Polyviologen Modified Glassy Carbon Electrode Employed for Anodic Stripping Voltammetric Determination of Mercury(II)

In this study, a polyviologen modified glassy carbon electrode (PVGCE) was used to detect Hg(II) in aqueous solutions containing significant amounts of chloride anions in order to demonstrate the electroanalytical application of the electropolymerized polyviologen. The polyviologen thin film was formed on the electrode surface by applying a constant potential of ?1.0 V in the pH 4.2 Britton–Robinson (BR) buffer solution that contains 0.1 wt% of viologen oligomers. The PVGCE was found capability to improve the detection limit of Hg(II) in the solutions with high concentration of chloride because Hg(II) forms negative complex ions HgCl that can be accumulated to PVGCE by the anion‐exchange characteristic of polyviologen. With 5 minutes accumulation at ?0.2 V, the adsorbed HgCl anions were reduced to Hg and deposited on the electrode surface, and were determined with the following anodic stripping differential pulse voltammetry (ASDPV). The dependence of anodic stripping current versus concentration was linear from 1 ppb (5 nM) to 100 ppb (0.5 μM) with a regression coefficient of 0.9959.     

Stripping Analysis of Trace Arsenic Based on the MnOx/AuNPs Composite Film Modified Electrode in Alkaline Media

A simple, rapid fabricated and sensitive modified electrode for detection of As(III) in alkaline media was proposed. The modified electrode was prepared by co‐electrodeposition of manganese oxides (MnO_x) and gold nanoparticles (AuNPs) on the glassy carbon electrode (GCE) with cyclic voltammetry. Linear sweep anodic stripping voltammetry (LS‐ASV) was employed for the determination of arsenic (III) without interference from Cu(II), Hg(II), and other coexisting metal ions. A lower detection limit of 0.057 µg L^?1 (S/N=3) were obtained with a accumulation time of 200 s. The proposed method was successfully applied to determine arsenic (III) in real water samples with satisfactory recoveries.     

Sensitive and Green Method for Determination of Chemical Oxygen Demand Using a Nano‐copper Based Electrochemical Sensor

Copper nanoparticles (nano‐Cu) were electrodeposited on the surface of glassy carbon electrode (GCE) potentiostatically at −0.6 V vs. Ag/AgCl for 60 s. The developed nano‐copper modified glassy carbon electrode (nano‐Cu/GCE) was optimized and utilized for electrochemical assay of chemical oxygen demand (COD) using glycine as a standard. The surface morphology and chemical composition of nano‐Cu/GCE were investigated using scanning electron microscope (SEM) and energy dispersive X‐ray spectrometer (EDX), respectively. The electrochemical behavior was investigated using linear sweep voltammetry (LSV) which is characterized by a remarkable anodic peak at ∼0.6 V, compared to bare GCE. This indicates that nano‐Cu enhances significantly the electrochemical oxidation of glycine. The effect of different deposition parameters, such as Cu²⁺ concentration, deposition potential, deposition time, pH, and scan rate on the response of the developed sensor were investigated. The optimized nano‐Cu/GCE based COD sensor exhibited a linear range of 15 to 629.3 ppm, and a lower limit of detection (LOD) of 1.7 ppm (S/N=3). This developed method exhibited high tolerance level to chloride ion (0.35 M chloride ion has minimal influence). The analytical utility of the prepared COD sensor was demonstrated by investigating the COD recovery (99.8±4.3) and the assay of COD in different water samples. The results obtained were verified using the standard dichromate method.     

Determination of Lead(II) Using Screen‐Printed Bismuth‐Antimony Film Electrode

This work presents a disposable bismuth‐antimony film electrode fabricated on screen‐printed electrode (SPE) substrates for lead(II) determination. This bismuth‐antimony film screen‐printed electrode (Bi‐SbSPE) is simply prepared by simultaneously in situ depositing bismuth(III) and antimony(III) with analytes on the homemade SPE. The Bi‐SbSPE can provide an enhanced electrochemical stripping signal for lead(II) compared to bismuth film screen‐printed electrodes (BiSPE), antimony film screen‐printed electrodes (SbSPE) and bismuth‐antimony film glassy carbon electrodes (Bi‐SbGC). Under optimized conditions, the Bi‐SbSPE exhibits attractive linear responses towards lead(II) with a detection limit of 0.07 µg/L. The Bi‐SbSPE has been demonstrated successfully to detect lead in river water sample.     

Gold Nanoparticle Modified Electrodes Show a Reduced Interference by Cu(II) in the Detection of As(III) Using Anodic Stripping Voltammetry

Interference by Cu(II) causes serious problems in the detection of As(III) using anodic stripping voltammetry at gold electrodes. The behavior of Cu(II) and As(III) were examined at both a gold macro electrode and two kinds of gold nanoparticle modified electrodes, one where gold particles are deposited on glassy carbon (GC) and the other where basal plane pyrolytic graphite (BPPG) is the substrate. The sensitivity of As(III) detection was higher on gold nanoparticle modified electrodes than those on a macro gold electrode by up to an order of magnitude. In addition, the stripping peak of As(III) was narrower and more symmetric on a gold nanoparticle‐modified GC electrode, leading to analytical data with a lower limit of detection. At a macro gold electrode, the peak currents of Cu(II) were higher than those on gold nanoparticle modified electrodes. Accordingly, through the use of gold nanoparticle modified electrodes, the effect of copper interference to the arsenic detection can be reduced.     

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.     

Pt‐Nanoparticle Incorporated Carbon Paste Electrode for the Determination of Cu(II) Ion by Anodic Stripping Voltammetry

Pt‐nanoparticles were synthesized and introduced into a carbon paste electrode (CPE), and the resulting modified electrode was applied to the anodic stripping voltammetry of copper(II) ions. The synthesized Pt‐nanoparticles were characterized by cyclic voltammetry, scanning electron microscopy and X‐ray photoelectron spectroscopy techniques to confirm the purity and the size of the prepared Pt‐nanoparticles (ca. 20 nm). This incorporated material seems to act as catalysts with preconcentration sites for copper(II) species that enhances the sensitivity of Cu(II) ions to Cu(I) species at a deposition potential of ?0.6 V in an aqueous solution. The experimental conditions, such as, the electrode composition, pH of the solution, pre‐concentration time, were optimized for the determination of Cu(II) ion using as‐prepared electrode. The sensitivity changes on the different binder materials and the presence of surfactants in the test solution. The interference effect of the coexisted metals were also investigated. In the presence of surfactants, especially TritonX‐100, the Cu(II) detection limit was lowered to 3.9×10^?9 M. However, the Pt‐nanoparticle modified CPE begins to degrade when the period of deposition exceeds to 10 min. Linear response for copper(II) was found in the concentration range between 3.9×10^?8 M and 1.6×10^?6 M, with an estimated detection limit of 1.6×10^?8 M (1.0 ppb) and relative standard deviation was 4.2% (n=5).     

Square-wave adsorptive stripping voltammetry at glassy carbon electrode for selective determination of manganese. Application to some industrial samples

A new method to determine manganese by voltammetry after controlled adsorptive accumulation of the manganese–ammonium–acetate at the glassy carbon electrode is described. The manganese complex gives well-defined voltammetric peak at pH 4.0 and 9.0. Cathodic stripping voltammetry combined with the Osteryoung square-wave mode at the glassy carbon electrode gave rise to both sensitivity and selectivity of the determination of manganese in some industrial samples. The method offers enhanced sensitivity in comparison to analogous measurements presented in the literature. The detection limit with 5 min accumulation is 0.022 μg l⁻¹ . Simultaneous determination of manganese in presence of Cu(II), Pb(II) and Zn(II) could be easily done using anodic stripping voltammetry at pH 4.0. Calibration plots are constructed and the method was checked with the aid of standard industrial reference samples giving values of standard deviations between 1.2 and 1.8.     

Detection of lead(II) using an glassy carbon electrode modified with Nafion, carbon nanotubes and benzo-18-crown-6

A glassy carbon electrode was modified with Nafion, carbon nanotubes and benzo-18-crown-6 to give an electrode for the selective determination of lead(II) via square wave anodic stripping voltammetry. The use of carbon nanotubes with their extraordinary electrical conductivity and strong adsorption ability warrants high sensitivity. Benzo-18-crown-6 is employed as a “molecular scavenger” because of its excellent selectivity for lead(II). The modified electrode shows enhanced sensitivity, reproducibility and selectivity for lead(II) even without applying an electrical potential during the accumulation time. It responds linearly to lead(II) in the 1 to 30 nM concentration range (with a correlation coefficient of 0.9992) after a 10-min accumulation time. The detection limit is 1 nM. The sensor exhibits excellent selectivity over other heavy metal ions such as Cd(II), Cu(II), Zn(II), and Hg(II).

Simultaneous Electrochemical Detection of Co(II) and Cu(II) by 1‐Diazo‐2‐Naphthol‐4‐Sulfonic Acid/MWCNTs Modified Electrode

This work describes a simple preparation of 1‐diazo‐2‐naphthol‐4‐sulfonic acid (1,2,4‐acid) and multiwalled carbon nanotubes (MWCNTs) modified glassy carbon electrode (GCE) for the simultaneous detection of Co(II) and Cu(II). MWCNTs, with their good conductivity and large surface area, were drop‐casted onto the surface of the GCE prior to the electrodeposition of 1,2,4‐acid, a metal chelating agent. Co(II) and Cu(II) were simultaneously measured by differential pulse anodic stripping voltammetry (DPASV) in a batch system. Under optimum conditions, the linear range of Co(II) was between 0.10 and 2.5 μg mL⁻¹ with an LOD of 80 ng mL⁻¹. Two linear ranges were obtained for Cu(II), 0.0050 to 0.030 μg mL⁻¹ and 0.040 to 0.25 μg mL⁻¹,with an LOD of 2.4 ng mL⁻¹. The method offered a high operational stability for up to 52 measurements (RSD=3.4 % for Co(II) and 2.6 % for Cu(II)) and good reproducibility (RSD=1.2 % for Co(II) and 1.7 % for Cu(II)). In the simultaneous detection of Co(II) and Cu(II), there was no effect from common interferences found in wastewater. The method was successfully applied in real water samples with good recoveries (88.2±0.8 to 102.0±0.8 % for Co(II) and 96.5±0.4 to 103.8±0.9 % for Cu(II)) and the results were in good agreement with those obtained from inductively coupled plasma optical emission spectrometry (ICP‐OES) (P >0.05).     

Manganese Detection Using Stencil‐printed Carbon Ink Electrodes on Transparency Film

Mn concentrations were determined using square‐wave cathodic stripping voltammetry (CSV) with inexpensive, stencil‐printed carbon ink electrodes generated on polypropylene transparency films. Using an optimized pH 5 ammonium acetate buffer and addition of 1,4‐benzoquinone, a detection limit as low as 500 nM (30 ppb) was achieved. Addition of 1,4‐benzoquinone improved peak potential reproducibility and height, while addition of 3.5 % w/w sodium chloride to the background solution approximately doubled the sensitivity (μA/ppm). Tolerance tests with interfering metals were conducted and the method was found to be resilient to chromium(VI), iron(III), magnesium(II), nickel(II), and zinc(II), but susceptible to aluminum(III), copper(II), iron(II), and lead(II) at concentration ratios at or below one. This technique was successfully used to measure Mn levels in yerba mate and green tea samples as an example application.     

Thiol‐Functionalized Silica Thin Film Modified Electrode in Determination of Mercury Ions in Natural Water

The use of a thin thiol‐functionalized silica film modified glassy carbon electrode in the determination of Hg(II) ions in a natural water sample is described. A typical measurement involves two successive steps: a glassy carbon electrode coated with a thin mesoporous silica film containing 10% of mercaptopropyl groups, according to the MPTMS/TEOS ratio in the starting sol‐gel, was first immersed into the accumulation medium for 15 min, then removed, and finally transferred into a detection solution containing KCl 1.0 mol L^?1 where detection was performed by anodic stripping voltammetry. In this medium the previously accumulated Hg²⁺ species complexed by the thiol groups in an open circuit preconcentration step is then directly reduced at ?0.6 V during 60 s prior to be quantified by a differential pulse anodic scan from ?0.6 to 0.3 V (vs. Ag/AgCl). A stripping peak appeared at about ?0.01 V, which is directly proportional to the quantity of the analyte previously accumulated into the film. The best results were obtained under the following conditions: 100 mV pulse amplitude and 10 mV s^?1 scan rate in 1.0 mol L^?1 KCl solution pH 2.0. Using such parameters a linear dynamic range from 1.00 to 10.0×10^?8 mol L^?1 Hg(II) was observed with a limit of detection of 4.3 nmol L^?1 for an accumulation time of 15 min. Hg(II) spiked in a natural water sample was determined between 97.0 and 101.4% mean recovery at 10^?8 mol L^?1 level. The results indicate that this electrode is sensitive and selective for the Hg(II)determination.     

Ultrasensitive Voltammetric Detection of Trace Lead(II) and Cadmium(II) Using MWCNTs‐Nafion/Bismuth Composite Electrodes

Multiwall carbon nanotubes were dispersed in Nafion (MWCNTs‐NA) solution and used in combination with bismuth (MWCNTs‐NA/Bi) for fabricating composite sensors to determine trace Pb(II) and Cd(II) by differential pulse anodic stripping voltammetry (DPASV). The electrochemical properties of the MWCNTs‐NA/Bi composites film modified glassy carbon electrode (GCE) were evaluated. The synergistic effect of MWCNTs and bismuth composite film was obtained for Pb(II) and Cd(II) detection with improved sensitivity and reproducibility. Linear calibration curves ranged from 0.05 to 100 μg/L for Pb(II) and 0.08 to 100 μg/L for Cd(II). The determination limits (S/N=3) were 25 ng/L for Pb and 40 ng/L for Cd, which compared favorably with previously reported methods in the area of electrochemical Pb(II) and Cd(II) detection. The MWCNTs‐NA/Bi composite film electrodes were successfully applied to determine Pb(II) and Cd(II) in real sample, and the results of the present method agreed well with those of atomic absorption spectroscopy.     

Sub‐ppt Level Detection of Mercury(II) Based on Anodic Stripping Voltammetry with Prestripping Step at an In Situ Formed Bismuth Film Modified Glassy Carbon Electrode

Sensitive and selective detection of Hg²⁺ in solution is a challenging work. An anodic stripping voltammetry with prestripping step at an in situ formed bismuth film modified glassy carbon electrode was proposed for detection of mercury(II) in solution. This prestripping step was able to decrease the background and improve the signal‐to‐noise ratio and thus enhance the sensitivity. With this method, highly sensitive and selective detection of Hg²⁺ with a ppt‐level detection limit of 0.5 ng L^?1 could be achieved. Moreover, this method provides low interference, rapid and extreme simple and convenience, and hold great promise for in situ Hg²⁺ determination.     

Silica‐modified Electrodes for Electrochemical Detection of Malachite Green

New silica‐modified glassy carbon electrodes prepared with three different sorts of ordered mesoporous silica (OMS) were characterized and tested for the electrochemical detection of Malachite Green (MG). The electrodes were prepared by drop casting using silica suspensions and, for stability sake, a Nafion coating was deposited on the electrode top by the same technique. Square wave anodic stripping voltammetry was used to investigate the effect of various experimental parameters (deposition time, solution pH, silica type and concentration) on the performance of the modified electrodes. The best electrode (GC/MCM‐41‐NH₂/Nafion) with detection limit 0.36 μM, sensitivity 0.164±0.003 A/M; linear domain 1–6 μM was applied to detect MG in a commercial product commonly used as biocide in aquaria for ornamental fish.     

Adsorptive Stripping Voltammetric Detection of Tea Polyphenols at Multiwalled Carbon Nanotubes‐Chitosan Composite Electrode

This study reports the catalytic oxidation and detection of tea polyphenols (TPs) at glassy‐carbon electrode modified with multiwalled carbon nanotubes‐chitosan (MWCNTs‐CS) film. The adsorption of TPs at the surface of the MWCNTs through π–π conjugation prevents the aggregation of nanotubes and induces a stable MWCNTs suspension in water over 30 days. Based on the adsorptive accumulation of polyphenols at MWCNTs, TPs is sensitively and selectively detected by adsorptive stripping voltammetry. The accumulation conditions and pH effect on the adsorptive stripping detection were examined. The linear range was found to be 100 to 1000 mg L^?1 with a detection limit of 10 mg L^?1 (S/N=3) for 2.5 min accumulation. Additionally, the MWCNTs‐CS electrode is easily renewed by applying positive potential to remove the adsorbed TPs. This method was successfully applied to determine TPs in commercially available teas with satisfied result compared with that of conventional spectrometric analysis.     

Determination of Mercury by Anodic Stripping Voltammetry with a Gold Nanoparticle‐Modified Glassy Carbon Electrode

The aim of this work is the development of a procedure for the determination of aqueous Hg(II) by anodic stripping voltammetry at a gold nanoparticle‐modified glassy carbon electrode (AuNPs‐GCE). The signal of aqueous Hg(II) was measured in the square wave mode; the effect of potential scan parameters, deposition potential and deposition time on the analytical signal was examined. The supporting electrolyte was 0.06 M HCl. The repeatability, the linearity, the accuracy, the detection limit of the procedure and the interferences of other cations and of anions were evaluated. The performance of the AuNPs‐GCE was compared with those of a solid (SGE) and a film (FGE) gold electrode: the AuNPs‐GCE showed to provide lower detection limits and higher repeatability. The renewable surface permits to eliminate memory effects, to maintain a stable baseline and response, and to avoid frequent mechanical cleaning steps. The applicability of the AuNPs‐GCE for Hg(II) determination in drinking waters, sediments and pharmaceuticals was demonstrated.     

Electrocatalytic Properties of a Novel Poly‐1‐Naphthylamine‐Modified Electrode Using Ascorbic Acid as Molecule Probe

A glassy carbon electrode was modified with an electropolymerized film of 1‐naphthylamine in aqueous solution. The electrocatalytic properties of this modified electrode (ME) were investigated using ascorbic acid (AA) as probe molecule. The electrochemical behavior of AA in buffer solution was examined by voltammetry and amperometry. The results showed that the ME exhibited good electrocatalytic activity towards the oxidation of AA, as a consequence, it can be used as amperometric sensor of this analyte in a flow injection system with good sensitivity. Calibration curves were linear over the concentration range 0.05–1.50 mM with a phosphate buffer solution pH 3 as the carrier, the detection limit was 1 ppm (S/N=3). The methods were applied to the determination of AA in beverages and pharmaceutical products. A good correlation with a reference method was attained.     

Immunosensing of NT‐proBNP via Cu2+‐based MOFs Biolabeling and in situ Microliter‐droplet Anodic Stripping Voltammetry

Immunoassay of amino‐terminal pro‐B‐type natriuretic peptide (NT‐proBNP) was conducted using Cu²⁺‐1,3,5‐benzenetricarboxylic acid metal‐organic frameworks (HKUST‐1 MOFs) as the secondary antibody label, and in situ microliter‐droplet anodic stripping voltammetry detection of Cu²⁺ in 0.1 M HNO₃+1 M NaCl directly on the glassy carbon immunoelectrode. Electrochemical methods, quartz crystal microbalance, scanning electron microscopy and energy dispersive spectroscopy were employed for material and electrode characterizations. Under optimized conditions, the limit of detection (S/N=3) was 0.33 fg mL^?1, and the analysis of NT‐proBNP in clinical serum samples returned good results.     

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).