Highly Sensitive and Selective Adsorptive Stripping Voltammetric Method Employing a Lead Film Screen‐printed Electrode for Determination of Cobalt as its Nioximate Complex

A carbon screen‐printed electrode modified in‐situ with lead film (PbF‐SPCE) was applied for the adsorptive stripping voltammetric determination of Co(II) in the form of a complex with 1,2‐cyclohexanedione dioxime. Lead film was electrochemically deposited in situ on SPCE from a 0.2 M ammonia buffer solution (pH 8.7) containing 5 ? 10^?5 M Pb(NO₃)₂ and 5 ? 10^?5 M nioxime. Due to the very low LOD (0.003 µgL^?1, i.e., 0.05 nmol L^?1 Co(II); t_acc=120s), the developed procedure could be rated among the most sensitive methods employing SPEs. The Ni(II) signal was significantly lower than the Co(II) one and the separation of Ni(II) and Co(II) peaks was even better at the PbF‐SPCE than at the hanging mercury drop electrode.     

Fast Simultaneous Adsorptive Stripping Voltammetric Determination of Ni(II) and Co(II) at Lead Film Electrode Plated on Gold Substrate

A fast adsorptive stripping voltammetric procedure for simultaneous determination of Ni(II) and Co(II) in the presence of nioxime as a complexing agent at an in situ plated lead film electrode was described. The time of determination of these ions was shortened due to the application of gold as a substrate for lead film. At gold substrate lead film formation and accumulation of Ni(II) and Co(II) complexes with nioxime proceeds simultaneously. To obtain a stable signals for both ions a simple procedure of activation of the electrode was proposed. Calibration graphs for an accumulation time of 20 s were linear from 5×10^?9 to 1×10^?7 mol L^?1 and from 5×10^?10 to 1×10^?8 mol L^?1 for Ni(II) and Co(II), respectively. The procedure with the application of a lead film electrode on a gold substrate was validated in the course of Ni(II) and Co(II) determination in certified reference materials.     

Determination of Trace of Cobalt in Complex Matrices by Adsorptive Stripping Voltammetry at a Lead Film Electrode

An adsorptive stripping voltammetric procedure for the determination of cobalt in a complex matrices at an in situ plated lead film electrode was described. The procedure exploits the enhancement effect of a cobalt peak observed in the system Co(II)–nioxime–piperazine‐1,4‐bis(2‐ethanesulfonic acid)–cetyltrimethylammonium bromide. The calibration graph was linear from 5×10^?10 to 2×10^?8 mol L^?1 and from 1×10^?10 to 1×10^?9 mol L^?1 for the accumulation times 120 and 600 s, respectively. The detection limit (based on the 3 σ criterion) for Co(II) following accumulation time of 600 s was 1.1×10^?11 mol L^?1. The interference of high concentrations of foreign ions and surfactants was studied.     

Catalytic Adsorptive Stripping Chronopotentiometry of Co(II)‐DMG‐Bromate System at an In Situ Plated Lead Film Electrode

A novel catalytic adsorptive stripping chronopotentiometric (CC‐CAdSCP) procedure for the determination of Co(II) traces was developed using a lead film electrode (PbFE). The PbFE was generated in situ on a glassy carbon support from a 0.1 M ammonia buffer containing 1×10^?5 M Pb(II), 6.5×10^?5 M DMG and the target metals. An addition of 0.2 M NaBrO₃ to the solution yielded an 11‐fold catalytic enhancement of chronopotentiometric response of the Co(II)‐DMG complex. The CC‐CAdSCP curves were well‐developed, sharp and reproducible (RSD 5.0 % for 5×10^?9 M Co(II)). The limit of detection for Co(II) for 210 s of accumulation time was 4×10^?10 M (0.024 µg L^?1). In addition, the elaborated method allowed the simultaneous quantification of Co(II) and Ni(II) simultaneously.     

Catalytic Adsorptive Stripping Voltammetric Determination of Cobalt and Nickel as Their α‐Furil Dioxime Complexes

The exploitation of the catalytic‐adsorptive effect in the Co(II)‐dioxime‐nitrite systems provides a significant increase of the Co adsorptive stripping voltammetric response and subsequently the influence of the interfering elements such as Ni and Zn is strongly diminished. The purpose of the present paper was to study voltammetric properties of Co and Ni in a supporting electrolyte containing ammonia buffer, α‐furil dioxime in the absence and in the presence of nitrite, by differential pulse polarography and adsorptive stripping voltammetry. Results of detailed studies aimed at optimizing the analytical parameters for simultaneous catalytic adsorptive stripping voltammetric determination of Co and Ni in the form of complexes with α‐furil dioxime in the presence of Zn matrix are presented. In the supporting electrolyte of composition 0.1 M NH₄Cl, 0.5 M NH₃, 4×10^?5 M αFD, 0.5 M NaNO₂ the linearity range amounts from 0.03 to 2.4 μg/L for Co and from 0.3 to 9 μg/L for Ni for 20 s of accumulation. The method enables the determination of Co and Ni in the presence of a great excess of Zn with the detection limit equal to 0.02 μg/L Co and 0.2 μg/L Ni obtained for a 20 s accumulation time.     

A Validated Voltammetric Procedure for Quantification of the Antifungal Drug Griseofulvin in Bulk Form,Tablets, and Biological Fluids at a Mercury Electrode

Abstract

Griseofulvin is an antifungal antibiotic used to treat various pathogenic mycotic diseases. The voltammetric behavior of griseofulvin at a hanging mercury drop electrode in Britton‐Robinson buffers of pH 2–11.5 was studied and discussed. A fully validated sensitive square‐wave adsorptive cathodic stripping voltammetric procedure was described for direct determination of bulk griseofulvin substance. The procedure was based on the reduction of the >C?O double bond of griseofulvin molecule following its preconcentration onto a hanging mercury drop electrode in a Britton‐Robinson buffer of pH 10. Limits of detection (LOD) and quantitation (LOQ) of 5.8×10^?10 M and 1.93×10^?9 M bulk griseofulvin were achieved, respectively. The proposed stripping voltammetric procedure was successfully applied to assay griseofulvin in tablets and in spiked human serum and urine samples. LOD of 8.65×10^?10 M and 6.6×10^?9 M and LOQ of 2.88×10^?9 M and 2.2×10^?8 M griseofulvin in spiked human serum and urine samples, respectively, were achieved.     

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).     

Lead Film Electrode Prepared with the Use of a Reversibly Deposited Mediator Metal in Adsorptive Stripping Voltammetry of Nickel

The paper presents the first report on application of a “hybrid” lead film electrode for the adsorptive stripping voltammetric determination of Ni(II) in the presence of nioxime as a complexing agent. The strategy to create a “hybrid” electrode is based on the combination of ex situ and in situ plating methods and the use of a reversibly deposited mediator metal (Zn) for the lead film formation. The surface morphology of a new sensor was characterized by atomic force microscopy. The detection limit for Ni(II) obtained at 120 s of accumulation time was 3.9×10^?11 mol L^?1. The proposed method was validated for the determination of nickel in water certified reference materials with good results.     

The new Micro‐set for Adsorptive Stripping Voltammetric Simultaneous Determination of Nickel and Cobalt Traces in Aqueous Media

This article the first reports on a fabrication and application of an electrochemical three electrode micro‐set containing: in situ plated lead film on carbon fiber working microelectrode, Ag/AgCl reference electrode and a platinum wire counter electrode placed in one casing for simultaneous Ni(II) and Co(II) traces determination by square wave adsorptive stripping voltammetry (SW AdSV). Ni(II) and Co(II) in forms of their complexes with nioxime were accumulated on the lead film plated on a carbon fibers microelectrode during standard procedure of measurement. Thanks to the fact that measurements were performed in micro‐vessel of a volume of 200 μl small amounts of reagents were used to prepare samples for measurements. In addition, because of the use of microelectrode, sample solutions were not mixed during accumulation step of measurements. This fact creates the possibility of conducting fields analysis. The experimental parameters (composition of the supporting electrolyte, potential and time of accumulation) and possible interference effects were investigated. The linear calibration graphs for Ni(II) and Co(II) were in the range from 2×10^?9 to 1×10^?7 mol L^?1 and from 2×10^?10 to 1×10^?8 mol L^?1 for Ni(II) and Co(II), respectively. The correctness of the proposed method was checked by determining Ni(II) and Co(II) in the certified reference material (SPS‐SW1) with satisfactory results.     

Voltammetric Behavior of Mifepristone (RU‐486) Using Square‐Wave and Adsortive Stripping‐Wave Techniques. Determination in Urine Samples

The behavior of Mifepristone (RU‐486) was studied by square‐wave technique, leading to two methods for its determination in aqueous samples and urine samples at pH 2. The application of the square‐wave (SW) without the adsorptive accumulation and stripping voltammetric (AdSV) show the maximum response at ?0.896 V using an accumulation potential of ?0.5 V. The effect of experimental parameters that affect this determination are discussed. For the stripping technique, Mifepristone proved to be more sensitive, yielding signals four times larger than those obtained by applying a square‐wave scan without the previous accumulation. The calibration plot to determine Mifepristone was linear in the range 2.4×10^?8 and 5.4×10^?7 M by stripping mode with an accumulation time t_acc of 30 s. The relative standard deviation obtained for concentration levels of Mifepristone as low as 2.0×10^?7 M with square‐wave was 1.17% (n=10) and with stripping square‐wave 2.02% (n=10) in the same day. The two proposed methods (SW and SWAdSV) were applied to the determination of Mifepristone in urine.     

Electrochemical Determination and in silico Studies of Fludarabine on NH2 Functionalized Multiwalled Carbon Nanotube Modified Glassy Carbon Electrode

A sensitive voltammetric technique has been developed for the determination of Fludarabine using amine‐functionalized multi walled carbon nanotubes modified glassy carbon electrode (NH₂‐MWCNTs/GCE). Molecular dynamics simulations, an in silico technique, were employed to examine the properties including chemical differences of Fludarabine‐ functionalized MWCNT complexes. The redox behavior of Fludarabine was examined by cyclic, differential pulse and square wave voltammetry in a wide pH range. Cyclic voltammetric investigations emphasized that Fludarabine is irreversibly oxidized at the NH₂‐MWCNTs/GCE. The electrochemical behavior of Fludarabine was also studied by cyclic voltammetry to evaluate both the kinetic (k_s and E_a) and thermodynamic (ΔH, ΔG and ΔS) parameters on NH₂‐MWCNTs/GCE at several temperatures. The mixed diffusion‐adsorption controlled electrochemical oxidation of Fludarabine revealed by studies at different scan rates. The experimental parameters, such as pulse amplitude, frequency, deposition potential optimized for square‐wave voltammetry. Under optimum conditions in phosphate buffer (pH 2.0), a linear calibration curve was obtained in the range of 2×10^?7 M–4×10^?6 M solution using adsorptive stripping square wave voltammetry. The limit of detection and limit of quantification were calculated 2.9×10^?8 M and 9.68×10^?8 M, respectively. The developed method was applied to the simple and rapid determination of Fludarabine from pharmaceutical formulations.     

Square-wave adsorptive stripping voltammetric determination of antihypertensive agent telmisartan in tablets and its application to human plasma

The adsorptive stripping voltammetry of telmisartan was investigated with a hanging mercury drop electrode. This compound produced a catalytic hydrogen wave at ?1.5 V in Britton Robinson buffer of pH 10.38, and the peak current increased with adsorptive accumulation at the electrode. Adsorptive stripping voltammetry with the catalytic hydrogen wave could provide a sensitive novel method for the determination of telmisartan. Various chemical and instrumental parameters affecting the monitored electroanalytical response were investigated and optimized for telmisartan determination. Under these optimized conditions the square-wave adsorptive stripping voltammetric (SW-AdSV) peak current showed a linear dependence on drug concentration over the range 0.05–3.00 μg/mL (1 × 10^?7?6 × 10^?6 M) (r = 0.999) with accumulation for 120 s at ?1.0 V vs. Ag/AgCl. The proposed electrochemical procedure was successfully applied for the determination of telmisartan in pharmaceutical tablets and human plasma. The results of the developed SW-AdSV method were comparable with those obtained by reported analytical procedures.     

Catalytic Adsorptive Stripping Voltammetry of Cobalt in the Presence of Dimethylglyoxime and Nitrite at In Situ Plated Lead–Copper Film Electrode

A lead‐copper film electrode was proposed for Co(II) determination by catalytic adsorptive stripping voltammetry. The electrode was plated in situ and hence the exchange of a solution after plating step was not required. At optimized conditions the calibration graph for Co(II) was linear from 5×10^?10 to 2×10^?8 mol L^?1 for accumulation time of 15 s. The relative standard deviation for Co(II) determination at concentration 5×10^?9 mol L^?1 was 4.1%. The detection limits for Co(II) were 1.2×10^?10 and 1.0×10^?11 mol L^?1 for an accumulation time of 15 and 180 s, respectively. The method was applied to Co(II) determination in certified reference material and other water samples.     

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.     

An adsorptive stripping voltammetry of nickel and cobalt at a solid lead electrode

For the first time, a solid lead electrode (PbE) was exploited for adsorptive stripping voltammetric determination of Ni(II) and Co(II) in the presence of nioxime as a complexing agent. The calibration graphs for Ni(II) and Co(II) were linear from 0.059 to 0.59 µg L^?1 and from 0.029 to 0.29 µg L^?1 (accumulation time 120 s), respectively. The analytical parameters such as the detection limit and separation of analytical signals obtained at the solid lead electrode were comparable with those obtained using a lead film electrode while better in comparison to those reported before for the bismuth film or solid bismuth electrodes. Co(II) could be determined in the presence of a large excess of Ni(II) and Zn(II). The proposed electrode was applied to determine Co(II) and Ni(II) traces in certified reference material and a natural water sample with satisfactory results.     

Fabrication of Bismuth/Multi-walled Carbon Nanotube Composite Modified Glassy Carbon Electrode for Determination of Cobalt

A bismuth/multi‐walled carbon nanotube (Bi/MWNT) composite modified electrode for determination of cobalt by differential pulse adsorptive cathodic stripping voltammetry is described. The electrode is fabricated by potentiostatic pre‐plating bismuth film on an MWNT modified glassy carbon (GC) electrode. The Bi/MWNT composite modified electrode exhibits enhanced sensitivity for cobalt detection as compared with the bare GC, MWNT modified and bismuth film electrodes. Numerous key experimental parameters have been examined for optimum analytical performance of the proposed electrode. With an adsorptive accumulation of the Co(II)‐dimethylglyoxime complex at ?0.8 V for 200 s, the reduction peak current is proportional to the concentration of cobalt in the range of 4.0×10^?10?1.0×10^?7 mol/L with a lower detection limit of 8.1×10^?11 mol/L. The proposed method has been applied successfully to cobalt determination in seawater and lake water samples.     

Determination of Copper at a Glassy Carbon Electrode Modified with Langmuir–Blodgett Film of p‐tert‐Butylthiacalix[4]arene

A new type of voltammetric sensor, Langmuir–Blodgett film of p‐tert‐butylthiacalix[4]arene modified glassy carbon electrode, was advanced and used for determining copper at trace levels by differential pulse stripping voltammetry. Calibration plot was found to be linear in the range of 2×10^?8 M to 5×10^?6 M; the detection limit was 2×10^?9 M. Possible recognition mechanism was also discussed. From determination of Copper in real samples (river, lake and tap water) it can be concluded that the method is rapid, sensitive in determining of copper and can be used in the analysis of natural water samples.     

New Protocol for Determination of Rifampicine by Adsorptive Stripping Voltammetry

For determinations of organic compounds by adsorptive stripping voltammetry till now the same material of the electrode has been used for the accumulation and stripping steps. This paper describes a new protocol for extending the range of organic compounds, which can be determined by adsorptive stripping voltammetry. In the proposed procedure the accumulation step was performed on the electrode modified by a lead film, which assures adsorption of the studied species on the modified electrode and then the stripping step of the accumulated substance was performed on the support of the lead film electrode. As an example rifampicine was accumulated by adsorption at the lead film electrode while in the stripping step lead film and then the accumulated rifampicine were oxidized at a glassy carbon electrode. Using an acetate buffer as a supporting electrolyte a calibration graph for rifampicine in the range from 2.5×10^?10 to 1×10^?8 mol L^?1 was obtained. The detection limit for rifampicine following 60 s accumulation time was equal to 9×10^?11 mol L^?1. The obtained detection limit was comparable or lower than reported previously for other stripping voltammetric procedures. The proposed procedure was applied to rifampicine determination in pharmaceutical preparation.     

Use of adsorptive square-wave anodic stripping voltammetry at carbon paste electrode for the determination of amlodipine besylate in pharmaceutical preparations

The antihypertensive drug amlodipine has been characterized voltammetrically in a carbon paste electrode by means of anodic stripping voltammetry. An adsorptive stripping method in a carbon paste electrode for trace determination of amlodipine has been described. Cyclic voltammetric studies indicated the oxidation of amlodipine besylate at the electrode surface through a single two-electron irreversible step fundamentally controlled by adsorption. A study of the variation in the peak current with solution variables such as pH, ionic strength, concentration of amlodipine, possible interference, and instrumental variables, such as preconcentration time and accumulation potential, has resulted in the optimization of the oxidation signal for analytical purposes. By anodic adsorptive anodic stripping voltammetry, the calibration plot was linear in the range 9.9 × 10^?9 ? 1.4 × 10^?7 M with a detection limit of 2 × 10^?10 M in a carbon paste electrode at pH 11.0. The procedure was successfully applied to the assay of amlodipine besylate in some commercial products in the market (Amlopres®, Amlodipine, and Norvasc®). The percentage recoveries were in agreement with those obtained by the reference method.     

Extraction of PCDD/PCDF from soil with supercritical CO2: Optimization by a three-level factorial design approach

A highly sensitive and selective voltammetric procedure is described for the simultaneous determination of eleven elements (Cd, Pb, Cu, Sb, Bi, Se, Zn, Mn, Ni, Co and Fe) in water samples. Firstly, differential pulse anodic stripping voltammetry (DPASV) with a hanging mercury drop electrode (HMDE) is used for the direct simultaneous determination of Cd, Pb, Cu, Sb and Bi in 0.1 M HCl solution (pH = 1) containing 2 M NaCl. Then, differential pulse cathodic stripping voltammetry (DPCSV) is used for the determination of Se in the same solution. Zn is subsequently determined by DPASV after raising the pH of the same solution to pH 4. Next, the pH of the medium is raised to pH 8.5 by adding NH₃/NH₄Cl buffer solution for the determination of Mn by DPASV. Ni and Co are determined in the same solution by differential pulse adsorptive stripping voltammetry (DPAdSV) after adding DMG (1 × 10^–4 M). Finally, 1 × 10^–5 M 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP) is added to the solution for the determination of Fe by DPAdSV. The optimal conditions are described. Relative standard deviations and relative errors are calculated for the eleven elements at three different concentration levels. The lower detection limits for the investigated elements range from 1.11 × 10^–10 to 1.05 × 10^–9 M, depending on the element determined. The proposed analysis scheme was applied for the determination of these eleven elements in some ground water samples.