conductive hydrogel is a composite conductive material formed by combining a conductive polymer with a nanogel structure of a hydrogel. Conductive hydrogels not only have potential applications in supercapacitors, sensors, and modulators, they can also be synthesized by many methods, such as copolymerization, crosslinking, and grafting. In this work, we successfully prepared three conductive composite hydrogels by in situ polymerization, namely polypyrrole sodium alginate conductive hydrogel, ferric chloride-doped polypyrrole sodium alginate hydrogel and doped polypyrrole sodium alginate hydrogel with sodium dodecylbenzene sulfonate. In addition, a series of characterizations were performed for the three conductive hydrogels described above. The results show that the polypyrrole sodium alginate hydrogel doped with ferric chloride forms a nanofiber network with a more stable structure and better electrochemical performance.

New functional components-doped conductive polypyrrole composite hydrogels are prepared via a self-assembled process, demonstrating potential applications in catalysis as well as electrochemical materials.     

Laminin-modified gellan gum hydrogels loaded with the nerve growth factor to enhance the proliferation and differentiation of neuronal stem cells

The reconstruction of peripheral nerves has lately received great attention as many patients suffer from peripheral nerve injury every year around the world. However, the damage to human nerve cells has different degrees of irreversibility due to a slow growth speed and low adhesion with the surrounding tissues. In an effort to overcome this challenge, we applied novel laminin (LN)-modified thiolated gellan gum (TGG) and loaded the nerve growth factor (NGF) as a tissue engineering scaffold for facilitating neuronal stem cell proliferation via a synergy effect for the ERK–MAPK pathway. TGG was characterized by ¹H NMR spectroscopy and scanning electron microscopy, and its rheological behavior was also studied. The NGF release curve fitted the Korsmeyer–Peppas model and belonged to a Fickian diffusion-controlled release mechanism. The neuronal stem cells from newborn SD rats could adhere tightly and proliferate at a relatively rapid speed, showing excellent biocompatibility and the ability to promote growth in the modified TGG. LN and NGF could decrease the apoptosis effects of neuronal stem cells, as shown via the flow cytometry results. In a three-dimensional culture environment, LN and NGF could facilitate neuronal stem cells to differentiate into neurons, as proved by immunofluorescence, q-PCR, and western blot analyses. Therefore, the rational design of the TGG gel loaded with NGF has promising applications in the reconstruction of peripheral nerves.

Laminin-modified thiolated gellan gum and loaded with the nerve growth factor in facilitateding neuronal stem cell proliferation and differentiation.     

Atomic scale study of black phosphorus degradation

Black phosphorus (BP) is a promising two-dimensional (2D) material for future electronic devices due to its unique properties of high carrier mobility and large band gap tunability. However, thinner crystalline BP is more readily degraded under ambient conditions. For BP-based electronic devices, degradation of the exfoliated BP is a key issue. However, the nanometer scale study of BP degradation is rare so far. Herein, we report an atomically resolved degradation process of the BP surface using atomic force microscopy under temperature- and humidity-controlled environments. The atomically resolved crystal surface of BP deteriorated due to surface etching after cleavage, and showed monolayer etching. The etching process is accelerated by applying a bias voltage to BP via a conductive tip. After the voltage-assisted BP etching, the BP etching product shows crystalline BP confirmed by Raman spectroscopy and atomic force microscopy. Our atomic scale study of BP will be useful for the future 2D-based electronic devices to overcome conventional silicon-based electronic devices.

Atomic scale degradation of black phosphorus has been revealed by atomic force microscopy.     

Enhanced production of optical (S)-acetoin by a recombinant Escherichia coli whole-cell biocatalyst with NADH regeneration

Acetoin is an important platform chemical with a variety of applications in foods, cosmetics, chemical synthesis, and especially in the asymmetric synthesis of optically active pharmaceuticals. It is also a useful breath biomarker for early lung cancer diagnosis. In order to enhance production of optical (S)-acetoin and facilitate this building block for a series of chiral pharmaceuticals derivatives, we have developed a systematic approach using in situ-NADH regeneration systems and promising diacetyl reductase. Under optimal conditions, we have obtained 52.9 g L⁻¹ of (S)-acetoin with an enantiomeric purity of 99.5% and a productivity of 6.2 g (L h)⁻¹. The results reported in this study demonstrated that the production of (S)-acetoin could be effectively improved through the engineering of cofactor regeneration with promising diacetyl reductase. The systematic approach developed in this study could also be applied to synthesize other optically active α-hydroxy ketones, which may provide valuable benefits for the study of drug development.

Enhanced production of optical (S)-acetoin by a recombinant Escherichia coli whole-cell biocatalyst with NADH regeneration systems.     

Biodegradable copolypeptide hydrogel prodrug accelerates dermal wound regeneration by enhanced angiogenesis and epithelialization

Hydrogels are one of the most promising wound dressings. However, their effectiveness on wound healing is still largely limited due to either the non-degradability or the release of non-therapeutic degradable products. Herein, a biodegradable copolypeptide hydrogel based on the glutamic acid and lysine was synthesized and applied as both wound dressing and therapeutic prodrug. The hydrogel can degrade in the existence of elevated degradative enzymes in a wound environment, which will release therapeutic amino acids to enhance the wound healing. In vivo results found that the hydrogel could effectively promote wound regeneration in both macroscopic and microscopic scales. Further investigation revealed that the wound healing effect of the hydrogel was highly attributed to its enhanced impact on angiogenesis, cell proliferation and re-epithelialization of the wound. All in all, the present study proves that the degradable copolypeptide hydrogel can efficiently improve wound healing and indicates its potent clinical application for wound regeneration.

Biodegradable hydrogel as a wound dressing and therapeutic prodrug promoting wound regeneration through enhanced angiogenesis and epithelialization.     

Nanofiller-conjugated percolating conductive network modified polymerization reaction characteristics of aromatic thermosetting copolyester resin

Deliberately controlled interfacial interactions between incorporated nanofiller particles and host polymer backbone chains constitute a critical element in the realm of polymer nanocomposites with tailorable multifunctional properties. We demonstrate the physicochemical effects induced by graphene nanoplatelets (GNP) of different sizes on the condensation polymerization reaction of aromatic thermosetting copolyester (ATSP) through the formation of electrically conductive percolating networks as enabled by interfacial interactions. Carboxylic acid and acetoxy-capped precursor oligomers of ATSP are solid-state mixed with chemically pristine GNP particles at various loading levels. Upon in situ endothermic condensation polymerization reaction, crosslinked backbone of the ATSP foam matrix is formed while the carbonaceous nanofillers are incorporated into the polymer network via covalent conjugation with functional end-groups of the oligomers. The controlled GNP size promotes different electrical percolation thresholds and ultimate electrical conductivities. Microstructural analysis demonstrates GNP distributions in the matrix as well as morphological modifications induced by the formation of conductive percolating GNP networks. Cure characteristics reveal the thermochemical changes prompted in the polymerization processes for GNP content above the requirement for percolation formation. Chemical spectroscopy of the ATSP nanocomposite morphology exhibits the formation of a robust interfacial coupling mechanism between the GNPs and ATSP backbone. The findings here may guide the developmental efforts of nanocomposites through better identifying roles of the morphology and content of nanofillers in polymerization processes.

Physicochemical effects induced by graphene nanoplatelets on the in situ polycondensation reaction of aromatic thermosetting copolyester through the formation of conductive percolating network assembled via interfacial interactions.