New Electrode Material GCE/AgNPs-LS/Hg Based on Nanosilver Produced with the Use of Biopolymers

A method of producing nanosilver by using lignosulfonic acid derivative and a new method of the obtained AgNPs-LS electrode material for developing a chemically modified GCE/AgNPs-LS/Hg electrode is presented. The data demonstrate that the modified electrode shows enhanced performance in determining Tl⁺ ions in comparison to unmodified electrode GCE. The stripping anodic peak current of thallium characterized in linearity over its concentration range from 1.22 ⋅ 10⁻⁸ to 1.15 ⋅ 10⁻⁷ mol dm⁻³, with detection limit 4.6 ⋅ 10⁻⁹ mol dm⁻³. It is assumed that the novel AgNPs-LS/Hg²⁺ complex is suitable for preparing functionalized nanostructured material and can be used as an electrochemical sensing platform for heavy metals.     

New electrode material GCE/AgNPs-D3 as an electrochemical sensor used for the detection of thallium ions

Optimal working parameters for the innovative electrode GCE/AgNPs-D3 were determined and the selectivity was assessed. The stripping anodic peak current of thallium characterized in linearity over range from 4.9 ⋅ 10⁻⁸ to 4.9 ⋅ 10⁻⁷ mol ⋅ dm⁻³, with LOD = 7.16 ppb (3.5 ⋅ 10⁻⁸ mol ⋅ dm⁻³). Furthermore, the new electrode showed more than sevenfold improvement in the thallium current signal compared to the unmodified electrode GCE. High selectivity was achieved using EDTA disodium salt as a complexing agent for other metals.     

The cathodic stripping voltammetric determination of traces of iodide with a hanging copper amalgam drop electrode

A hanging copper amalgam drop electrode (HCADE) is used for the determination of traces of iodide by cathodic stripping voltammetry. The cathodic stripping peak of copper(I) iodide from the HCADE is better defined than that of mercury(I) iodide from a hanging mercury drop electrode. Optimum conditions and interferences are reported. With a 3-min deposition time at ?0.1 V vs. SCE, the calibration plot is linear up to 2 × 10^?6 mol dm^?3 iodide. The detection limit for iodide with the HCADE under voltammetric conditions is 4 × 10^?8 mol dm^?3; this is lowered to 8 × 10^?9 mol dm^?3 by using the differential pulse stripping technique.     

Electroactivated Disposable Pencil Graphite Electrode – New,Cost-effective,and Sensitive Electrochemical Detection of Bioflavonoid Hesperidin

In this paper, for the first time, electroactivated disposable pencil graphite electrode (ePGE) was used for the detection of bioflavonoid hesperidin with cyclic and differential pulse voltammetry. The electroactivation efficiency of the pencil graphite electrode (PGE) was examined employing electrochemical impedance spectroscopy (EIS) and scanning electrochemical microscopy (SECM) and the enhancement of electron transfer kinetics of the PGE after the electroactivation was found. Hesperidin is irreversibly oxidized on the ePGE and its oxidation was the most pronounced at pH=5.0. Two electrode processes were detected, on one hand, a mixed diffusion and adsorption control was observed for the first electrode process. On the other hand, only diffusion control was observed in the second electrode process. Linear dependence between the peak current and the hesperidin concentration was obtained in the concentration range from 5×10⁻⁷ mol dm⁻³ to 1×10⁻⁵ mol dm⁻³ and the determined lower limit of detection (LOD) was 2×10⁻⁷ mol dm⁻³. Moreover, hesperidin in pharmaceutical formulation (containing active substance, hesperidin, and excipients) was quantified using ePGE. A good correlation was obtained between experimentally obtained hesperidin concentration by voltammetric analysis and concentration determined by standard HPLC technique (R²=0.9462).     

Electrode Modified with Cobalt Cyclohexylbutyrate for the Determination of Low Molecular Weight Thiol Group Bearing Compounds Using Catalytic Stripping Voltammetry

Glassy carbon electrode, modified with cobalt(II) cyclohexylbutyrate monohydrate immobilized in polystyrene matrix is usable for determination of thiol group bearing compounds both in oxidized and reduced forms using catalytic stripping voltammetry. The measurements are carried out in acetate buffer (pH 4.3) containing Tween 40. After the accumulation step at −850 mV vs. Ag/AgCl a peak at −170 mV is observed on linear sweep voltammogram, the height of which is proportional to the concentration of added thiol. Addition of carbon nanotubes into polystyrene film enhances the sensitivity of the modified electrode. The detection limit is 1×10⁻⁶ mol dm⁻³ for all studied thiols. The electrode can be regenerated by exposing it to the potential between 300–600 mV.     

Stripping Chronopotentiometry with Dry‐Preservable Supporting Electrolyte

The determination of some toxic metals by stripping chronopotentiometry with a supporting solution having an unconventional composition has been investigated with the aim of using such components in disposable measuring cells preservable in dry state and quite ready for use, only needing addition of a small volume of sample. The new supporting solution is prepared with a solid strong acid, p‐toluenesulfonic acid, in the place of the inorganic acids commonly used to improve the cation availability. The other components are, as usual, sodium chloride, which fixes the potential of the screen‐printed silver – silver chloride reference electrode, and mercury(II) chloride as the plating agent. This supporting solution has been tested in batch measurements with the mercury film glassy carbon electrode as well as with screen‐printed carbon‐ink electrodes, either with mercury film or bare. The physical shape of the mercury layer electrolytically deposited on screen‐printed carbon‐ink electrodes from a supporting solution containing 0.1 M p‐toluenesulfonic acid and 0.1 M sodium chloride has been investigated by scanning electron microscopy (SEM) and energy dispersive spectrometry (EDS) microanalysis. In chronopotentiometric stripping p‐toluenesulfonic acid performs as well as the usual inorganic strong acids, particularly in terms of sensitivity. At 0.1 mol dm^?3 it proved very suitable for the determination of toxic metals, in particular lead(II), at levels down to a few μg dm^?3. The overall results appear promising and can open new avenues for preparing disposable cells for on‐field stripping chronopotentiometric determination of toxic metals.     

Application of a copper-based mercury film electrode in cathodic stripping voltammetry

The utility of a copper-based mercury film electrode (MFE) in cathodic stripping voltammetry (c.s.v.) is tested by comparing the cyclic and stripping voltammograms obtained with this electrode for thiocyanate, tryptophane, cysteine and benzotriazole against those obtained with the hanging copper-amalgam drop electrode (HCADE) and the HMDE. The cathodic stripping peaks obtained at the copper-based MFE and the HCADE are usually narrower and higher and are located at more negative potentials than the peaks obtained at the HMDE. Lower detection limits and better separations of adjacent peaks are thus achieved, and useful peaks can be separated from the mercury waves obtained with the conventional HMDE. The advantage of the copper-based MFE over the HCADE is its simplicity of preparation and maintenance. Thiocyanate, tryptophane, cysteine and benzotriazole can be determined at the copper-based MFE by c.s.v. with detection limits of 1 × 10^?8, 1 × 10^?8, 5 × 10^?8 mol dm^?3, respectively.     

A PVC-based pentathia-15-crown-5 membrane potentiometric sensor for mercury(II)

Poly(vinyl chloride) (PVC)-based membrane of pentathia-15-crown-5 exhibits good potentiometric response for Hg²⁺ over a wide concentration range (2.51 × 10⁻⁵ to 1.00 × 10⁻¹ mol dm⁻³) with a slope of 32.1 mV per decade of Hg²⁺ concentration. The response time of the sensor is as fast as 20 s. The electrode has been used for a period of six weeks and exhibits fairly good discriminating ability towards Hg²⁺ in comparison to alkali, alkaline and some heavy metal ions. The electrode can be used in the pH range from 2.7 to 5.0.     

Enhancement of Li-ion battery performance of graphite anode by sodium ion as an electrolyte additive

Electrochemical performance of a graphite electrode for lithium-ion batteries was successfully and easily improved by sodium ion dissolved in an electrolyte solution. Sodium ion was added by dissolving 0.22 mol dm⁻³ NaClO₄ into a 1 mol dm⁻³ LiClO₄ ethylene carbonate–diethyl carbonate (1:1 by volume) electrolyte solution prior to charge–discharge cycle. By sodium-ion addition, an irreversible capacity at the initial cycle was obviously reduced, and reversible discharge capacities increased with better capacity retention. From ac impedance measurements, a graphite electrode in the sodium ion added electrolyte had much smaller interface resistance compared to that obtained in sodium ion free one. Furthermore, the electrode surface morphology observed by electron microscopes after charge–discharge tests got more uniform in the sodium added electrolyte.     

Adsorptive Stripping Voltammetric Determination of Nanomolar Concentration of Cerium(III) at a Carbon Paste Electrode Modified by N′‐[(2‐Hydroxyphenyl)Methylidene]‐2‐Furohydrazide

The aim of this work was to obtain an adsorptive stripping voltammetric method for the Ce(III) determination at a carbon paste electrode, chemically modified with N'‐[(2‐hydroxyphenyl)methylidene]‐2‐furohydrazide (NHMF). The electroanalytical procedure comprised two steps: the Ce(III) chemical accumulation at ?200 mV followed by the electrochemical detection of the Ce(III)/NHMF complex, using anodic stripping voltammetry. The factors, influencing the adsorptive stripping performance, were optimized including the modifier quantity in the paste, the electrolyte concentrations, the solution pH and the accumulation potential or time. The resulting electrode demonstrated a linear response over a wide range of Ce(III) concentration (5.0–90 nmol dm^?3). The detection limit was found to be 0.8 nmol dm^?3 on the basis of a signal to noise ratio of 3. The precision for six determinations of 10 and 55 nmol dm^?3 Ce(III) was 5.6% and 2.1% (relative standard deviation), respectively. Application of the procedure to the determination of cerium in phosphate rock and wastewater samples gave good results.     

A coated tubular solid-state chloride-selective electrode in flow-injection analysis

The construction, suitability and behaviour of a coated tubular solid-state chloride ion-selective electrode in continuous flow analysis are discussed. The flow-through cell is constructed easily from Tygon tubing and silver foil, which is treated to give a silver/silver chloride electrode. The optimum contact area is obtained with a tube 5 mm long and of 2 mm internal diameter, for a total flow rate of 4.7 cm³ min^?1; the carrier streams are 1.0 mol dm³ potassium nitrate. Response times are fast (3–4 s for 95% response). With 30-μl samples, the working range covers 5–5000 mg dm³ chloride with a reproducibility better than 1.7% (relative standard deviation); the stability of the system is excellent. Interferences are similar to those found in batch analysis with Ag/AgCl electrodes, but are less severe in the flow system; pH has no effect in the range 2–12. Results obtained for chloride in waters at a sample throughput rate of about 120 h^?1 agree well with results by a standard spectrophotometric automated method.     

An Electrochemical Sensor Based on Silver Nanoparticles‐Benzalkonium Chloride for the Voltammetric Determination of Antiviral Drug Tenofovir

A simple voltammetric nanosensor was described for the highly sensitive determination of antiviral drug Tenofovir. The benzalkonium chloride and silver nanoparticles were associated to build a nanosensor on glassy carbon electrode. Surface characterictics were achieved using scanning electron microscopic technique. The voltammetric measurements were performed in pH range between 1.0 and 10.0 using cyclic, adsorptive stripping differential pulse and adsorptive stripping square wave voltammetry. The linear dependence of the peak current on the square root of scan rates and the slope value (0.770) demonstrated that the oxidation of tenofovir is a mix diffusion‐adsorption controlled process in pH 5.70 acetate buffer. The linearity range was found to be 6.0×10⁻⁸–1.0×10⁻⁶ M, and nanosensor displayed an excellent detection limit of 2.39×10⁻⁹ M by square wave adsorptive stripping voltammetry. The developed nanosensor was successfully applied for the determination of Tenofovir in pharmaceutical dosage form. Moreover, the voltammetric oxidation pathway of tenofovir was also investigated at bare glassy carbon electrode comparing with some possible model compounds (Adenine and Adefovir).     

Direct determination of bismuth(III) in sea water by square-wave anodic stripping voltammetry at a glassy-carbon rotating-disk electrode

A method for the determination of bismuth(III) in untreated sea water at its natural pH of 8.1 is described. A bare glassy-carbon rotating-disk electrode is preconditioned by placing in the sample at an applied potential of ?0.8 V vs. Ag/AgCl for 20 min; after stripping to ?0.4 V, bismuth is accumulated for 5 min at ?0.8 V and finally stripped in the square-wave mode. The bismuth peak appears at ca. + 0.10 V vs. Ag/AgCl; peak height is linearly related to concentration up to 2×10^?10 mol dm^?3. The method is highly selective for bismuth. The concentration of Bi(III) in the investigated sample was (6±1)×10^?11 mol dm^?3, or 12±2 ng dm^?3. The different types of response obtained are discussed.     

Nafion/2,2'-bipyridyl-modified bismuth film electrode for anodic stripping voltammetry

This paper describes the fabrication, characterisation and the application of a Nafion/2,2′-bipyridyl/bismuth composite film-coated glassy carbon electrode (NC(Bpy)BiFE) for the anodic stripping voltammetric determination of trace metal ions (Zn²⁺, Cd²⁺ and Pb²⁺). The NC(Bpy)BiFE electrode is prepared by first applying a 2.5 mm³ drop of a coating solution containing 0.5 wt% Nafion and 0.1% (w/v) 2,2′-bipyridil (Bpy) onto the surface of a glassy carbon electrode, while the Bi film was plated in situ simultaneously with the target metal ions at −1.4 V. The main advantage of the polymer coated bismuth film electrode is that the sensitivity of the stripping responses is increased considerably due to the incorporation of the neutral chelating agent of 2,2′-bipyridyl (Bpy) in the Nafion film, while the Nafion coating improved the mechanical stability of the bismuth film and its resistance to the interference of surfactants. The key experimental parameters relevant to both the electrode fabrication and the voltammetric measurement were optimized on the basis of the stripping signals. With a 2 min deposition time in the presence of oxygen, linear calibration curves were obtained in a wide concentration range (about 2-0.001 μM) with detection limits of 8.6 nM (0.56 μg dm⁻³) for Zn²⁺, 1.1 nM (0.12 μg dm⁻³) for Cd²⁺ and 0.37 nM (0.077 μg dm⁻³) for Pb²⁺. For nine successive preconcentration/determination/electrode renewal experiments the standard deviations were between 3 and 5% at 1.2 μM for zinc and 0.3-0.3 μM concentration level for lead and cadmium, respectively, and the method exhibited excellent selectivity in the presence of the excess of several potential interfering metal ions. The analytical utility of the stripping voltammetric method elaborated was tested in the assay of heavy metals in some real samples and the method was validated by ICP-MS technique.     

Cathodic and anodic stripping determination of traces of adenine and adenosine based on accumulation of copper(I) compounds at mercury or amalgam electrodes

In the presence of adenine and adenosine, the copper(II)/copper(Hg) couple splits to the copper(II)/copper(I) and copper(I)/copper(Hg) couples. Sparingly soluble complexes of copper(I) with adenine and adenosine can be accumulated on the electrode surface either by reduction of Cu(II) ions or by oxidation of the copper amalgam electrode. The copper(I)/adenine deposit can be stripped either cathodically or anodically with detection limits of 5×10^?9 and 2×10^?8 mol dm^?3, respectively. The copper(I)/ adenosine complex yields only the cathodic stripping peak with a detection limit of 9×10^?6 mol dm^?3. The stripping peaks obtained for the copper(I)/adenine and copper(I)/ adenosine complexes are better defined and appear over a wider range of pH than the peaks related to the corresponding mercury compounds. Adenosine cannot be determined in the presence of adenine bur adenine can be determined in the presence of moderate amounts of adenosine.     

A potentiometric study of the complexation of manganese(II) by 2-mercapto-3-phenylpropenoate in solution

Complex formation between manganese(II) and 2-mercapto-3-phenylpropenoate (MPP) has been studied at 25°C and 100 mmol dm⁻³ NO₃⁻ in 30% (v/v) ethanol-water using glass electrode potentiometry. The titration data can be explained by the formation of the complex MnMPP, log β₁₁₀ = 5.407.     

Voltammetric Analysis of Cadmium and Lead (Undesirable Elements) in Brine,Supported by Solid Phase Extraction – the Right Solution of the Analytical Challenge

The stripping voltammetry at HMDE is proposed for Cd and Pb (undesirable ingredients) determination in the natural brine (C_Cl >43 g L⁻¹). Samples with so high salinity have to be significantly diluted. For ICP MS, a 10^5–6 times dilution is required, which disqualifies this method. The proposed procedure allows to determine Cd (0.001 μg L⁻¹) and Pb (0.005 μg L⁻¹) after only 100 times dilution. The thermal chloride stripping or isolation by Chelex 100 increase the quality of obtained data. The recovery study was performed. The LOQs are below recommendations related to the use of brines in balneology.     

Interaction between a stationary mercury electrode and a hydrogen bubble in an aqueous sodium dodecyl sulphate solution

The stability and rupture of thin liquid films formed from an aqueous solution of Na₂SO₄ (0.05 mol dm⁻³) in the presence of 5 × 10⁻⁵ mol dm⁻³ sodium dodecyl sulphate between a stationary mercury electrode and a hydrogen bubble has been investigated as a function of electrode potential. The electrostatic component of disjoining pressure has been calculated using the results of capacity measurement for the mercury-solution interface. Special attention has been paid to films formed on positively charged mercury surfaces. In this case, despite the positive electrode polarization, the outer Helmholtz plane potential is found to be negative due to the high surface activity of the dodecyl sulphate anion. The van der Waals component of disjoining pressure has been calculated on the basis of a double sheath model of the two interacting surfaces, taking into consideration the orientation of the adsorbed surfactant layers at the interfaces. Calculations of the total disjoining pressure can explain film stability at negative mercury potentials, but do not explain film rupture when the polarization of the mercury is positive. The existence of a hydrophobic attractive interaction is postulated in the latter case.     

Voltammetric Determination of Selected Aminoquinolines Using Carbon Paste Electrode

Optimum conditions have been found for voltammetric determination of mutagenic 5‐aminoquinoline, 6‐aminoquinoline and 3‐aminoquinoline by differential pulse voltammetry and adsorptive stripping differential pulse voltammetry on carbon paste electrode. The lowest limits of determination were found for adsorptive stripping differential pulse voltammetry in 0.1 mol dm^?3 H₃PO₄ (5×10^?7 mol dm^?3 , 1×10^?7 mol dm^?3, and 1×10^?7 mol dm^?3 for 5‐aminoquinoline, 6‐aminoquinoline and 3‐aminoquinoline, respectively). The possibility to determine mixtures of 8‐aminoquinoline with 3‐aminoquinoline or 5‐aminoquinoline or 6‐aminoquinoline, and mixtures of 5‐aminoquinoline with 3‐aminoquinoline or 6‐aminoquinoline by differential pulse voltammetry was verified. Binary mixtures of 8‐aminoquinoline with 3‐aminoquinoline or 6‐aminoquinoline, and of 3‐aminoquinoline with 5‐aminoquinoline could be successfully analyzed.     

Anodic stripping voltammetry with flow injection analysis

A flow cell with a wall-jet electrode design is used for anodic stripping voltammetry of lead at concentrations of about 10^?7 mol dm^?3. Maximum peak heights are obtained for narrow nozzle diameters and short nozzle-to-electrode distances. Linear calibration plots are obtainedfor almost four decades of change in concentration and can be extended by judicious choice of sample volume. Increasing sample throughput rates by increasing the solution flow rate decreases the analytical signal. Square wave voltammetry provides shorter analysis times and better sensitivity than differential pulse voltammetry.