Wet Spinning of Graphene Oxide Fibers with Different MnO2 Additives.

We present the fabrication of graphene oxide (GO) and manganese dioxide (MnO2) composite fibers via wet spinning processes, which entails the effects of MnO2 micromorphology and mass loading on the extrudability of GO/MnO2 spinning dope and on the properties of resulted composite fibers. Various sizes of rod and sea-urchin shaped MnO2 microparticles have been synthesized via hydrothermal reactions with different oxidants and hydrothermal conditions. Both the microparticle morphology and mass loading significantly affect the extrudability of the GO/MnO2 mixture. In addition, the orientation of MnO2 microparticles within the fibers is largely affected by their microscopic surface areas. The composite fibers have been made electrically conductive via chemical or thermal treatments and then applied as fiber cathodes in Zn-ion battery prototypes. Thermal annealing under an argon atmosphere turns out to be an appropriate method to avoid MnO2 dissolution and leaching, which have been observed in the chemical treatments. These rGO/MnO2 fiber cathodes have been assembled into prototype Zn-ion batteries with Zn wire as the anode and xanthan-gum gel containing ZnSO4 and MnSO4 salts as the electrolyte. The resulted electrochemical output depends on the annealing temperature and MnO2 distribution within the fiber cathodes, while the best performer shows stable cycling stability at a maximum capacity of ca. 80 mA h/g.

Nonwoven Membranes with Infrared Light-Controlled Permeability.

This study presents the development of the first composite nonwoven fiber mats (NWFs) with infrared light-controlled permeability. The membranes were prepared by coating polypropylene NWFs with a photothermal layer of poly(N-isopropylacrylamide) (PNIPAm)-based microgels impregnated with graphene oxide nanoparticles (GONPs). This design enables "photothermal smart-gating" using light dosage as remote control of the membrane's permeability to electrolytes. Upon exposure to infrared light, the GONPs trigger a rapid local increase in temperature, which contracts the PNIPAm-based microgels lodged in the pore space of the NWFs. The contraction of the microgels can be reverted by cooling from the surrounding aqueous environment. The efficient conversion of infrared light into localized heat by GONPs coupled with the phase transition of the microgels above the lower critical solution temperature (LCST) of PNIPAm provide effective control over the effective porosity, and thus the permeability, of the membrane. The material design parameters, namely the monomer composition of the microgels and the GONP-to-microgel ratio, enable tuning the permeability shift in response to IR light; control NWFs coated with GONP-free microgels displayed thermal responsiveness only, whereas native NWFs showed no smart-gating behavior at all. This technology shows potential toward processing temperature-sensitive bioactive ingredients or remote-controlled bioreactors.

Modeling the Triboelectric Behaviors of Elastomeric Nonwoven Fabrics.

Theoretical modeling of triboelectric nanogenerators (TENGs) is fundamental to their performance optimization, since it can provide useful guidance on the material selection, structure design, and parameter control of relevant systems. Built on the theoretical model of film-based TENGs, here, an analytical model is introduced for conductor-to-dielectric contact-mode nonwoven-based TENGs, which copes with the unique hierarchical structure of nonwovens and details the correlation between the triboelectric output (maximum transferred charge density) and nonwoven structural parameters (thickness, solidity, and average fiber diameter). A series of styrene-ethylene-butylene-styrene nonwoven samples are fabricated through a melt-blowing process to map nonwoven structural features within certain ranges, while an ion-injection protocol is adopted to quantify the triboelectric output with superior consistency and reproducibility. With a database containing structural features and triboelectric output of 43 nonwoven samples, a good model fitting is achieved via nonlinear regression analysis in Python, which also shows good predictive power and suggests the existing of tribo-output maxima at a specific thickness, solidity, or average fiber diameter when other structural parameters are fixed. The model is also successfully applied to a group of polypropylene meltblown nonwovens, which verifies its universality on meltblown-nonwoven-based TENGs.

Modified gaphene oxide (GO) particles in peptide hydrogels: a hybrid system enabling scheduled delivery of synergistic combinations of chemotherapeutics.

The scheduled delivery of synergistic drug combinations is increasingly recognized as highly effective against advanced solid tumors. Of particular interest are composite systems that release a sequence of drugs with defined kinetics and molar ratios to enhance therapeutic effect, while minimizing the dose to patients. In this work, we developed a homogeneous composite comprising modified graphene oxide (GO) nanoparticles embedded in a Max8 peptide hydrogel, which provides controlled kinetics and molar ratios of release of doxorubicin (DOX) and gemcitabine (GEM). First, modified GO nanoparticles (tGO) were designed to afford high DOX loading and sustained release (18.9% over 72 h and 31.4% over 4 weeks). Molecular dynamics simulations were utilized to model the mechanism of DOX loading as a function of surface modification. In parallel, a Max8 hydrogel was developed to release GEM with faster kinetics and achieve a 10-fold molar ratio to DOX. The selected DOX/tGO nanoparticles were suspended in a GEM/Max8 hydrogel matrix, and the resulting composite was tested against a triple negative breast cancer cell line, MDA-MB-231. Notably, the composite formulation afforded a combination index of 0.093 ± 0.001, indicating a much stronger synergism compared to the DOX-GEM combination co-administered in solution (CI = 0.396 ± 0.034).

Dual-Core Supercapacitor Yarns: An Enhanced Performance Consistency and Linear Power Density.

Pliable energy-storage devices have attracted great attention recently due to their important roles in rapid-growing wearable/implantable electronic systems among which yarn-shaped supercapacitors (YSCs) are promising candidates since they exhibit great design versatility with tunable sizes and shapes. However, existing challenges of YSCs include an inferior power output and poor performance consistency as compared to their planar counterparts, mainly due to their unique linear geometry and curved interfaces. Here, a YSC comprising wet-spun fibers of reduced graphene oxide and MXene sheets is demonstrated, which exhibits prominent decreases in the equivalent series resistance and thus increases in the power output upon increasing the length, which is contradictory to the common expectations of a typical YSC, showing revolutionary promises for practical applications. A much higher power density (2502.6 µW cm-2) can be achieved at an average energy density of 27.1 µWh cm-2 (linearly, 510.9 µW cm-1 at 5.5 µWh cm-1) via our unique dual-core design. The YSCs also present good stability upon stretching and bending, compatible with further textile processing. This work provides new insights into the fabrication of textile-based energy-storage devices for real-world applications.

Screen Printing of Graphene Oxide Patterns onto Viscose Nonwovens with Tunable Penetration Depth and Electrical Conductivity.

Graphene-based e-textiles have attracted great interest because of their promising applications in sensing, protection, and wearable electronics. Here, we report a scalable screen-printing process along with continuous pad-dry-cure treatment for the creation of durable graphene oxide (GO) patterns onto viscose nonwoven fabrics at controllable penetration depth. All the printed nonwovens show lower sheet resistances (1.2-6.8 kΩ/sq) at a comparable loading, as those reported in the literature, and good washfastness, which is attributed to the chemical cross-linking applied between reduced GO (rGO) flakes and viscose fibers. This is the first demonstration of tunable penetration depth of GO in textile matrices, wherein GO is also simultaneously converted to rGO and cross-linked with viscose fibers in our processes. We have further demonstrated the potential applications of these nonwoven fabrics as physical sensors for compression and bending.

Electrospun Mat of Poly(vinyl alcohol)/Graphene Oxide for Superior Electrolyte Performance.

Here, we describe an electrospun mat of poly(vinyl alcohol) (PVA) and graphene oxide (GO) as a novel solid-state electrolyte matrix, which offers better performance retention upon drying after infiltrated with aqueous electrolyte. The PVA-GO mat overcomes the major issue of conventional PVA-based electrolytes, which is the ionic conductivity decay upon drying. After exposure to 45 ± 5% relative humidity at 25 °C for 1 month, its conductivity decay is limited to 38.4%, whereas that of pure PVA mat is as high as 84.0%. This mainly attributes to the hygroscopic nature of GO and the unique nanofiber structure within the mat. Monolithic supercapacitors have been derived directly on the mat via a well-developed laser scribing process. The as-prepared supercapacitor offers an areal capacitance of 9.9 mF cm-2 at 40 mV s-1 even after 1 month of aging under ambient conditions, with a high device-based volumetric energy density of 0.13 mWh cm-3 and a power density of 2.48 W cm-3, demonstrating great promises as a more stable power supply for wearable electronics.

Graphene-Fiber-Based Supercapacitors Favor N-Methyl-2-pyrrolidone/Ethyl Acetate as the Spinning Solvent/Coagulant Combination.

One-dimensional flexible fiber supercapacitors (FSCs) have attracted great interest as promising energy-storage units that can be seamlessly incorporated into textiles via weaving, knitting, or braiding. The major challenges in this field are to develop tougher and more efficient FSCs with a relatively easy and scalable process. Here, we demonstrate a wet-spinning process to produce graphene oxide (GO) fibers from GO dispersions in N-methyl-2-pyrrolidone (NMP), with ethyl acetate as the coagulant. Upon chemical reduction of GO, the resulting NMP-based reduced GO (rGO) fibers (rGO@NMP-Fs) are twice as high in the surface area and toughness but comparable in tensile strength and conductivity as that of the water-based rGO fibers (rGO@H2O-Fs). When assembled into parallel FSCs, rGO@NMP-F-based supercapacitors (rGO@NMP-FSCs) offered a specific capacitance of 196.7 F cm-3 (147.5 mF cm-2), five times higher than that of rGO@H2O-F-based supercapacitors (rGO@H2O-FSCs) and also higher than most existing wet-spun rGO-FSCs, as well as those FSCs built with metal wires, graphene/carbon nanotube (CNT) fibers, or even pseudocapacitive materials. In addition, our rGO@NMP-FSCs can provide good bending and cycling stability. The energy density of our rGO@NMP-FSCs reaches ca. 6.8 mWh cm-3, comparable to that of a Li thin-film battery (4 V/500 µAh).

Nerve guidance conduits from aligned nanofibers: improvement of nerve regeneration through longitudinal nanogrooves on a fiber surface.

A novel fibrous conduit consisting of well-aligned nanofibers with longitudinal nanogrooves on the fiber surface was prepared by electrospinning and was subjected to an in vivo nerve regeneration study on rats using a sciatic nerve injury model. For comparison, a fibrous conduit having a similar fiber alignment structure without surface groove and an autograft were also conducted in the same test. The electrophysiological, walking track, gastrocnemius muscle, triple-immunofluorescence, and immunohistological analyses indicated that grooved fibers effectively improved sciatic nerve regeneration. This is mainly attributed to the highly ordered secondary structure formed by surface grooves and an increase in the specific surface area. Fibrous conduits made of longitudinally aligned nanofibers with longitudinal nanogrooves on the fiber surface may offer a new nerve guidance conduit for peripheral nerve repair and regeneration.

Three-dimensional polycaprolactone scaffold via needleless electrospinning promotes cell proliferation and infiltration.

Electrospinning has been widely used in fabrication of tissue engineering scaffolds. Currently, most of the electrospun nanofibers performed like a conventional two-dimensional (2D) membrane, which hindered their further applications. Moreover, the low production rate of the traditional needle-electrospinning (NE) also limited the commercialization. In this article, disc-electrospinning (DE) was utilized to fabricate a three-dimensional (3D) scaffold consisting of porous macro/nanoscale fibers. The morphology of the porous structure was investigated by scanning electron microscopy images, which showed irregular pores of nanoscale spreading on the surface of DE polycaprolactone (PCL) fibers. Protein adsorption assessment illustrated the porous structure could significantly enhance proteins pickup, which was 55% higher than that of solid fiber scaffolds. Fibroblasts were cultured on the scaffold. The results demonstrated that DE fiber scaffold could enhance initial cell attachment. In the 7 days of culture, fibroblasts grew faster on DE fiber scaffold in comparison with solid fiber, solvent cast (SC) film and TCP. Fibroblasts on DE fibers showed a stretched shape and integrated with the porous surface tightly. Cells were also found to migrate into the DE scaffold up to 800µm. Results supported the use of DE PCL fibers as a 3D tissue engineering scaffold in soft tissue regeneration.

Fabrication of a chitosan/bioglass three-dimensional porous scaffold for bone tissue engineering applications.

Bone defects caused by trauma and disease have become urgent problems. Three-dimensional (3D) porous scaffolds for bone tissue engineering should ideally have an interconnected porous structure, good biocompatibility and mechanical properties similar to those of natural bones. In the present study, a chitosan/bioglass (CS/BG) 3D porous scaffold was constructed by initially preparing a CS fibre 3D porous scaffold by needle-punching, and then depositing BG on the scaffold by dip-coating. The CS/BG 3D porous scaffold had an interconnected porous structure, with a porosity of 77.52% and a pore size around 50 µm. Water absorption values of the CS fibre 3D porous scaffold and the corresponding CS/BG scaffold were 570% and 59%, respectively. The BG present in the latter significantly decreased the swelling of the CS fibres, thus improving the stability of the scaffolds. The CS/BG 3D porous scaffold possessed good mechanical properties, with a compression strength of 7.68 ± 0.38 MPa and an elastic modulus of 0.46 ± 0.02 GPa, which are well-matched to those of trabecular bone. In vitro cell assay results demonstrated that the CS/BG 3D porous scaffold had good biocompatibility, which facilitates the spreading and proliferation of human bone marrow stromal cells (hBMSCs). The CS/BG 3D porous scaffold is thus a suitable material for bone tissue engineering.