Screen-Printed Stretchable Supercapacitors Based on Tin Sulfide-Decorated Face-Mask-Derived Activated Carbon Electrodes with High Areal Energy Density.

In this work, tin sulfide nanosheets decorated on face-mask-derived activated carbon have been explored as electrode material for electrochemical supercapacitors. A hydrothermal route was employed to grow tin sulfide on the surface and inside of high-surface-area face-mask-derived activated carbon, activated at 850 °C, to produce a hierarchical interconnected porous composite (ACFM-850/TS) structure. The presence of tin sulfide in the porous carbon framework exposed the surface active sites for rapid adsorption/desorption of electrolyte ions and ensured high utilization of the porous carbon surface. Furthermore, the porous ACFM-850 framework prevented the stacking/agglomeration of tin sulfide sheets, thereby enhancing the charge-transport kinetics in the composite electrodes. Benefiting from the synergistic effect of tin sulfide and ACFM-850, the resulting ACFM-850/TS composite exhibited an attractive specific capacitance of 423 F g-1 at a 0.5 A g-1 current density and superior rate capability (71.3% at a 30 A g-1 current density) in a 1.0 M Na2SO4 electrolyte. In addition, we fabricated a planar symmetric interdigitated supercapacitor on a stretchable Spandex fabric using an ACFM-850/TS composite electrode and carboxymethyl cellulose/NaClO4 as a solid-state gel electrolyte employing a scalable screen-printing process. The as-prepared stretchable supercapacitors displayed an ultrahigh energy density of 9.2 µWh cm-2 at a power density of 0.13 mW cm-2. In addition, they exhibited an excellent cyclic stability of 64% even after 10,000 charge-discharge cycles and 42% after 1000 continuous stretch (at 25% stretching)/release cycles. Such screen-printed interdigitated planar supercapacitors with activated carbon composite electrodes and a solid-state gel electrolyte act as promising low-cost energy-storage devices for wearable and flexible integrated electronic devices.

Scalable slot-die coated flexible supercapacitors from upcycled PET face shields.

Upcycling Covid19 plastic waste into valuable carbonaceous materials for energy storage applications is a sustainable and green approach to minimize the burden of waste plastic on the environment. Herein, we developed a facile single step activation technique for producing activated carbon consisting of spherical flower like carbon nanosheets and amorphous porous flakes from used PET [poly(ethylene terephthalate)] face shields for supercapacitor applications. The as-obtained activated carbon exhibited a high specific surface area of 1571 m2 g-1 and pore volume of 1.64 cm3 g-1. The specific capacitance of these carbon nanostructure-coated stainless steel electrodes reached 228.2 F g-1 at 1 A g-1 current density with excellent charge transport features and good rate capability in 1 M Na2SO4 aqueous electrolyte. We explored the slot-die coating technique for large-area coatings of flexible high-performance activated carbon electrodes with special emphasis on optimizing binder concentration. Significant improvement in electrochemical performance was achieved for the electrodes with 15 wt% Nafion concentration. The flexible supercapacitors fabricated using these electrodes showed high energy and power density of 21.8 W h kg-1 and 20 600 W kg-1 respectively, and retained 96.2% of the initial capacitance after 10 000 cycles at 2 A g-1 current density. The present study provides a promising sustainable approach for upcycling PET plastic waste for large area printable supercapacitors.

Activated Carbon Utilization from Corn Derivatives for High-Energy-Density Flexible Supercapacitors.

Porous activated carbons from four types of corn derivatives (husk, fiber, grain, and cob) are compared for the first time regarding their structural, morphological, and electrochemical characteristics for application as electrode materials in flexible supercapacitors. Benefiting from its hierarchical porous structure, appropriate amount of N and O functional groups, large specific surface area (1804 m2 g-1), and high degree of graphitization, the activated carbon from corn grains displayed the best electrochemical performance as an electrode material for supercapacitor applications; when tested in a three-electrode configuration, it had a high specific capacitance (411 F g-1 at 1.0 A g-1) and an excellent rate capacity (85.7% capacitance retention at 30 A g-1) in an aqueous 6 M KOH electrolyte. The high specific surface area and high degree of graphitization of the activated carbon from corn grains (AC grain) played crucial roles in its excellent energy storage performance. Most importantly, the flexible supercapacitor that was assembled with slot-die coated AC grain electrodes and a hydroxyethyl cellulose (HEC)/KOH biopolymer electrolyte delivered an outstanding electrochemical performance with an energy density of 31.1 Wh kg-1 at 215 W kg-1 and ultrahigh cyclic stability (91.3% capacitance retention after 10 000 cycles at a current density of 5 A g-1). Also, the assembled flexible supercapacitor maintained an energy density of 20.03 Wh kg-1 even under a high power density of 28.01 kW kg-1. These findings conclude that the porous carbon material obtained from corn grains has enormous potential as a high-performance electrode material for supercapacitors.

Effect of Ambient Environment on Laser Reduction of Graphene Oxide for Applications in Electrochemical Sensing.

Electrochemical sensors play an important role in a variety of applications. With the potential for enhanced performance, much of the focus has been on developing nanomaterials, in particular graphene, for such sensors. Recent work has looked towards laser scribing technology for the reduction of graphene oxide as an easy and cost-effective option for sensor fabrication. This work looks to develop this approach by assessing the quality of sensors produced with the effect of different ambient atmospheres during the laser scribing process. The graphene oxide was reduced using a laser writing system in a range of atmospheres and sensors characterised with Raman spectroscopy, XPS and cyclic voltammetry. Although providing a slightly higher defect density, sensors fabricated under argon and nitrogen atmospheres exhibited the highest average electron transfer rates of approximately 2 × 10-3 cms-1. Issues of sensor reproducibility using this approach are discussed.

Morphology control of nickel nanoparticles prepared in situ within silica aerogels produced by novel ambient pressure drying.

Silica aerogels are low density solids with high surface area and high porosity which are ideal supports for catalyst materials. The main challenge in aerogel production is the drying process, which must remove liquid from the pores of the wet gel while maintaining the solid network. In this work, the synthesis of silica aerogels and nickel-doped silica aerogels by a low energy budget process is demonstrated. Silica aerogels are produced by ambient drying using ammonium bicarbonate, rather than a conventional low surface tension solvent. Heating dissociates the ammonium bicarbonate, so generating CO2 and NH3 within the pores of the wet gel which prevents pore collapse during drying. Nickel-doped aerogels were produced by reducing nickel ions within pre-synthesised silica aerogels. The morphology of the resulting nickel particles-spheres, wires and chains-could be controlled through an appropriate choice of synthesis conditions. Materials were characterized using nitrogen adsorption/desorption isotherms, scanning electron microscopy, Fourier-transform infrared spectroscopy, thermogravimetric analysis and X-ray diffraction. The surface area of undoped aerogel is found to increase with the concentration of ammonium bicarbonate salts from 360 to 530 m2 g-1, and that of nickel-doped silica aerogel varies from 240 to 310 m2 g-1 with nickel doping conditions.

Bioinspired Synthesis of Monolithic and Layered Aerogels.

Aerogels are the least dense and most porous materials known to man, with potential applications from lightweight superinsulators to smart energy materials. To date their use has been seriously hampered by their synthesis methods, which are laborious and expensive. Taking inspiration from the life cycle of the damselfly, a novel ambient pressure-drying approach is demonstrated in which instead of employing low-surface-tension organic solvents to prevent pore collapse during drying, sodium bicarbonate solution is used to generate pore-supporting carbon dioxide in situ, significantly reducing energy, time, and cost in aerogel production. The generic applicability of this readily scalable new approach is demonstrated through the production of granules, monoliths, and layered solids with a number of precursor materials.

Synthesis of porous zinc-based/zinc oxide composites via sol-gel and ambient pressure drying routes.

Porous Zn-based and ZnO composites are successfully fabricated via the sol-gel process and ambient pressure drying method using hexane as the drying solvent for the reduction in capillary force during drying process. Various highly porous Zn-based phases (Zn1-based and Zn5-based) that are studied by X-ray diffraction analysis, scanning electron microscopy and transmission electron microscopy show that they contribute through heat treatment (at 200 °C) to the development of ambient pressure dried nanoporous wurtzite (hexagonal) ZnO. A macroporous flower-like structure consisting of nanosheets is observed in porous Zn-based composites, and nanoporous structure is observed within platelets of ZnO nanoparticles. Possible routes for preparing highly porous Zn-based/ZnO composites are discovered by detailing the process for ambient pressure drying synthesis of porous wurzite ZnO.

Oral administration of amphotericin B nanoparticles: antifungal activity, bioavailability and toxicity in rats.

Amphotericin B (AMB) is used most commonly in severe systemic life-threatening fungal infections. There is currently an unmet need for an efficacious (AMB) formulation amenable to oral administration with better bioavailability and lower nephrotoxicity. Novel PEGylated polylactic-polyglycolic acid copolymer (PLGA-PEG) nanoparticles (NPs) formulations of AMB were therefore studied for their ability to kill Candida albicans (C. albicans). The antifungal activity of AMB formulations was assessed in C. albicans. Its bioavalability was investigated in nine groups of rats (n = 6). Toxicity was examined by an in vitro blood hemolysis assay, and in vivo nephrotoxicity after single and multiple dosing for a week by blood urea nitrogen (BUN) and plasma creatinine (PCr) measurements. The MIC of AMB loaded to PLGA-PEG NPs against C. albicans was reduced two to threefold compared with free AMB. Novel oral AMB delivery loaded to PLGA-PEG NPs was markedly systemically available compared to Fungizone® in rats. The addition of 2% of GA to the AMB formulation significantly (p < 0.05) improved the bioavailability from 1.5 to 10.5% and the relative bioavailability was > 790% that of Fungizone®. The novel AMB formulations showed minimal toxicity and better efficacy compared to Fungizone®. No nephrotoxicity in rats was detected after a week of multiple dosing of AMB NPs based on BUN and PCr, which remained at normal levels. An oral delivery system of AMB-loaded to PLGA-PEG NPs with better efficacy and minimal toxicity was formulated. The addition of glycyrrhizic acid (GA) to AMB NPs formulation resulted in a significant oral absorption and improved bioavailability in rats.

Synthesis and Characterisation of Reduced Graphene Oxide/Bismuth Composite for Electrodes in Electrochemical Energy Storage Devices.

A reduced graphene oxide/bismuth (rGO/Bi) composite was synthesized for the first time using a polyol process at a low reaction temperature and with a short reaction time (60 °C and 3 hours, respectively). The as-prepared sample is structured with 20-50 nm diameter bismuth particles distributed on the rGO sheets. The rGO/Bi composite displays a combination of capacitive and battery-like charge storage, achieving a specific capacity value of 773 C g-1 at a current density of 0.2 A g-1 when charged to 1 V. The material not only has good power density but also shows moderate stability in cycling tests with current densities as high as 5 A g-1 . The relatively high abundance and low price of bismuth make this rGO/Bi material a promising candidate for use in electrode materials in future energy storage devices.

Green reduction of graphene oxide using alanine.

There remains a real need for the easy, eco-friendly and scalable preparation method of graphene due to various potential applications. Chemical reduction is the most versatile method for the large scale production of graphene. Here we report the operating conditions for a one-step, economical and green synthesis method for the reduction of graphene oxide using a biomolecule (alanine). Graphene oxide was produced by the oxidation and exfoliation of natural graphite flake with strong oxidants using Hummers method (Hummers and Offeman, 1958), but the method was revised in our laboratory to set up a safe and environmentally friendly route. The reduction of graphene oxide was investigated using alanine at various operating conditions in order to set up optimum conditions (treatment time, temperature and concentration of the reagent). Samples have been characterized by using UV-Visible spectroscopy, Fourier transform infrared spectroscopy, transmission electron microscopy, Raman spectroscopy and X-ray diffraction analysis.

Enhanced removal of nickel(II) ions from aqueous solutions by SDS-functionalized graphene oxide.

In this paper, a one-pot and easy-to-handle method at room temperature without additional chemicals for the modification of graphene oxide (GO) with surfactant is found. Removal of nickel (II) ions from aqueous solutions by GO and surfactant (sodium dodecyl sulphate) modified graphene oxide (SDS-GO) was studied spectrophotometrically at room temperature as a function of time, initial concentration and pH. Adsorption capacity of the adsorbent was increased dramatically (from 20.19 to 55.16 mg/g found by Langmuir model) due to the functionalization of the surface by SDS. The driving force of the adsorption of Ni(II) ions is electrostatic attraction and Ni(II) ions adsorbed on the GO surface chemically besides ion exchange.

Metallic nickel nanoparticles and their effect on the embryonic development of the sea urchin Paracentrotus lividus.

The presence of nanoparticles in many industrial applications and daily products is making it nowadays crucial to assess their impact when exposed to the environment. Metallic nickel nanoparticles (Ni NPs) are of high industrial interest due to their ability to catalyze the reversible hydration of CO2 to carbonic acid at ambient conditions. We characterized metallic Ni NPs by XRD, HRTEM and EDS and determined the solubility of free nickel ions from 3 mg/L metallic Ni NPs in seawater by ICP-MS over 96 h, which was below 3%. Further, embryonic development of the sea urchin Paracentrotus lividus was investigated for 48 h in the presence of metallic Ni NPs (0.03 mg/L to 3 mg/L), but no lethal effects were observed. However, 3 mg/L metallic Ni NPs caused a size reduction similar to 1.2 mg/L NiCl2*6 H2O. The obtained results contribute to current studies on metallic Ni NPs and point to their consequences for the marine ecosystem.

Stealth Amphotericin B nanoparticles for oral drug delivery: In vitro optimization.

PURPOSE: Amphotericin B (AmB) is an effective anti-fungal and anti-leishmanial agent. However, AmB has low oral bioavailability (0.3%) and adverse effects (e.g., nephrotoxicity). The objectives of this study were to improve the oral bioavailability by entrapping AmB in pegylated (PEG) poly lactide co glycolide copolymer (PLGA-PEG) nanoparticles (NPs). The feasibility of different surfactants and stabilizers on the mean particle size (MPS) and entrapment efficiency were also investigated. MATERIALS AND METHODS: NPs of AmB were prepared by a modified emulsification diffusion method employing a vitamin E derivative as a stabilizer. Physicochemical properties and particle size characterization were evaluated using Fourier Transform Infra-Red spectroscopy (FTIR), differential scanning calorimetry, scanning electron microscopy and transmission electron microscopy. Moreover, in vitro dissolution profiles were performed for all formulated AmB NPs. RESULTS: MPS of the prepared spherical particles of AmB ranged from 26.4 ± 2.9 to 1068 ± 489.8 nm. An increased stirring rate favored AmB NPs with a smaller MPS. There was a significant reduction in MPS, drug content and drug release, when AmB NPs were prepared using the diblock polymer PLGA-PEG with 15% PEG. Addition of three emulsifying agents poly vinyl pyrrolidone (PVP), Vitamin E (TPGS) and pluronic F-68 to AmB formulations led to a significant reduction in particle size and increase in drug entrapment efficiency (DEE) compared to addition of PVP alone. FTIR spectroscopy demonstrated a successful loading of AmB to pegylated PLGA-PEG copolymers. PLGA-PEG copolymer entrapment efficiency of AmB was increased up to 56.7%, with 92.7% drug yield. After a slow initial release, between 20% and 54% of AmB was released in vitro within 24 h phosphate buffer containing 2% sodium deoxycholate and were best fit Korsmeyer-Peppas model. In conclusion, PLGA-PEG diblock copolymer with 15% PEG produced a significant reduction (>70%) in MPS with highest drug content. The percentage of PEG in the copolymer and the surfactant/stabilizer used had a direct effect on AmB release in vitro, entrapment efficiency and MPS. These developed formulations are feasible, effective and improved alternatives to other carriers for oral delivery of AmB.

Metal-enhanced luminescence of silicon quantum dots: effects of nanoparticles and molecular electron donors and acceptors on the photofading kinetics.

Alkyl-capped silicon quantum dots (SiQDs) show enhanced luminescence when drop cast as films on glass slides in mixtures with Ag or Au nanoparticles or the electron donor ferrocene (Fc). Metal enhancement of quantum dot photoluminescence (PL) is known to arise from a combination of the intense near-field associated with the surface plasmon of the metal on the rate of absorption and the decrease in the lifetime of the excited state. Here we present evidence that an additional factor is also involved: electron transfer from the metal to the quantum dot. Under CW irradiation with an argon ion laser at 488 nm, SiQDs undergo a reversible photofading of the PL as the particles photoionize. A steady-state condition is established by the competition between photoionization and electron-hole recombination. The fading of the initial PL I0 to the steady-state value I∞ can be modelled by a simple first order decay with a lognormal distribution of rates, which reflects the heterogeneity of the sample. In the presence of Ag and Au nanoparticles, the modal rate constants of photofading increase by factors of up to 4-fold and the ratio I0/I∞ decreases by factors up to 5-fold; this is consistent with an increase in the rate of electron-hole recombination facilitated by the metal nanoparticles acting as sources of electrons. Further support for this interpretation comes from the enhancement in PL observed in photofading experiments with films of SiQDs mixed with Fc; this compound is a well-known one-electron donor, but shows no plasmon band which complicates the estimation of PL enhancement with Ag NPs.

Therapeutic monitoring of amphotericin B in Saudi ICU patients using UPLC MS/MS assay.

Amphotericin B (AmB) is the first-line agent for the treatment of life-threatening invasive fungal infections. The aim of this study was to monitor AmB in critically ill Saudi patients in ICU after i.v. administration of 0.68 ± 0.1 mg/kg/day Fungizone®. A selective, sensitive and precise UPLC MS/MS method was developed to measure AmB concentrations in these patients. Seven ICU patients with creatinine clearance (ClCr) >40 mL/min were included. AmB levels were analyzed using a Waters Aquity UPLC MS/MS system, a BEH Shield RP18 column and detection via electrospray ionization source with positive ionization mode. The precision and accuracy of the developed UPLC method in the concentration range of 200-4000 ng/mL show no significant difference among inter- and-intra-day analysis (p > 0.05). Linearity was observed over the investigated range with correlation coefficient, r > 0.995 (n = 6/day). The pharmacokinetics of AmB in these patients, at steady state, showed a high terminal half-life of 124.6 ± 73.4 h, with a highest concentration of 513.9 ± 281.1 ng/mL, a lowest concentration 316.4 ± 129.0 ng/mL and a mean clearance 91.1 ± 39.2 mL/h/kg. The pharmacokinetics of AmB in critically ill Saudi patients in ICU was studied using a fully validated assay. A weak correlation (r = -0.22) of AmB Cl with ClCr was obtained, which suggests the need for further investigation in a larger population.

Silver nanoparticle toxicity in sea urchin Paracentrotus lividus.

Silver nanoparticles (AgNPS) are an important model system for studying potential environmental risks posed by the use of nanomaterials. So far there is no consensus as to whether toxicity is due to AgNPs themselves or Ag(+) ions leaching from their surfaces. In sea urchin Paracentrotus lividus, AgNPs cause dose dependent developmental defects such as delayed development, bodily asymmetry and shortened or irregular arms, as well as behavioural changes, particularly in swimming patterns, at concentration ∼0.3 mg/L AgNPs. It has been observed that AgNPs are more toxic than their equivalent Ag(+) ion dose.

Smooth and conductive DNA-templated Cu2O nanowires: growth morphology, spectroscopic and electrical characterization.

DNA strands have been used as templates for the self-assembly of smooth and conductive cuprous oxide (Cu2O) nanowires of diameter 12-23 nm and whose length is determined by the template (16 µm for λ-DNA). A combination of spectroscopic, diffraction and probe microscopy techniques showed that these nanowires comprise single crystallites of Cu2O bound to the DNA molecules which fused together over time in a process analogous to Ostwald ripening, but driven by the free energy of interaction with the template as well as the surface tension. Electrical characterization of the nanowires by a non-contact method, scanned conductance microscopy and by contact mode conductive AFM showed the wires are electrically conductive. The conductivity estimated from the AFM cross section and the zero-bias conductance in conductive AFM experiments was 2.2-3.3 S cm⁻¹. These Cu2O nanowires are amongst the thinnest reported and show evidence of strong quantum confinement in electronic spectra.

Preparation and characterization of conductive and photoluminescent DNA-templated polyindole nanowires.

Polyindole (PIn) nanowires were formed on a lambda-DNA template by chemical oxidation of indole using aqueous FeCl3. The resulting nanowires are smooth, regular, conductive and had diameters in the range of 5-30 nm. These features allow them to be aligned by molecular combing and studied by scanned conductance microscopy, conductive AFM, and two-terminal I-V measurements. Using this combination of measurements, we find that the conductivity of PIn/DNA nanowires is between 2.5 and 40 S cm(-1) at room temperature, which is substantially greater than that in previous reports on the bulk polyindole conductivity (typically 10(-2)-10(-1) S cm(-1)). The conductance at zero bias shows an Arrhenius-type of dependence on temperature over the range of 233 to 373 K, and the values observed upon heating and cooling are repeatable within 5%; this behavior is consistent with a hopping mechanism of conductivity.

Evaporation and deposition of alkyl-capped silicon nanocrystals in ultrahigh vacuum.

Nanocrystals are under active investigation because of their interesting size-dependent properties and potential applications. Silicon nanocrystals have been studied for possible uses in optoelectronics, and may be relevant to the understanding of natural processes such as lightning strikes. Gas-phase methods can be used to prepare nanocrystals, and mass spectrometric techniques have been used to analyse Au and CdSe clusters. However, it is difficult to study nanocrystals by such methods unless they are synthesized in the gas phase. In particular, pre-prepared nanocrystals are generally difficult to sublime without decomposition. Here we report the observation that films of alkyl-capped silicon nanocrystals evaporate upon heating in ultrahigh vacuum at 200 degrees C, and the vapour of intact nanocrystals can be collected on a variety of solid substrates. This effect may be useful for the controlled preparation of new quantum-confined silicon structures and could facilitate their mass spectroscopic study and size-selection.