A simple method for electroanalytical determination of ceftiofur in UHT milk samples using square-wave voltammetry technique

A simple electroanalytical method was developed to determine the antibiotic ceftiofur (CF) in milk. The method is based on the adsorptive accumulation of the drug on a hanging mercury-drop electrode (HMDE) and the accompanying initiation of a negative square wave, which yielded well-defined cathodic peaks at −0.60 V (1C) and −0.91 V (2C) vs. Ag/AgCl. Calibration graphs were constructed and statistical parameters were evaluated. At pH 2.5, the square-wave voltammetry method revealed linearity from 52.4 to 524 ng mL⁻¹ (r = 0.997), which is in accordance with the tolerance level of 100 ng mL⁻¹ for CF as a residue in bovine milk established by the Food and Drug Administration (FDA) and the European Union. The limits of detection and quantification were 1.86 and 6.20 ng mL⁻¹, respectively. The method was tested to determine CF in spiked milk samples using HPLC as reference method.     

Pulse anodic stripping voltammetric determination of copper with an amoxicillin–nafion modified glassy carbon electrode

The analysis of Cu²⁺ by pulse anodic stripping voltammetry using a Nafion-modified glassy Carbon electrode incorporated with Amoxicillin is described. A significant increase in the voltammetric response was achieved at the modified electrode compared to a bare glassy carbon electrode. Cu²⁺ was accumulated in HAc–NaAc buffer (pH 3.6) at a potential of −0.7 V (vs. Ag/AgCl) for a certain time and then determined by pulse anodic stripping voltammetry. Parameters and conditions, such as the mass of Nafion, the concentration of Amoxicillin, the pH of medium, the accumulation potential, and the accumulation time were optimized. Under the optimum conditions, the calibration curve was linear in the range 8 × 10⁻¹⁰–2 × 10⁻⁸ M with a correlation coefficient of 0.9998 and relative standard deviation 4.87% (n = 5). The detection limit was 1.3 × 10⁻¹⁰ M. A study of interfering substances was also performed and the analytical utility of the method was demonstrated by applying to various pharmaceutical products.     

Anodic behaviour of fulvestrant and its voltammetric determination in pharmaceuticals and human serum on highly boron-doped diamond electrode using differential pulse adsorptive stripping voltammetry

The electrochemical oxidation of fulvestrant was made on highly boron-doped diamond electrode using differential pulse adsorptive stripping voltammetry. The highest current intensities were obtained by applying +1.10 V during 150 s for boron-doped diamond electrode. For boron-doped diamond electrode, linear responses were obtained for the concentrations between 1 × 10⁻⁶ and 8 × 10⁻⁵ M in standard samples and between 1 × 10⁻⁶ and 4 × 10⁻⁵ M in serum samples. The repeatability of the method was 0.55 RSD% for differential pulse adsorptive stripping voltammetry. The analytical values of the method are demonstrated by quantitative determination of fulvestrant in pharmaceutical formulations and human serum, without the need for separation or complex sample preparation, since there was no interference from the excipients and endogenous substances. Selectivity, reproducibility, and accuracy of the developed methods were demonstrated by recovery studies.     

Adsorptive stripping voltammetric determination of podophyllotoxin,an antitumour herbal drug,at multi-walled carbon nanotube paste electrode

Adsorption stripping voltammetry, a very sensitive electroanalytical method, was employed to determine podophyllotoxin, a kind of antitumour herbal drug at a multi-wall carbon nanotube (MWCNT)-modified carbon paste electrode (CPE) surface. In the following anodic sweep from 0.5 to 1.5 V, podophyllotoxin, adsorbed at the MWCNT-modified CPE surface, was oxidized and yielded a sensitive oxidation peak with E _1/2/E _p approximately 1.16 V/1.18 V over the scan rates of 10–120 mV s⁻¹. From CV and SWV studies of podophyllotoxin in the acetate buffers of various pH values, it was found that protons were involved in the oxidation of the drug at the H⁺/e⁻ ratio of one (∆E _p/pH = 56 mV at 25 °C). Its electrochemical behaviour was irreversible. The experimental conditions, such as supporting electrolyte, pH value, accumulation time, ionic strength and scan rate, were optimized for the measurement of podophyllotoxin. The best results were obtained in 0.02 M acetate/acetic acid buffer (pH 4.6) containing 0.04 M KCl (1:49, v/v) for 60 s accumulation. The oxidation peak current varies linearly with the concentration of podophyllotoxin over the range of 199–1796 pg mL⁻¹. The limits of detection and quantification of the pure drug are 4.5 and 14.96 pg mL⁻¹, with the correlation coefficient, r = 0.998 and the relative standard deviation, RSD = 1.3% (n = 5). This new method was successfully applied to the determination of podophyllotoxin in a plant sample of the rhizome of Podophyllum hexandrum. Recoveries were 99.173–101.231%. The relative standard deviations of intraday and interday analyses for podophyllotoxin were 0.55 and 0.61%, respectively (n = 3).     

Square-wave adsorptive stripping voltammetric determination of candesartan cilexetil in pharmaceutical formulations

A sensitive, simple and rapid square-wave adsorptive stripping voltammetric method was developed and validated for the determination of candesartan cilexetil in pharmaceutical formulations. The proposed method was based on electrochemical reduction of candesartan cilexetil at a hanging mercury drop electrode in phosphate buffer at pH 5.0. A well-defined reduction peak was observed at −1340 mV with 30 s of accumulation time and −1100 mV of accumulation potential. Under these optimized conditions, the square-wave adsorptive stripping voltammetric peak current showed a linear correlation on drug concentration over the range of 0.25–1.34 μg mL⁻¹ with a correlation coefficient of 0.9986 for the proposed method. The detection and quantitation limits for this method were 1 × 10⁻² and 2.5 × 10⁻¹ μg mL⁻¹, respectively. The results obtained for intra-day and inter-day precision (as RSD%) were between 1.10 and 3.90%. This method was applied successfully for the determination of candesartan cilexetil in its tablet dosage forms with mean recoveries of 101.13 ± 0.78% with RSD of 2.06% for 8 mg tablet and 99.84 ± 0.89% with RSD of 2.36% for 16 mg tablet. The results obtained from the developed square-wave adsorptive stripping voltammetric method were compared with those obtained by the analytical method reported in the literature.     

Simultaneous determination of trace aluminum (III), copper (II) and cadmium (II) in water samples by square-wave adsorptive cathodic stripping voltammetry in the presence of oxine

A validated adsorptive cathodic stripping voltammetry method is described for simultaneous determination of Al(III), Cu(II) and Cd(II) in water samples. In acetate buffer (pH 5) containing 10 μM oxine, these metal ions were determined as oxine complexes following adsorptive accumulation onto the HMDE at −0.05 V versus Ag/AgCl/KCl_s. The best signal to noise ratio was obtained using a square wave of scan increment 10 mV, frequency 120 Hz, and pulse-amplitude 25 mV. Limits of detection as low as 0.020 μg L⁻¹ Al(III), 0.012 μg L⁻¹ Cu(II) and 0.028 μg L⁻¹ Cd(II) were achieved. Interference due to various cations (K(I), Na(I), Mg(II), Ca(II), Mn(II), Fe(III), Bi(III), Sb(III), Se(IV), Pb(II), Zn(II), Ni(II), Co(II)), anions (Cl⁻, NO³⁻, SO₄ ²⁻, PO₄ ³⁻) and ascorbic acid was minimal as the measured signals change by 4% at the maximum. The stripping voltammetry method was successfully applied for simultaneous determination of Al(III), Cu(II) and Cd(II) in tap and natural bottled water samples.     

Modified glassy carbon electrode with Nafion/MWNTs as a sensitive voltammetric sensor for the determination of paeonol in pharmaceutical and biological samples

A simple, highly sensitive method was reported for directly voltammetric determination of paeonol in drug samples and human biological samples. Nafion/multi-wall carbon nanotubes’ (MWNTs) composite film was coated on the glassy carbon electrode. The adsorptive voltammetric behavior of paeonol on the Nafion/MWNTs-modified electrode was investigated using cyclic voltammetry (CV) and differential pulse anodic stripping voltammetry (DPASV). The results indicated that the Nafion/MWNTs-modified electrode could remarkably enhance electrocatalytic activity toward the oxidation of paeonol, and showed an excellent resistance capability toward the electrode passivation. A highly sensitive voltammetric sensor was developed for the detection of paeonol in pharmaceutical and biological samples. Under the optimum conditions, the anodic peak current was proportional to paeonol concentration in the range of 6.0 × 10⁻⁷–6.0 × 10⁻⁵ M with a detection limit of 4.0 × 10⁻⁷ M. Some kinetic parameters were determined, and multi-step mechanism for oxidation of paeonol was proposed.     

A new method for the simultaneous determination of Fe(III), Cu(II), Pb(II), Zn(II), Cd(II), and Ni(II) in wine using differential pulse polarography

A new and simple differential pulse polarographic method for the analysis of wine has been established. With this method, it was possible to determine simultaneously six trace elements in wine. There was no need for time consuming extraction and separation procedures with danger of contamination. The polarogram of wet digested wine was taken initially in pH 2 acetate buffer and Pb, Cd, and Zn were determined by standard additions. Ethylene diamine tetraacetic acid (EDTA) was added and pH was increased to six by addition of NaOH. Fe and Cu were determined subsequently. The ammonia buffer, pH 9.5, was identified as the best medium for separation and determination of Ni and Zn. The quantities of trace elements were found as Cu 290 ± 20 μg L⁻¹, Fe 8960 ± 50 μg L⁻¹, Pb 148 ± 17 μg L⁻¹, Cd 16 ± 8 μg L⁻¹, Zn 460 ± 25 μg L⁻¹, and Ni 78 ± 17 μg L⁻¹.     

Optimization of an anode for arsenic(V) extraction

Electrochemical methods has led to the preparation of a poly(pyrrole)-modified steel electrode (SS/PPy) for testing and optimizing the polymer doping/undoping process for arsenic(V) removal. Potentiodynamic (cyclic voltammetry) electropolymerization optimal range was between −0.200 and 0.980 V vs SCE. On the other hand, the potentiostatic optimal working potential was 0.980 V. SS/PPy-modified electrode prepared under either of these optimum conditions displayed a doping/undoping process occurring at 0.700 and −0.200 V, respectively. Hence, As(V) extraction or removal was performed by incorporating the cation to SS/PPy applying a 0.700 V constant potential. Then, As(V) doped SS/PPy was transferred to another cell, in which the undoping potential (−0.200 V) was applied to remove the ion from the polymer matrix, completing thus the extraction cycle (EC). This way, for instance, with a SS of 10 cm² geometric area and potentiostatic deposition carried out for 10 min, arsenic removal rates over 77 % were attained for 10 EC of 60 s each. This outcome allows predicting a promising future for the method as As(V) extractor from aqueous solutions. Furthermore, the modified electrode exhibited acceptable conditions for developing a likely arsenic sensor, since a linear current vs As(V) concentration relationship exits, at least in the order of concentrations used herein (50–500 ppm).     

Polymethylthiophene/Nafion-modified glassy carbon electrode for selective detection of dopamine in the presence of ascorbic acid

The possible use of an electrode modified with electroactive conductive poly(3-methylthiophene) (PMeT)/Nafion as a chemical sensor was investigated for the voltammetric analysis of Dopamine (DA). The electrochemical behavior of dopamine was examined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) techniques. By using a PMeT-modified glassy carbon (GC/PMeT) electrode, DA and Ascorbic Acid (AA) signals could be separated but the AA at high concentrations still caused significant interference by overlapping the DA peak. In comparison to the GC/PMeT electrode, the glassy carbon (GC/Nafion/PMeT) electrode modified with hybrid film Nafion/PMeT was found to permit a superior separation by shifting the oxidation of AA peak toward the less positive potential. The DPV curves for a mixture of DA and AA at an GC/Nafion/PMeT electrode in a 0.1 M H₂SO₄ solution showed peaks of DA and AA, at 0.45 and 0.21 V, respectively, indicating that the difference in the oxidation potential was 240 mV. In the 0.1 M H₂SO₄ solution, the oxidation peak current on the differential pulse voltammograms for the GC/PMeT electrode increased linearly with the concentration of DA in the range 1 × 10⁻⁶ to 1 × 10⁻³ M, and the oxidation peak current on the differential pulse voltammograms for the GC/Nafion/PMeT electrode in the range 5 × 10⁻⁷ to 2 × 10⁻⁴ M. The DA detection sensitivity of the GC/Nafion/PMeT electrode (26.7 μA μM⁻¹ cm⁻²) was 22 times higher than that of the GC/PMeT electrode (1.21 μA μM⁻¹ cm⁻²).     

Determination of cadmium (II) using H<Subscript>2</Subscript>O<Subscript>2</Subscript>-oxidized activated carbon modified electrode

Pristine activated carbon (AcC) was oxidized by H₂O₂ under ultrasonic conditions. Compared with pristine AcC, the H₂O₂-oxidized AC possesses higher accumulation ability to trace levels of Cd²⁺. Based on this, a highly sensitive, simple and rapid electrochemical method was developed for the determination of Cd²⁺. In 0.01 mol L⁻¹ HClO₄ solution, Cd²⁺ was effectively accumulated at the surface of H₂O₂-oxidized AcC modified paste electrode, and then reduced to Cd under −1.10 V. During the following potential sweep from −1.10 to −0.50 V, reduced Cd was oxidized and a sensitive stripping peak appears at −0.77 V. The stripping peak current of Cd²⁺ changes linearly with concentration over the range 5.0 × 10⁻⁸ to 5.0 × 10⁻⁶ mol L⁻¹. The limit of detection was found to be 3.0 × 10⁻⁸ mol L⁻¹ for 2-min accumulation. Finally, this new sensing method was successfully used to detect Cd²⁺ in waste water samples.     

Carbon nanotube-modified glassy carbon electrode for anodic stripping voltammetric detection of Uranyle

A multi-wall carbon nanotube (MWNT) modified glassy carbon electrode (GCE) is described for the measurement of trace levels of uranium by anodic stripping voltammetry. In a pH 4.4 NaAc-Hac buffer containing 0.010 mol L⁻¹ Mg(NO₃)₂, UO₂ ²⁺ was adsorbed onto the surface of a MWNT film coated glassy carbon electrode and then reduced at −0.40 V vs. Ag/AgCl. During the positive potential sweep the reduced uranium was oxidized and a well-defined stripping peak appeared at +0.20 V vs. Ag/AgCl. Low concentrations of Mg²⁺ significantly enhanced the stripping peak currents since they induced UO₂ ²⁺ to adsorb at the electrode surface. The response was linear up to 1.2 × 10⁻⁷ mol L⁻¹ and the relative standard deviation at 2.0 × 10⁻⁸ mol L⁻¹ uranium was 5.2%. Potential interferences were examined. The attractive behavior of the new “mercury-free” uranium sensor holds promise for on-site environmental and industrial monitoring of uranium.     

Study on simultaneous measurements of trace gallium(III) and germanium(IV) by adsorptive stripping voltammetry using mercury film electrode

Simultaneous adsorptive stripping voltammetric method for the determination of trace gallium(III) and germanium(IV) based on the adsorption of gallium(III) and germanium(IV)-catechol complex on the cyclic renewable mercury film silver based electrode (Hg(Ag)FE) is presented. The calibration graph is linear from 1.25 nM (0.09 μg L⁻¹) to 90 nM (6.27 μg L⁻¹) with correlation coefficient of 0.999 for gallium and from 2.5 nM (0.18 μg L⁻¹) to 160 nM (12.3 μg L⁻¹) with correlation coefficient of 0.998 for germanium for a preconcentration time of 30 s. The detection limit for a preconcentration time of 60 s is as low as 25 ng L⁻¹ for gallium and 58 ng L⁻¹ for germanium. The proposed method was successfully applied by studying the natural samples and simultaneous recovery of Ga(III) and Ge(IV) from spiked water and sediment samples.     

Electrochemical investigations of an anticancer drug in the presence of sodium dodecyl sulfate as an enhancing agent at carbon paste electrode

In the present work, the electrochemical behavior of an anticancer drug, gemcitabine hydrochloride (GMB) was studied in the presence of a surface active agent (surfactant) at carbon paste electrode (CPE). GMB showed an oxidation peak at 1.101 V. The presence of sodium dodecyl sulfate (SDS) in the electrolyte was found to enhance the oxidation signal of GMB at CPE. The oxidation peak current of GMB in the presence of SDS was observed to be the function of accumulation time, scan rate, pH of the medium, and concentration of GMB. Accumulation time greatly influenced the peak current but did not exhibit significant influence on the peak potential. Based on this, a novel, sensitive, and convenient differential pulse voltammetric method was developed for the determination of GMB in the concentration range of 5.0 × 10⁻⁸–3.0 × 10⁻⁴ M with a limit of detection value of 8.2 × 10⁻⁹ M. The proposed procedure was successfully applied for the determination of GMB in pharmaceutical formulations and spiked biological samples.     

Selective determination of uric acid in the presence of ascorbic acid at poly(<Emphasis Type="Italic">p</Emphasis>-aminobenzene sulfonic acid)-modified glassy carbon electrode

The electrocatalytic behavior of uric acid has been investigated with a glassy carbon electrode modified with p-aminobenzene sulfonic acid through electrochemical polymerization. This resulting electrode shows an excellent electrocatalytic response to uric acid and ascorbic acid, with a peak-to-peak separation of 0.267 V in a 0.1 mol L⁻¹ phosphate buffer solution (PBS) at pH 7.0. These results indicate that the proposed electrode can eliminate the serious interference of ascorbic acid, which coexists with uric acid in body fluids. Differential pulse voltammetry (DPV) was used for detecting uric acid with selectivity and sensitivity. The anodic peak current of uric acid was proportional to its concentration in the range of 1.2 × 10⁻⁷–8.0 × 10⁻⁴ mol L⁻¹, with a detection limit of 4.0 × 10⁻⁸ mol L⁻¹. The proposed method has been applied with satisfactory results to the determination of uric acid in human urine without any pretreatment.     

Determination of Underivatized Long Chain Fatty Acids Using HPLC with an Evaporative Light-Scattering Detector

A high-performance liquid chromatographic method with an evaporative light-scattering detector has been developed for the separation and quantitative analysis of four underivatized long chain fatty acids in four different oil matrices. An isocratic elution mode using methanol/water/acetic acid and an Agilent Eclipse XDB-C18 analytical column was used. Calibration curves of the four fatty acids (FA) were well correlated (r ² > 0.999) within the range of 1–10 mg mL⁻¹ for linoleic acid, 0.8–10 mg mL⁻¹ for stearic acid and 0.5–10 mg mL⁻¹ for the other FA. Four oil samples were examined; camellia oil, olive oil, Brucea javanica oil and sesame oil. Good agreement was found with the standard gas chromatographic (GC) method. The proposed method offers distinct advantages over the official GC method; better separation and precision, and the sample components do not need to be derivatized.     

Homogeneous electrocatalytic oxidation of <Emphasis Type="SmallCaps">d</Emphasis>-penicillamine with ferrocyanide at a carbon paste electrode: application to voltammetric determination

The electrooxidation of d-penicillamine (d-PA) was studied in the presence of ferrocyanide as a homogeneous mediator at the surface of a carbon paste electrode in aqueous media using cyclic voltammetry (CV) and chronoamperometry. Under optimum pH in CV the oxidation of d-PA occurs at a potential about 380 mV less positive than that in the absence of ferrocyanide. The catalytic oxidation peak current was dependent on the d-PA concentration and a linear calibration curve was obtained in the ranges 4.0 × 10⁻⁵–2.0 × 10⁻³ M and 8.0 × 10⁻⁶–1.8 × 10⁻⁴ M of d-PA with CV and differential pulse voltammetry (DPV) methods, respectively. The detection limits (3σ) were determined as 1.9 × 10⁻⁵ and 3.2 × 10⁻⁶ M by CV and DPV methods. This method was also used for the determination of d-PA in pharmaceutical preparations by the standard addition method.     

Direct electrochemistry of chemically modified catalase immobilized on an oxidatively activated glassy carbon electrode

Catalase (Ct) was modified using Woodward’s reagent K (WRK) as a specific modifier of carboxyl residues. The modified Ct was immobilized on an oxidatively activated glassy carbon electrode surface to investigate its direct electrochemistry. Using cyclic voltammetry an irreversible reduction peak was obtained at approximately −0.362 V vs. Ag/AgCl in buffer solution, pH 7, and at a scan rate of 0.1 V s⁻¹. The electrochemical parameters, including charge-transfer coefficient (0.27), apparent heterogeneous electron transfer rate constant (13.51 ± 0.42 s⁻¹) and formal potential of the Ct film (−0.275 V) were determined. The prepared enzyme electrode exhibited a response to H₂O₂.     

Electrocatalytic oxidation of glutathione at carbon paste electrode modified with 2,7-<Emphasis Type="Italic">bis</Emphasis> (ferrocenyl ethyl) fluoren-9-one: application as a voltammetric sensor

Electrooxidation of glutathione (GSH) was studied at the surface of 2,7-bis (ferrocenyl ethyl) fluoren-9-one modified carbon paste electrode (2,7-BFEFMCPE). Cyclic voltammetry (CV), double potential-step chronoamperometry, and differential pulse voltammetry (DPV) were used to investigate the suitability of this ferrocene derivative as a mediator for the electrocatalytic oxidation of GSH in aqueous solutions with various pH. Results showed that pH 7.00 is the most suitable pH for this purpose. At the optimum pH, the oxidation of GSH at the surface of this modified electrode occurs at a potential of about 0.410 V versus Ag|AgCl|KCl_sat. The kinetic parameters such as electron transfer coefficient, α = 0.61, and rate constant for the chemical reaction between GSH and redox site in 2,7-BFEFMCPE, k _h = 1.73 × 10³ cm³ mol⁻¹ s⁻¹, were also determined using electrochemical approaches. Also, the apparent diffusion coefficient, D _app, for GSH was found to be 5.0 × 10⁻⁵ cm² s⁻¹ in aqueous buffered solution. The electrocatalytic oxidation peak current of GSH showed a linear dependence on the glutathione concentration, and linear calibration curves were obtained in the ranges of 5.2 × 10⁻⁵ M to 4.1 × 10⁻³ M and 9.2 × 10⁻⁷ M to 1.1 × 10⁻⁵ M with cyclic voltammetry and differential pulse voltammetry methods, respectively. The detection limits (3σ) were determined as 1.4 × 10⁻⁵ M and 5.1 × 10⁻⁷ M for the CV and DPV methods, respectively. This method was also examined as a selective, simple, and precise new method for voltammetric determination of GSH in real sample such as hemolysed erythrocyte.     

Fabrication of carbon nanotube and dysprosium nanowire modified electrodes as a sensor for determination of curcumin

Two sensitive sensors for determination of curcumin (CM) were described. CM can be detected using multiwall carbon nanotube (MWCNT)-modified electrodes and dysprosium nanowire carbon paste electrode using the technique of adsorptive stripping voltammetry (AdSV) in stationary solution and the fast Fourier transform voltammetry at the flowing solution. Both electrodes did show less passivation effect that occurs on the unmodified electrodes and displayed better stability and reproducibility. This electrode enabled selective determination of CM in the presence of interfering species. Under optimized conditions, CM could be detected over a linear range with a detection limit of 5.0 × 10⁻⁹ mol L⁻¹ and 5.0 × 10⁻¹⁰ mol L⁻¹ for the traditional square wave and fast Fourier transform square wave voltammetry (FFTSWV) with RSD between 0.2 and 0.5%. Comparison with other reported methods showed these studies are about 100 times more sensitive than previous ones. Good selectivity and high sensitivity obtained by Square wave voltammetry can open new possibilities of direct CM determination.