Development of a carbon nanotubes paste electrode modified with crosslinked chitosan for cadmium(II) and mercury(II) determination

A functionalized carbon nanotubes paste electrode modified with cross-linked chitosan for the determination of trace amounts of cadmium(II) and mercury(II) by linear anodic stripping voltammetry is described. Under optimal experimental conditions, the peak current was linear in the Cd(II) concentration range from 5.9 × 10⁻⁸ to 1.5 × 10⁻⁶ mol L⁻¹ with a detection limit of 9.8 × 10⁻⁹ mol L⁻¹ and, for Hg(II) from 6.7 × 10⁻⁹ to 8.3 × 10⁻⁸ mol L⁻¹with a detection limit of 2.4 × 10⁻⁹ mol L⁻¹. The proposed method was successfully applied for the determination of Hg(II) in natural and industrial wastewater samples, and Cd(II) in sediments, human urine, natural, and industrial wastewater samples.     

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.     

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.     

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.     

Voltammetric sensor based on ordered mesoporous carbon for folic acid determination

With ordered mesoporous carbon (OMC) as the modifier, a voltammetric sensor for folic acid (FA) was constructed on a glassy carbon electrode (GCE). Due to the good characteristics of OMC, FA exhibited an enhanced electrochemical response and lower reduction potential in the neutral solution. In addition, the experimental parameters such as pH values, accumulation time and potential were optimized. Using the differential pulse voltammetry (DPV) measurement, the peak current was found to be linear with FA concentration in the range from 5.0 × 10⁻¹⁰ to 1.0 × 10⁻⁷ M with a lower detection limit of 6.0 × 10⁻¹¹ M (S/N = 3). Also, in real samples analysis, the as-prepared sensor successfully gives satisfying results.     

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.     

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.     

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.     

Flow electroanalytical system based on cyclam-modified graphite felt electrodes for lead detection

A flow sensor for trace analysis of lead, using cyclam-modified graphite felt as working electrode is reported here. The detection is performed in two steps: the preconcentration of Pb²⁺ ions by complexation with immobilized cyclam and the analysis by linear sweep stripping voltammetry. Cyclam ligands are covalently immobilized onto the graphite felt by chemical reactions on amino acid linkers, previously attached to the electrode by an electrochemical process. A surface concentration of about 12% is estimated by cyclic voltammetry analyses, using redox probes. The factors, affecting the performances of the flow sensor are reported, such as the flow rate and the volume of the analyzed solution used during the preconcentration step. A calibration curve typical of an equilibrium process is obtained for lead ions with a limit of detection able to reach 2.5 × 10⁻⁸ mol L⁻¹, showing the ability of the cyclam-modified electrode to complex Pb²⁺ ions. The flow sensor shows a good selectivity toward lead in the presence of Cu²⁺ and Zn²⁺ ions.     

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%.     

Simultaneous determination of dopamine,ascorbic acid and uric acid on ordered mesoporous carbon/Nafion composite film

Here we report the selective, sensitive and simultaneous determination of dopamine (DA), ascorbic acid (AA) and uric acid (UA) on ordered mesoporous carbon (OMC)/Nafion composite film. Insoluble OMC was dispersed into ethanol in the presence of 0.5% Nafion, resulting in a stable and well-distributed OMC/Nafion suspension. After evaporation of ethanol, a uniform OMC/Nafion composite film-coated glassy carbon electrode (GCE) was achieved by simple casting deposition. The OMC/Nafion electrode shows ideal reversibility in 5 mM K₃[Fe(CN)₆] in the range of 0.02–0.50 V s⁻¹, indicating a fast electron-transfer kinetics. Moreover, due to the strong catalytic function of OMC, the overlapping voltammetric response of DA, AA and UA is well-resolved from each other with lowered oxidation potential and enhanced oxidation currents. The mechanism for the oxidation of AA, DA and UA at the OMC/Nafion film was also studied. By using differential pulse voltammetry (DPV), detection limits of 0.5, 20 and 4.0 μM were obtained for DA, AA and UA, respectively. The practical application of the electrode is successfully demonstrated for the determination of DA, AA and UA simultaneously in standard and real samples, without any preliminary treatment.     

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.     

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.     

Application of surfactant modified zeolite membrane electrode towards potentiometric determination of perchlorate

Potentiometric electrodes based on the incorporation of surfactant-modified zeolite Y (SMZ) particles into poly vinyl chloride (PVC) membranes were described. The electrode characteristics were evaluated regarding the response towards perchlorate ions. PVC membranes plasticized with dioctyl phthalate and without lipophilic additives (co-exchanger) are used throughout this study. The influence of membrane composition on the electrode response was studied. The electrode exhibited a Nernstian response towards perchlorate in the concentration range of 7.9 × 10⁻⁶–8.0 × 10⁻² M with a slope of 59.7 ± 0.9 mV per decade of perchlorate concentration with a working pH range of 1.7–9.5 with a fast response time of ≤10 s. The lower and upper detection limits were 4.07 × 10⁻⁷ and 0.13 M, respectively. The electrode response to perchlorate remains constant in the temperature range of 20–40 °C and in the presence of 2.5 × 10⁻⁶–1 × 10⁻² M NaNO₃. The selectivity coefficients for perchlorate anion as test species with respect to other anions were determined. The proposed modified zeolite-PVC electrode can be used for at least 30 days without any considerable divergence in potential. It was applied as indicator electrode in water samples with satisfactory results. The results of this study and our previous work show HDTMA plays different roles according to the zeolite type and matrix, as HDTMA-zeolite Y in a carbon paste matrix showed a good Nernstian behavior towards phosphate anion.     

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.     

Preparation of poly N,N-dimethylaniline/ferrocyanide film modified carbon paste electrode: Application to electrocatalytic oxidation of l-cysteine

Functionalized poly N,N-dimethylaniline film was prepared by adsorption of ferrocyanide onto the polymer forming at the surface of carbon paste electrode (CPE) in aqueous solution. The electrocatalytic ability of poly N,N-dimethylaniline/ferrocyanide film modified carbon paste electrode (PDMA/FMCPE) was demonstrated by oxidation of l-cysteine. Cyclic voltammetry and chronoamperometry techniques were used to investigate this ability. In the optimum pH (6.00), the electrocatalytic ability about 480 mV and the catalytic reaction rate constant, (k_h), can be seen 3.08 × 10³ M⁻¹ s⁻¹. The catalytic oxidation peak current determined by cyclic voltammetry method was linearly dependent on the l-cysteine concentration and the linearity range obtained was 8.00 × 10⁻⁵ –2.25 × 10⁻³ M. Detection limit of this method was determined as 6.17 × 10⁻⁵ M (2σ). At a fixed potential under hydrodynamic conditions (stirred solution), the calibration plot was linear over the l-cysteine concentration range 7.40 × 10⁻⁶ M–1.38 × 10⁻⁴ M. The detection limit of the method was 6.38 × 10⁻⁶ M (2σ).     

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.     

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.     

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.     

Crown ether-dendrimer based potentiometric Na sensor electrode

Poly(vinyl chloride) (PVC)-based membranes of silacrown end grafted carbosilane dendrimer (I) with sodium tetraphenylborate (NaTPB) as an anion inhibitor and dibutylphthalate (DBP), dioctylphthalate (DOP), dibutyl (butyl) phosphonate (DBBP) and 1-chloronaphthalene (CN) as plasticizing solvent mediators were prepared and used as Na⁺-selective electrodes. Optimum performance was observed with the membrane having I–PVC–NaTPB–DOP in the ratio 1:33:1:65 (w/w). The electrode works well over a wide concentration range 1.5 × 10⁻⁶–1.0 × 10⁻¹ M with Nernstian compliance 56.0 mV/decade between pH 5.8 and 9.2 with a fast response time of about 15 s. The selectivity relative to alkali, alkaline earth and transition heavy metal ions is good. The selectivity coefficient values towards potassium ions have been calculated to be 2.3 × 10⁻⁴ by utilizing Fixed Interference Method. The proposed electrode could be used for at least 2 months without considerable alteration in its potential. The effect of nonionic surfactants Tween 20, Tween 80, Triton X 100, Span 20 and Span 60 on the potentiometric properties of the sodium selective membrane was also studied.