An enhanced oxime-based biomimetic electrochemical sensor modified with multifunctional AuNPs–Co<Subscript>3</Subscript>O<Subscript>4</Subscript>–NG composites for dimethoate determination

An enhanced oxime-based electrochemical sensor decorated with gold nanoparticles (AuNPs) and Co₃O₄ hexagonal nanosheets coupled with nitrogen-doped graphene has been developed for dimethoate determination dramatically. The introduction of Co₃O₄ hexagonal nanosheets tackles agglomeration of AuNPs and also enhances the sensitivity of electrochemical sensors greatly. The structure and properties of the synthesized composites were characterized by scanning electron microscopy, X-ray diffraction, Raman spectroscopy and Fourier transform infrared spectroscopy, confirming the successful modification of 2-(4-mercaptobutoxy)-1-naphthaldehyde oxime and Co₃O₄ supported AuNPs in a great experiment. In addition, differential pulse voltammetry further revealed that the developed electrochemical sensor exhibited excellent selectivity, sensitivity and stability in real samples analysis. Under optimal conditions, the modified sensor displayed a broad linear range from 1?×?10^?14 M to 1?×?10^?6 M with a fairly low detection limit of 8.4?×?10^?14 M (S/N?=?3) and was expected to act as a superior method for dimethoate determination.     

Cyclic voltammetry and impedance spectroscopy analysis for graphene-modified solid-state electrode transducers

The transducer of solid-state electrodes based on an epoxy-graphite composite was modified by two different methods, such as direct mixed and layer deposition of graphene (commercial and synthesized by electrochemical exfoliation of graphite). The modified electrodes were characterized by cyclic voltammetry and impedance spectroscopy. Also, scanning electron microscopy (SEM) was carried out to acquire information concerning the morphology of the composite electrode. Voltammetric measurements, in presence of [Fe(CN)₆]^3? as electroactive standard, determined a quasi-reversible electrochemical behavior under linear diffusion control. Electronic transference for modified and unmodified electrodes was compared. Solid-state electrode modified by inclusion of synthesized graphene showed a better electronic transference at electrode surface, due to the lower potential difference between anodic and cathodic peaks (ΔE = 125 mV) with respect to unmodified electrode (ΔE = 160 mV). Impedance spectroscopy characterization of electrode bodies in solid-state it was revealed a higher electronic conductivity and a supercapacitive behavior for the modified composites (values of intrinsic capacitances in the order of nanofarads) due to inclusions of graphite and graphene in the epoxy matrix. These inclusions were verified through SEM microscopy. The electronic conductivity and the supercapacitive character contributed both to the enhancement of electronic transference at electrode surface.     

Oxygen reduction on electrodeposited silver catalysts in alkaline solution

In this study, silver was electrochemically deposited onto glassy carbon (GC) substrate using constant potential regime and tested for oxygen reduction reaction (ORR) in alkaline media. The surface morphology of Ag/GC electrodes was studied by scanning electron microscopy (SEM). It was established that after 10 s of deposition, a number of Ag nanoparticles with the size of 15 nm are produced that grow to about 45 nm after 300 s of electrodeposition. The ORR studies were conducted in 0.1 M KOH solution employing the rotating disk electrode (RDE) method. The Tafel slope at low current densities for electrodeposited silver is in the range from ?70 to ?80 mV. The RDE measurements showed that the electron transfer number (n) is 3.5 for smaller amounts of electrodeposited Ag, and it increases with increasing the loading of Ag on the GC surface. These n values suggest that the electroreduction of oxygen on Ag/GC electrodes proceeds mainly to water.     

High-sensitive amperometric hydrazine sensor based on chemically synthesized zinc nitroprusside nanoparticle-supported carbon ceramic electrode

Zinc nitroprusside (ZnNP) nanoparticles were fabricated at the surface of zinc powder-doped carbon ceramic electrode (CCE) by a chemical derivatization process. This modified electrode was characterized by scanning electron microscopy, atomic force microscopy and cyclic voltammetry techniques. The charge transfer rate constant (k _s) and charge transfer coefficient (α) were calculated for the electron exchange reaction of the ZnNP thin film. The ZnNP nanoparticle-modified CCE (ZnNP|CCE) showed good electrocatalytic activity toward hydrazine oxidation. The limit of detection (S/N = 3) and sensitivity were found to be 0.16 µM and 0.21 µA/µM, respectively. The mechanism of hydrazine electrooxidation at the electrode surface was studied. Finally, the ZnNP|CCE was successfully used for the determination of trace amount of hydrazine in different spiked and real samples.     

Direct electrochemistry and electrocatalysis of cytochrome <Emphasis Type="Italic">c</Emphasis> based on dandelion-like Bi<Subscript>2</Subscript>S<Subscript>3</Subscript> nanoflowers

The direct electrochemistry and electrocatalysis of cytochrome c (Cyt c) based on dandelion-like bismuth sulfide (d-Bi₂S₃) nanoflowers have been developed. The morphologies and composition of the d-Bi₂S₃ were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy dispersive X-ray spectroscopy (EDS). Then, the electrochemical behaviors of Cyt c immobilized within the d-Bi₂S₃/chitosan film and its electrocatalytic ability toward hydrogen peroxide (H₂O₂) reduction were investigated by cyclic voltammetry. The electron transfer rate constant was estimated to be 13.1 s^?1, suggesting that a fast direct electron transfer was realized. The prepared Cyt c/d-Bi₂S₃/chitosan nanobiocomposite-modified electrode possessed excellent electrocatalytic ability toward H₂O₂ reduction that showed linearity in the range from 0.5 μM to 1.56 mM with a correlation coefficient of 0.9993. The detection limit was 0.2 μM on signal-to-noise ratio of 3. In addition, the d-Bi₂S₃ nanoflowers may be also applied to direct electron transfer of other redox proteins.     

Effect of solvents on the morphology of NiCo<Subscript>2</Subscript>O<Subscript>4</Subscript>/graphene nanostructures for electrochemical pseudocapacitor application

The large internal surface areas and outstanding electrical and mechanical properties of graphene have prompted to blend graphene with NiCo₂O₄ to fabricate nanostructured NiCo₂O₄/graphene composites for supercapacitor applications. The use of graphene as blending with NiCo₂O₄ enhances the specific capacitance and rate capability and improves the cyclic performance when compared to the pristine NiCo₂O₄ material. Here, we synthesized two different nanostructured morphologies of NiCo₂O₄ on graphene sheets by solvothermal method. It has been suggested that the morphologies of oxides are greatly influenced by dielectric constant, thermal conductivity, and viscosity of solvents employed during the synthesis. In order to test this concept, we have synthesized nanostructured NiCo₂O₄ on graphene sheets by facile solvothermal method using N-methyl pyrrolidone and N,N-dimethylformamide solvents with water. We find that mixture of N-methyl pyrrolidone and water solvent favored the formation of nanonet-like NiCo₂O₄/graphene (NiCoO-net) whereas mixture of N,N-dimethylformamide and water solvent produced microsphere-like NiCo₂O₄/graphene (NiCoO-sphere). Electrochemical pseudocapacitance behavior of the two NiCo₂O₄/graphene electrode materials was studied by cyclic voltammetry, chronopotentiometry, and electrochemical impedance spectroscopy techniques. The supercapacitance measurements on NiCoO-net and NiCoO-sphere electrodes showed specific capacitance values of 1060 and 855 F g^?1, respectively, at the current density of 1.5 A g^?1. The capacitance retention of NiCoO-net electrode is 93 % while that of NiCoO-sphere electrode is 77 % after long-term 5000 charge-discharge cycles at high current density of 10 A g^?1.     

Synthesis and study of catalysts of electrochemical oxygen reduction reaction based on polymer complexes of nickel and cobalt with Schiff bases

The article presents the results of studies of new nanosize catalysts of electrochemical oxygen reduction reaction (ORR) obtained using the method of thermal decomposition of polymer complexes of nickel and cobalt with tetradentate (N₂O₂) Schiff bases. The catalysts are characterized using the methods of thermogravimetry, electrochemical quartz microgravimetry, scanning electron microscopy with X-ray microanalysis, XPS. The ORR process on electrodes modified by the above catalysts was studied using the voltammetry and rotating disk electrode techniques. The obtained catalysts manifested high specific activity per initial polymer mass (more than 600 mA/mg).     

Electrocatalytic oxidation of salicylic acid at a carbon paste electrode impregnated with cerium-doped zirconium oxide nanoparticles as a new sensing approach for salicylic acid determination

Cerium-doped zirconium oxide (Ce/ZrO₂) was introduced as a highly efficient electrocatalyst for electrooxidation of salicylic acid (SA). The electrocatalyst material was synthesized via co-precipitation of cerium and zirconium ions, and then the resulting solid was heat-treated at high temperature to create crystallized cerium-doped zirconium oxide nanoparticles. The obtained material was characterized by scanning electron microscopy and X-ray diffraction methods. The Ce/ZrO₂-modified carbon paste electrode (Ce/ZrO₂-CPE) exhibited a distinct oxidative peak for SA, whereas no signal was observed for SA at unmodified carbon paste electrode at the same experimental conditions. Cyclic voltammetry and electrochemical impedance spectroscopy were applied to investigate the electrocatalytic performance of the electrode and SA electrooxidation mechanism. Square wave voltammetry was used to capture the analytical signal of SA. The electrode composition was optimized to increase the SA signal. Using the optimized electrode, it became possible to determine SA in the concentration range of 5.0–1000.0 μM with detection limit of 1.1 μM (3S_b/m). The electrode showed very high sensitivity of 1013.5 μA mM^?1 cm^?2 which is remarkably better than the previously reported SA sensors. The proposed method was successfully applied for the determination of SA in human serum, milk, and pharmaceutical samples.     

Ag nanoparticles decorated Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/chitosan nanocomposite: synthesis,characterization and application toward electrochemical sensing of hydrogen peroxide

We studied a rapid, sensitive and selective amperometric sensor for determination of hydrogen peroxide by electrodeposited Ag NPs on a modified glassy carbon electrode (GCE). The modified GCE was constructed through a step by step modification of magnetic chitosan functional composite (Fe₃O₄–CH) and high-dispersed silver nanoparticles on the surface. The resulted Ag@Fe₃O₄–CH was characterized by various analytical methods including Fourier transform infrared spectroscopy, X-ray diffraction, transmission electron microscopy, scanning electron microscopy and cyclic voltammetry. The proposed sensor employed Ag@Fe₃O₄–CH/GCE as the working electrode with a linear current response to the hydrogen peroxide concentration in a wide range from 0.01 to 400 µM with a low limit of detection (LOD = 0.0038 µM, S/N = 3). The proposed sensor showed superior reproductivity, sensitivity and selectivity for the detection of hydrogen peroxide in environmental and clinical samples.     

Effect of the substitutional groups on the electrochemistry,kinetic of thermal decomposition and kinetic of substitution of some uranyl Schiff base complexes

Uranyl(VI) complexes, [UO₂(X-saloph)(solvent)], where saloph denotes N,N’-bis(salicylidene)-1,2-phenylenediamine and X = NO₂, Cl, Me, H; were synthesized and characterized by ¹H NMR, IR, UV–Vis spectroscopy, thermal gravimetry (TG), cyclic voltammetry, elemental analysis (C.H.N) and X-ray crystallography. X-ray crystallography of [UO₂(4-nitro-saloph)(DMF)] revealed coordination of the uranyl by the tetradentate Schiff base ligand and one solvent molecule, resulting in seven-coordinated uranium. The complex of [UO₂(4-nitro-saloph)(DMF)] was also synthesized in nano form. Transmission electron microscopy image showed nano-particles with sizes between 30 and 35 nm. The TG method and analysis of Coats-Redfern plots revealed that the kinetics of thermal decomposition of the complexes is of the first-order in all stages. The kinetics and mechanism of the exchange reaction of the coordinated solvent with tributylphosphine was investigated by spectrophotometric method. The second-order rate constants at four temperatures and the activation parameters showed an associative mechanism for all corresponding complexes with the following trend: 4-Nitro > 4-Cl > H > 4-Me. It was concluded that the steric and electronic properties of the complexes were important for the reaction rate. For analysis of anticancer properties of uranyl Schiff base complexes, cell culture and MTT assay was carried out. These results showed a reduction of jurkat cell line concentration across the complexes.     

Structure and Stability of Gold Nanoparticles Synthesized Using <Emphasis Type="Italic">Schinus molle</Emphasis> L. Extract

In this work, we exhibited the results of the green synthesis of gold nanoparticles by aqueous extract of Schinus molle L. leaves. The chemical reaction was carried out by varying the plant extract/precursor salt ratio concentration in the aqueous solution. The structural characterization of the nanoparticles was performed using X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). XRD analysis showed that the as-synthesized AuNPs have a face-centered cubic structure. SEM and TEM observations indicated that most of the obtained particles have multiple twinning structures (MTP). The synthesized Au-MTP have particle sizes in the range of 10–60 nm, most of them with an average size of about 24 nm. However, triangular Au plate particles were also obtained, having an average size of 180 nm. Fourier transforms infrared spectroscopy and shows that the functional groups responsible for the chemical reduction of AuNPs are phenolic compounds present in the S. molle L. leaf.     

Dip-coating deposition of resistive BiVO<Subscript>4</Subscript> thin film and evaluation of their photoelectrochemical parameters under distinct sources illumination

Resistive monoclinic bismuth vanadate (BiVO₄) nanocrystals in the form of thin films were obtained by the solution combustion synthesis coupled with the dip-coating deposition process. The structure, morphology, and optical properties of BiVO₄ nanocrystals were characterized by means of x-ray diffraction (XRD), scanning electron microscopy (SEM), and UV-Vis spectroscopy. The photoelectrochemical properties were obtained by cyclic voltammetry and chronoamperometry techniques in potassium chloride (KCl) electrolyte solution under distinct visible light sources irradiation condition. Under blue InGaN light emitting diode (LED) irradiation, the electrode has a better efficiency, faster response time (260 ms), and faster decay time (65 ms), when compared with the irradiation by dichroic lamp. Besides, the photocurrent density (j _ph) is approximately 39 times higher than j _ph obtained under dichroic lamp. The performance analysis based on the methylene blue degradation reaction has shown that the BiVO₄ material has higher electroactivity under InGaN LED irradiation condition, with estimated k _obs value of 200 × 10^?4 min^?1, which is a little higher than the value obtained with dichroic lamp illumination. In the dark condition, the BiVO₄ presented much lower photocatalytic activity.     

Self-assembly of ultra-small gold nanoparticles on an indium tin oxide electrode for the enzyme-free detection of hydrogen peroxide

A novel enzyme-free electrochemical sensor for H₂O₂ was fabricated by modifying an indium tin oxide (ITO) support with (3-aminopropyl) trimethoxysilane to yield an interface for the assembly of colloidal gold. Gold nanoparticles (AuNPs) were then immobilized on the substrate via self-assembly. Atomic force microscopy showed the presence of a monolayer of well-dispersed AuNPs with an average size of ~4 nm. The electrochemical behavior of the resultant AuNP/ITO-modified electrode and its response to hydrogen peroxide were studied by cyclic voltammetry. This non-enzymatic and mediator-free electrode exhibits a linear response in the range from 3.0?×?10^?5 M to 1.0?×?10^?3 M (M?=?mol?·?L^?1) with a correlation coefficient of 0.999. The limit of detection is as low as 10 nM (for S/N?=?3). The sensor is stable, gives well reproducible results, and is deemed to represent a promising tool for electrochemical sensing.

Synthesis of monodisperse pancake-like Bi<Subscript>2</Subscript>WO<Subscript>6</Subscript> with prominent photocatalytic performances

Uniform Bi₂WO₆ pancakes were prepared via a solvothermal route in a solvent mixture of glycerol (Gly) and water (V/V = 1). A variety of techniques including scanning electron microscopy, transmission electron micrographs, X-ray powder diffraction, Brunauer–Emmett–Teller, FT-IR spectra, and UV–Vis diffuse reflectance spectra, were employed to characterize the structure and properties of the as-obtained Bi₂WO₆. It was found that Bi₂WO₆ pancakes showed prominent photocatalytic performance for the degradation of rhodamine B (RhB) under visible light (λ ≥ 420 nm) irradiation, which can be attributed to its good crystallization, large surface area, unique morphology and structural features.     

One-Pot Green Synthesis of Hematite (α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>) Nanoparticles by Ultrasonic Irradiation and Their In Vitro Cytotoxicity on Human Keratinocytes CRL-2310

Greener and ecofriendly approaches to the synthesis of hematite (α-Fe₂O₃) nanoparticles are important for various biomedical applications. The authors describe on a facile, one-pot method for synthesizing hematite nanoparticles (HNPs) using ultrasonic irradiation of iron(III) oxide solution containing the aqueous root extract of Arisaema amurense, which was used as both reducing and stabilizing agents. The synthesized HNPs were characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, thermogravimetric analysis (TGA), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM), and vibrating sample magnetometry (VSM). FT-IR analysis indicated the presence of stabilizing groups such as hydroxyl (–OH), C–O, and amide (–NH–) on the surfaces of HNPs. TEM analysis revealed the formation of near spherical HNPs of average size 24.55 ± 6.9 nm. VSM confirmed the ferromagnetic nature of the HNPs with a saturation magnetization (Ms) at 1.25 emu/g and remanent magnetization (Mr) at 0.50 emu/g at 301 K. The electrochemical behavior of glassy carbon (GC)/HNPs electrode was studied using cyclic voltammetry (CV). MTT assays of the HNPs exhibited in vitro concentration-dependent cytotoxicity to human keratinocytes CRL-2310, which indicated the synthesized HNPs are compatible with requirements for in vivo biomedical applications at lower concentrations.     

Kolanut (<Emphasis Type="Italic">Cola nitida</Emphasis>) Mediated Synthesis of Silver–Gold Alloy Nanoparticles: Antifungal,Catalytic, Larvicidal and Thrombolytic Applications

This study investigated use of leaf, seed, seed shell and pod extracts of Cola nitida for the green synthesis of silver-alloy nanoparticles (Ag–AuNPs). The Ag–AuNPs formed were dark brown with maxima absorbance in the range of 497–531 nm. FTIR peaks at 3290–3396 and 1635–1647 cm^?1 showed that proteins were the capping and stabilization molecules for the synthesis of Ag–AuNPs. While leaf, seed and seed shell extract-mediated Ag–AuNPs had near spherical morphology, anisotropic structures of sphere, rod, hexagon and triangle were formed by pod extract. The polydispersed particles were 17–91 nm in size, with crystalline characteristics and prominent presence of Ag and Au in the EDX spectra. Ag–AuNPs inhibited growth of Aspergillus flavus, A. fumigatus and A. niger by 69.51–100 %. Exposure of Anopheles mosquito larvae to Ag–AuNPs resulted in 80–100 % mortality in 24 h. Catalytic degradation of >90 and >60 % were obtained for malachite green and methylene blue respectively after 24 h. The particles displayed potent blood anticoagulant and thrombolytic activities, indicative of their potentials in the management blood coagulation disorders. This study showed that C. nitida can be used for green synthesis of Ag–AuNPs, which is the first report of its kind.     

Effect of the electrode material on the oxygen reduction at the nonstoichiometric lanthanum fluoride/electrode interface

The voltammetry method with a linear potential scan is used for investigating the effect the electrode material (Ni, Co, electrodes on the basis of cobalt oxides modified with carbon) exerts on the reduction of gaseous oxygen at interfaces solid fluoride-conducting electrode LaF₃:Eu²⁺/electrode, O₂, and conjugated processes. Properties of the modified electrodes are characterized by the impedance spectroscopy, scanning electron microscopy, and x-ray photoelectron spectroscopy methods. The oxygen reaction is irreversible at the LaF₃:Eu²⁺|Ni (or Co) interfaces. At the interface of LaF₃:Eu²⁺ with modified electrodes Co (C n at %), where n = 5 and 9, mobile forms of oxygen are reversible and the reduction of gaseous and chemisorbed oxygen is controlled by diffusion with different effective kinetic parameters.     

Biogenic synthesis from <Emphasis Type="Italic">Prunus</Emphasis> × <Emphasis Type="Italic">yedoensis</Emphasis> leaf extract,characterization, and photocatalytic and antibacterial activity of TiO<Subscript>2</Subscript> nanoparticles

Green synthesis of TiO₂ nanoparticles (NPs) from Prunus × yedoensis leaf extract (PYLE), and their application for removal of phosphate and their antibacterial activity, were studied for the first time. NPs were obtained using a green chemistry approach from 0.1 M TiO₂ and PYLE at ratio of 1:1 (v/w). Initial confirmation of production of TiO₂ NPs was provided by a color change from white to light yellow, then calcination was performed at 500 °C for 1 h. The TiO₂ NPs were characterized using various analytical techniques such as ultraviolet–visible (UV–Vis) spectroscopy, X-ray diffraction analysis, Fourier-transform infrared spectroscopy, Raman spectroscopy, UV–Vis diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, and high-resolution transmission electron microscopy. The results indicated that the optimal amount of TiO₂ NPs for removal of phosphate was 10 mg/l (10 ppm) with duration of 25 min. Furthermore, the antibacterial activity of TiO₂ NPs was also investigated using two different bacteria (Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli) in aqueous medium. The results revealed highly efficient sunlight-driven photocatalytic and antibacterial activity of TiO₂ NPs.     

An innovative electrochemical approach for voltammetric determination of levodopa using gold nanoparticles doped on titanium dioxide nanotubes

Catalytic nanotubes made from titanium dioxide (TiO₂-NTs) and covered with gold nanoparticles (Au-NPs) were prepared via galvanic deposition of the Au-NPs on the TiO₂-NTs. The morphology and surface characteristics of the resulting electrodes were investigated using scanning electron microscopy and energy-dispersive X-ray spectroscopy. The results indicated that the Au-NPs were homogeneously deposited on the surface of TiO₂-NTs which consist of individual tubes of about 40?C80?nm in diameter. The AuNPs with a size of 80?C100?nm are well-dispersed on the surface of the TiO₂-NTs. The electro-catalytic activity of the electrodes towards the electro-oxidation of levodopa was studied by cyclic voltammetry, differential puls voltammetry. The results showed that the electrodes exhibit a considerably higher activity toward the oxidation of levodopa. The oxidation peak current linearly depends on the concentration of levodopa in the 10 to 70???M concentration range. Levodopa was determined by the method in pharmaceutical preparations, and results were found to be satisfactory.

Fluoroferrate templated with HAmTAZ: X-ray single crystal,thermal behaviour,vibrational study and magnetic characterization

A new metal–organic compound FeF₆(HAmTAZ)₃ which (HAmTAZ = 3-amino-1,2,4-triazole) was hydrothermally synthesized from an equimolar mixture of FeF₂ and FeF₃ with HAmTAZ, aqueous HF and ethanol solvent at 410 K yielded a new hybrid class I fluoroferrate. The structure was characterized by single-crystal X-ray diffraction data. The crystal structure of FeF₆(HAmTAZ)₃ crystallizes in the trigonal system space group R3c with a = b = 12.5230 (6) Å, c = 18.5950 (16) Å, γ = 120° and Z = 6. The structure was built up from isolated octahedral FeF₆ separated by [HAmTAZ]⁺ cations. The thermal analysis has shown that the decomposition undergoes two steps between 475 and 775 K. IR and mass spectrometry have been used to confirm the presence of the organic molecule in the crystal lattice and determine the evacuated vapours during the decomposition, respectively. The magnetization of the title compound has no revealed any ferromagnetic component in the range of magnetic field from ?20 to 20 KOe at room temperature.