Determination of trace vanadium(V) by adsorptive anodic stripping voltammetry on an acetylene black paste electrode in the presence of alizarin violet

A sensitive and simplified voltammetric method is developed for the determination of trace amounts of vanadium(V) by adsorptive anodic stripping voltammetry using an acetylene black (AB) paste electrode. The method is based on the preconcentration of the V(V)–alizarin violet (AV) complex at open circuit while stirring the solution for 90 s in 0.15 mol dm⁻³ hexamethylenetetraamine–hydrochloric acid buffer (pH 4.4), the adsorbed complex is then oxidized, producing a response with a peak potential of 564 mV when scanning linearly from 0 to 1000 mV. For voltammetric determination of V(V), the parameters influencing the peak current have been optimized. Under the selected conditions, the peak current and concentration of V(V) accorded with linear relationship in the range of 8.0 × 10⁻¹⁰ mol dm⁻³–1.0 × 10⁻⁷ mol dm⁻³ (c_AV = 2.0 × 10⁻⁶ mol dm⁻³) and 1.0 × 10⁻⁷ mol dm⁻³–8.0 × 10⁻⁶ mol dm⁻³ (c_AV = 2.0 × 10⁻⁵ mol dm⁻³), the detection limit (three times signal to noise) was estimated to be 6.0 × 10⁻¹⁰ mol dm⁻³ for 90 s accumulation. The relative standard deviation (RSD) is 1.9% and 2.3% for V(V) concentrations of 1.0 × 10⁻⁷ mol dm⁻³ and 1.0 × 10⁻⁸ mol dm⁻³ respectively. Finally, this proposed method was successfully applied to the determination of V(V) in natural water samples.     

One-impedance for one-concentration impedimetry as an electrochemical method for determination of the trace zirconium ion

A new method is established for the electrochemical detection of zirconium ion (Zr(IV)) based on electrochemical impedance spectroscopy transduction method, and hydroxamated gold surface recognition system. The method successfully served for the detection of Zr(IV) with a wide dynamic range of 1.0 × 10⁻⁹ to 5.0 × 10⁻⁵ mol L⁻¹, and a detection limit in nmol L⁻¹ scale. Construction of the calibration curve by “one-impedance for one-concentration” method developed here helped us to save the experimental time by saving the data acquisition time by a factor of ∼20, and further, eliminating data approximation and parameter extraction times.     

A stannum/bismuth/poly(p-aminobenzene sulfonic acid) film electrode for measurement of Cd(II) using square wave anodic stripping voltammetry

In the present work, a new method for a trace analysis of metal cadmium ion has been developed on the stannum/bismuth/poly(p-aminobenzene sulfonic acid) film electrode in combination with square wave anodic stripping voltammetry. This new electrode was prepared by in situ depositing stannum, bismuth and target metal on the poly(p-aminobenzene sulfonic acid)(p-ABSA) coated glassy carbon electrode. Some key factors including the pH of measure solution, the proper proportion between Bi(III) and Sn(II), the preconcentration time and the preconcentration potential have been studied and optimized. Compared with the traditional bismuth-film electrode, the stannum/bismuth/poly(p-ABSA) film electrode displayed higher stripping current response. In addition, it has the advantages of better stability and less toxicity. Under the optimum conditions, the linear calibration graph for Cd(II) in the concentration range of 0.5–55 μg L⁻¹ was obtained and the detection limit was 0.32 μg L⁻¹. The method was applied to the analysis of cadmium ion in tap water sample with satisfactory results.     

A differential pulse voltammetric method for simultaneous determination of ascorbic acid,dopamine, and uric acid using poly (3-(5-chloro-2-hydroxyphenylazo)-4,5-dihydroxynaphthalene-2,7-disulfonic acid) film modified glassy carbon electrode

A stable modified glassy carbon electrode based on the poly 3-(5-chloro-2-hydroxyphenylazo)-4,5-dihydroxynaphthalene-2,7-disulfonic acid (CDDA) film was prepared by electrochemical polymerization technique to investigate its electrochemical behavior by cyclic voltammetry. The properties of the electrodeposited films, during preparation under different conditions, and their stability were examined. The homogeneous rate constant, k_s, for the electron transfer between CDDA and glassy carbon electrode was calculated as 5.25(±0.20) × 10² cm s⁻¹. The modified electrode showed electrocatalytic activity toward ascorbic acid (AA), dopamine (DA), and uric acid (UA) oxidation in a buffer solution (pH 4.0) with a diminution of their overpotential of about 0.12, 0.35, and 0.50 V for AA, DA, and UA, respectively. An increase could also be observed in their peak currents. The modified glassy carbon electrode was applied to the electrocatalytic oxidation of DA, AA, and UA, which resolved the overlapping of the anodic peaks of DA, AA, and UA into three well-defined voltammetric peaks in differential pulse voltammetry (DPV). This modified electrode was quite effective not only for detecting DA, AA, and UA, but also for simultaneous determination of these species in a mixture. The separation of the oxidation peak potentials for ascorbic acid–dopamine and dopamine–uric acid were about 0.16 V and 0.17 V, respectively. The final DPV peaks potential of AA, DA and UA were 0.28, 0.44, and 0.61 V, respectively. The calibration curves for DA, AA, and UA were linear for a wide range of concentrations of each species including 5.0–240 μmol L⁻¹ AA, 5.0–280 μmol L⁻¹ DA, and 0.1–18.0 μmol L⁻¹ UA. Detection limits of 1.43 μmol L⁻¹ AA, 0.29 μmol L⁻¹ DA and 0.016 μmol L⁻¹ UA were observed at pH 4. Interference studies showed that the modified electrode exhibits excellent selectivity toward AA, DA, and UA.     

Investigation of polarographic interference between Se(IV) and Cr(VI), its elimination and application to Gerede river water

Trace chromium(VI) determination plays an important role since it is carcinogenic agent and toxic pollutant. For this purpose a direct method is developed using differential pulse polarography, DPP. When selenite was added into solutions of some ions such as copper(II), lead(II), cadmium(II), zinc(II), and chromium(VI) their DP polarographic peak decreased. This kind of interference will cause large errors in the determinations, its elimination is very important. The interference between selenite and Cr(VI) ions could be eliminated in B-R (Britton-Robbinson) buffer at pH 8.5. In this work the effect of components present in buffer has been investigated and it was found that phosphate and borate eliminated the formation of Cr–Se intermetallic compound formation. While it was possible to determine 1 × 10⁻⁵ M Cr(VI) in the presence of 100 times more selenite as (1.0 ± 0.1) × 10⁻⁵ M, in borate medium, it was possible to determine (1.0 ± 0.05) × 10⁻⁵ M in phosphate medium. In the presence of selenite detection limit (S/N = 3) was 9.0 × 10⁻⁸ M Cr(VI) by using either phosphate or borate This method was applied to Gerede river water, after oxidation all Cr(III) present into Cr(VI).     

Selective electrochemical sensing of calcium dobesilate based on an ordered mesoporous carbon-modified pyrolytic graphite electrode

Cyclic voltammetric investigation of calcium dobesilate (CD) in aqueous acid media was carried out by using an ordered mesoporous carbon-modified pyrolytic graphite electrode (OMC/PGE). A pair of well-defined redox peaks of CD was observed at the OMC/PGE, showing its good elelctrochemial response towards CD. The anodic current is linear with CD concentration in the range of 1.0 × 10⁻⁷–1.3 × 10⁻³ mol L⁻¹, with a detection limit of 4.0 × 10⁻⁸ mol L⁻¹. Meanwhile, the proposed electrode can avoid some interference coexisting with CD, such as uric acid, serotonin, and ascorbic acid. The proposed method can be potentially applied for selective electrochemical sensing of CD in physiological condition.     

Electrochemical layer-by-layer modified imprinted sensor based on multi-walled carbon nanotubes and sol–gel materials for sensitive determination of thymidine

A novel electrochemical sol–gel imprinted sensor for sensitive and convenient determination of thymidine was developed. Thin film of molecularly imprinted sol–gel polymers with specific binding sites for thymidine was cast on carbon electrode by electrochemical deposition. Multi-walled carbon nanotubes (MWCNTs) were introduced for the enhancement of electronic transmission and sensitivity. The morphology and performance of the imprinted film was characterized by scanning electron microscopy (SEM), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), differential pulse voltammetry (DPV) and amperometric measurements (i–t) in detail. The results showed that the imprinted film exhibited high selectivity toward thymidine. The linear range is over the range from 2 to 22 μmol L⁻¹, and the linear regression equation for thymidine is I = 0.867C + 0.232 with the detection limit of 1.6 × 10⁻⁹ mol L⁻¹(S/N = 3). The imprinted sensor was successfully employed to detect thymidine in some zidovudine-tablet samples.     

Electroanalytical determination of sildenafil in Viagra tablets using screen-printed and conventional carbon paste electrodes

This work compares the electroactivity of a conventional carbon-paste electrodes and screen-printed carbon electrodes. Potentiometric sensors responsive to sildenafil citrate (SILC) drug (the active component of Viagra) are described, characterized, compared and used for drug assessment. The proposed carbon paste electrode is fully characterized in terms of plasticizer type, response time, life span, soaking time, titrant, pH and temperature. The electrodes exhibited linear response with a Nernstian slope of 58.20 ± 1 and 58.82 ± 0.5 mV decade⁻¹ for SILC in the concentration range from 1.0 × 10⁻⁷ to 1.0 × 10⁻² and 5.30 × 10⁻⁷ to 1.0 × 10⁻² mol L⁻¹ with good reproducibility for CPE and SPE, respectively. Both CPE and SPE could be used in the pH range 3.0–5.0 and the isothermal coefficient is found to be 0.98 and 0.85 mV/°C, respectively. The limit of detection was found to be 9.0 × 10⁻⁸ and 3.5 × 10⁻⁷ mol L⁻¹ for CPE and SPE, respectively. They were applied to potentiometric determination of SILC in pure state and pharmaceutical preparation under batch conditions. The CPE and SPE sensors display good selectivity for SILC drug over large number of inorganic cations, sugars and amino acids commonly used in drug formulations. The CPE and SPE show high selectivity for the drug under investigation. The results obtained using the fabricated CPE is compared with those obtained by SPE for spiked pharmaceutical samples.     

Ultrasensitive determination of tungsten(VI) on pikomolar level in voltammetric catalytic adsorptive catechol-chlorate(V) system

The renewable mercury film electrode, applied for the determination of tungsten(VI) ultra traces using differential pulse catalytic adsorptive cathodic stripping voltammetry (DPCAdSV) with presence of catechol as a ligand and chlorate(V) is presented. The calibration graph obtained for W(VI) is linear from 0.025 nM (4.5 ng L⁻¹) to 130 nM (23.9 μg L⁻¹) for a preconcentration time of 30 s, with correlation coefficient of 0.9989. For the renewable mercury electrode (Hg(Ag)FE) with a surface area of 4.4 mm² the detection limit for a preconcentration time of 60 s is as low as 0.2 ng L⁻¹. The repeatability of the method at a concentration level of the analyte as low as 0.09 μg L⁻¹, expressed as RSD is 3.1% (n = 5). The proposed method was successfully applied and validated by studying the certified reference material CTA-VTL-2 and simultaneously recovery of W(VI) from spiked water samples.     

Adsorptive stripping voltammetric determination of vanadium(V) witch chloranilic acid using cyclic renewable mercury film silver based electrode

The cyclic renewable mercury film silver based electrode (Hg(Ag)FE), applied for the determination of vanadium(V) traces using differential pulse adsorptive cathodic stripping voltammetry (DP AdCSV) with presence of chloranilic acid as a ligand is presented. The calibration graph obtained for V(V) is linear from 0.25 nM (12.7 ng L⁻¹) to 150 nM (7.6 μg L⁻¹) for a preconcentration time of 20 s, with correlation coefficient of 0.9992. For a Hg(Ag)FE with a surface area of 6.6 mm² the detection limit for a preconcentration time of 90 s is as low as 0.5 ng L⁻¹. The repeatability of the method at a concentration level of the analyte as low as 1.3 μg L⁻¹, expressed as RSD is 2.1% (n = 5). The proposed method was successfully applied and validated by studying the certified reference materials TMRAIN-95, SPS-SW1, SPS-SW2 and simultaneously recovery of V(V) from spiked water samples.     

Electrochemical and spectral studies of self-assembled monolayer of 1,8,15,22-tetraaminophthalocyanatocobalt(II) on indium tin oxide surface

Self-assembled monolayer (SAM) of 1,8,15,22-tetraaminophthalocyanatocobalt(II) (4α-Co^IITAPc) was prepared on indium tin oxide (ITO) electrode by spontaneous adsorption from dimethylformamide (DMF) solution containing 4α-Co^IITAPc. The SAM of 4α-Co^IITAPc formed on ITO electrode was characterized by cyclic voltammetry, Raman and UV–visible spectroscopic techniques. The cyclic voltammogram (CV) of 4α-Co^IITAPc SAM shows two pairs of well-defined redox peaks corresponding to Co^III/Co^II and Co^IIIPc⁻¹/Co^IIIPc⁻². The surface coverage (Γ) was calculated by integrating the charge under the anodic wave corresponding to Co^II oxidation and it was found to be 2.25 × 10⁻¹⁰ mol cm⁻². Raman spectrum obtained for the SAM of 4α-Co^IITAPc on ITO surface shows strong stretching and breathing bands of Pc macrocycle, pyrrole ring and isoindole ring. Further, the –NH₂ bending mode of vibration was absent for the SAM of 4α-Co^IITAPc on ITO surface which indirectly confirmed that all the amino groups of 4α-Co^IITAPc are involved in bonding with ITO surface. UV–visible spectrum for the SAM of 4α-Co^IITAPc on ITO surface shows an intense B-band, Q-band and n–π^∗ transition with slight broadening when compared to that of 4α-Co^IITAPc in DMF.     

Penetration of weakly acidic polyelectrolytes into PVC membrane containing quaternary ammonium salt for potentiometry both by ion exchange and by coextraction with proton

The ion exchange of anionic polyelectrolytes (APEs) on the PVC membrane containing tridodecylmethylammonium bromide as a carrier was analyzed by monitoring elution of the bromide from and penetration of APEs into the membrane. The equilibration time for exchange by APEs was around three times longer than that by a common anion of perchlorate. Heparin at 10⁻⁴ mol L⁻¹ and poly(vinyl sulfate) (PVS) at 10⁻² mol L⁻¹ could completely replace the bromide in the membrane, while polyacrylate (PA) at 10⁻² mol L⁻¹ could not. The chemical amount of the penetrated PVS was comparable to that of the eluted bromide, while that of PA was much larger than that of the eluted bromide and even the total amount of the carrier. PA penetrated into the organic phase within the membrane by coextraction with proton as well as by ion exchange, so as to avoid geometric restriction on multiple ion-pair formation.     

Selective determination of dopamine in the presence of ascorbic acid at a multi-wall carbon nanotube-poly(3,5-dihydroxy benzoic acid) film modified electrode

A sensitive and selective method for determination of dopamine (DA) using multi-wall carbon nanotube (MWCNT)-poly(3,5-dihydroxy benzoic acid) [poly(DBA)] modified electrode is developed. The modified electrode shows excellent electrocatalytic activity toward the oxidation of dopamine in phosphate buffer solutions at pH 7.4. Using cyclic voltammetry, the linear range of 1 × 10⁻⁷–7.0 × 10⁻⁵ M in the interference of 500 μM ascorbic acid (AA) and the detection limit of 1.0 × 10⁻⁸ M were estimated for the measurement of DA in pH 7.4 phosphate buffer solutions. The value of DA current retained 98.36% of the initial response current after the modified electrode exposed to the air for one week. The interference studies showed that the modified electrode excludes effectively large excess of AA. The kinetic characteristics of the transfer of DA demonstrated that the electron propagation between DA and electrode was accelerated at MWCNT-poly(DBA) modified electrode. The work provided a valid and simple approach to selectively detect dopamine in the presence of AA in physiological environment.     

Electrocatalytic oxidation of hydrazine using glassy carbon electrode modified with carbon nanotube and terpyridine manganese(II) complex

Here, we report a simple and extremely effective method to modify a glassy carbon (GC) electrode with carbon nanotubes (CNTs) and [Mn(CH₃COO)(CH₃OH)₂(pyterpy)]ClO₄, (pyterpy = 4′-(4-pyridyl)-2,2′:6′,2′′-terpyridine) complex. The kinetics of the reaction between, the terpyridine manganese(II) complex, mediator and hydrazine has been characterized using cyclic voltammetry and rotating disk electrode voltammetry. The catalytic currents were proportional to the concentration of hydrazine giving rise to calibration curves characterized by two linear segments. The linear segment over the concentration range of 1.00 × 10⁻³–1.05 mM could be used with analytical purposes to determination of hydrazine with a detection limit of 0.50 μM and a sensitivity of 0.038 μA/μM. The heterogeneous rate constant, k′ for the oxidation of hydrazine at the surface of the modified electrode was determined by rotating disk electrode voltammetry using the Koutecky–Levich plot. The transfer coefficient (α) for electrocatalytic oxidation of hydrazine and the diffusion coefficient of this substance under the experimental conditions were also investigated. The resulting modified electrode retains its initial response for at least one month if stored dry in air.     

Sensitive electrochemical detection of hydroquinone with carbon ionogel electrode based on BMIMPF6

An ionic liquid (IL) 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF₆) based carbon ionogel electrode (CIE) was fabricated for the sensitive voltammetric sensing of hydroquinone (HQ) in this paper. Due to the specific characteristics of the prepared working electrode, HQ exhibited an enhanced electrochemical response on CIE with a pair of well-defined redox peaks appeared in pH 2.5 phosphate buffer solution. The electrochemical behaviors of HQ on CIE were investigated by different electrochemical methods such as cyclic voltammetry and differential pulse voltammetry with the electrochemical parameters calculated. Under the optimal conditions the oxidation peak currents exhibited good linear relationship with the HQ concentration in the range from 0.13 to 100.0 μmol L⁻¹ with the detection limit of 0.07 μmol L⁻¹ (3σ). The CIE showed separated electrochemical response to HQ and catechol in the mixture solution. The proposed method was successfully applied to HQ detection in artificial wastewater with the recovery in the range from 98.9% to 102.0%.     

Electrochemical impedimetry of electrodeposited poly(propylene imine) dendrimer monolayer

Voltammetric and electrochemical impedance spectroscopic (EIS) studies of generation one poly(propylene imine) (G1 PPI) dendrimer as an electroactive and catalytic nanomaterials both in solution and as an electrode modifier based on a simple one step electrodeposition method is presented. The G1 PPI exhibited a reversible one electron redox behaviour at E^0′ ca 210 mV in phosphate buffer pH 7.2 with diffusion coefficient and Warburg coefficient of 7.5 × 10⁻¹⁰ cm² s⁻¹ and 8.87 × 10⁻⁴ Ω s^−1/2 respectively. Cyclic voltammetric electrodeposition of a monolayer of G1 PPI on glassy carbon electrode was carried out between −100 mV and 1100 mV for 10 cycles. The nanoelectrode was electroactive in PBS at E^0′ ca 220 mV. Kinetic profiles such as time constant (4.64 × 10⁻⁵ s rad⁻¹), exchange current (1.55 × 10⁻⁴ A) and heterogeneous rate constant (4.52 × 10⁻³ cm s⁻¹) obtained from EIS showed that the dendrimer layer catalysed the redox reaction of Fe^2+/3+ in [Fe(CN)₆]^3−/4− redox probe.     

Silver nanoparticles modified carbon nanotube paste electrode for simultaneous determination of dopamine and ascorbic acid

A novel modified carbon-paste electrode was employed for the simultaneous determination of dopamine (DA) and ascorbic acid (AA) with good selectivity and high sensitivity. Silver nanoparticle and carbon nanotube modified carbon-paste electrode (Ag/CNT–CPE) displayed excellent electrochemical catalytic activities towards dopamine (DA) and ascorbic acid (AA). The oxidation overpotentials of DA and AA were decreased significantly compared with those obtained at the bare CPE. Differential pulse voltammetry was used for the simultaneous determination of DA and AA. The peak separation between DA and AA was 67 mV. The calibration curves for DA and AA were obtained in the range of 8.0 × 10⁻⁷–6.4 × 10⁻⁵ M and 3.0 × 10⁻⁵–2.0 × 10⁻³ M, respectively. The lowest detection limits (S/N = 3) were 3.0 × 10⁻⁷ M and 1.2 × 10⁻⁵ M for DA and AA, respectively. Method was applied to the determination of DA and AA in real samples.     

Highly temperature dependent mass-transport parameters for ORR in Nafion® 211

Nafion® 211 differs from previous versions of Nafion in that the membrane is cast from a dispersion rather than being melt-extruded. As such, the water sorption properties are different, as is the rate of increase in water content with temperature. Kinetic and mass-transport parameters for dispersion-cast Nafion® 211 were determined using solid-state electrochemistry in the temperature range 30–70 °C, 100% relative humidity, and 30 psi oxygen pressure. Exchange current densities, Tafel slopes, and transfer coefficients for ORR in Nafion® 211, are similar to those observed in Nafion® 117; mass-transport parameters are not. At 30 °C and 100% RH oxygen solubility and the diffusion coefficient is determined to be 1.16 × 10⁻⁵ mol cm⁻³ and 1.13 × 10⁻⁶ cm² s⁻¹, respectively. Oxygen permeability at 30 °C (1.28 × 10⁻¹¹ mol cm⁻¹ s⁻¹) is lower than in Nafion® 117 (5.31 × 10⁻¹¹ mol cm⁻¹ s⁻¹) by factor of 4, while at T > 60 °C the permeability of Nafion® 211 increases significantly to values higher than Nafion® 117, and is correlated with the increase in water content and hydration number (λ) with temperature.     

Simultaneous determination of epinephrine and uric acid at a gold electrode modified by a 2-(2,3-dihydroxy phenyl)-1, 3-dithiane self-assembled monolayer

In the present paper, the use of a gold electrode modified by 2-(2,3-dihydroxy phenyl)-1,3-dithiane self-assembled monolayer (DPDSAM) for the determination of epinephrine (EP) and uric acid (UA) was described. Initially, cyclic voltammetry was used to investigate the redox properties of this modified electrode at various scan rates. The apparent charge transfer rate constant, k_s, and transfer coefficient, α, were calculated. Next, the mediated oxidation of EP at the modified electrode was described. At the optimum pH of 8.0, the oxidation of EP occurs at a potential about 155 mV less positive than that of an unmodified gold electrode. The values of electron transfer coefficients (α = 0.356), catalytic rate constant (k = 1.624 × 10⁴ M⁻¹ s⁻¹) and diffusion coefficient (D = 1.04 × 10⁻⁶ cm² s⁻¹) were calculated for EP, using electrochemical approaches. Based on differential pulse voltammetry, the oxidation of EP exhibited a dynamic range between 0.7 and 500.0 μM and a detection limit (3σ) of 0.51 μM. Furthermore, simultaneous determination of EP and UA at the modified electrode was described. Finally, this method was used for the determination of EP in EP ampoule.     

Electrochemistry of magnolol and interaction with DNA

The electrochemical behaviors of magnolol have been studied at glassy carbon electrode using cyclic voltammetry, linear sweep voltammetry and chronocoulometry. Moreover, its interaction with DNA was investigated in solution by electrochemical methods and ultraviolet–visible spectroscopy. The experiment results indicated that the electrochemical oxidation of magnolol was an irreversible process with one proton and one electron transfer. The electron transfer coefficient (α) was calculated to be 0.441 ± 0.001. At the scan rate from 100 mV/s to 450 mV/s, the electrode process was controlled by the adsorption step and at the range of 600–950 mV/s the electrochemical oxidation was diffusion controlled process. The corresponding electrochemical rate constant (k_s) was 0.0760 ± 0.0001 s⁻¹. Through chronocoulometry experiment, the diffusion coefficient (D) and the surface concentration (Γ) were obtained as (3.76 ± 0.01) × 10⁻⁷ cm²/s and (2.98 ± 0.01) × 10⁻¹⁰ mol/cm². In addition, the interaction of magnolol and DNA was ascribed to be electrostatic interaction and the calculated association constant (β) and Hill coefficient (m) were 1.14 × 10⁵ M⁻¹ and 0.973. At last a sensitive and convenient electrochemical method was proposed for the determination of magnolol.