Capability of a carbon-polyvinylchloride composite electrode for the detection of dopamine, ascorbic acid and uric acid

In this work, the composite carbon-polyvinylchloride (C-PVC) was used as an electrode for the detection of dopamine, ascorbic acid, uric acid and their mixtures by differential pulse voltammetry (DPV). The results showed that the untreated C-PVC electrode was selective and stable for the oxidation of dopamine in a mixture containing uric acid and an excess of ascorbic acid in acidic medium. The pre-treated C-PVC electrode in a neutral medium exhibited good resolution of the mixture components in the micro molar concentration range of DA. The ageing of the C-PVC electrode during longer time periods did not affect the peak potential and the detection of dopamine, uric acid and ascorbic acid in 0.1 M H₂SO₄. The practical analytical utility of the C-PVC electrode was demonstrated by the measurement of uric acid in human urine and serum samples without any preliminary pre-treatment.     

Electrocatalytic oxidation and simultaneous determination of uric acid and ascorbic acid on the gold nanoparticles-modified glassy carbon electrode

A new gold nanoparticles-modified electrode (GNP/LC/GCE) was fabricated by self-assembling gold nanoparticles to the surface of the l-cysteine-modified glassy carbon electrode. The modified electrode showed an excellent character for electrocatalytic oxidization of uric acid (UA) and ascorbic acid (AA) with a 0.306 V separation of both peaks, while the bare GC electrode only gave an overlapped and broad oxidation peak. The anodic currents of UA and AA on the modified electrode were 6- and 2.5-fold to that of the bare GCE, respectively. Using differential pulse voltammetry (DPV), a highly selective and simultaneous determination of UA and AA has been explored at the modified electrode. DPV peak currents of UA and AA increased linearly with their concentration at the range of 6.0 × 10⁻⁷ to 8.5 × 10⁻⁴ mol L⁻¹ and 8.0 × 10⁻⁶ to 5.5 × 10⁻³ mol L⁻¹, respectively. The proposed method was applied for the detection of UA and AA in human urine with satisfactory result.     

Voltammetric determination of ascorbic acid and dopamine in the same sample at the surface of a carbon paste electrode modified with polypyrrole/ferrocyanide films

Functionalized polypyrrole film were prepared by incorporation of [Fe(CN)₆]⁴⁻ as a doping anion, during the electropolymerization of pyrrole onto a carbon paste electrode in an aqueous solution by potentiostatic method. The electrochemical behavior of dopamine (DA) and ascorbic acid (AA) in one solution was studied at the surface of bare and modified carbon paste electrodes using cyclic voltammetry (CV), linear sweep voltammetry (LSV) and differntial pulse voltammetry (DPV) methods. The well separated anodic peaks for oxidation of DA and AA were observed at the surface of the modified carbon paste electrode under optimum condition (pH 6.00), which can be used for determination of these species simultaneously in mixture by LSV and DPV methods. The linear analytical curves were obtained in the ranges of 0.10-1.00 mM and 0.10-0.95 mM for ascorbic acid and 0.10-1.20 mM and 0.20-0.95 mM for dopamine concentrations using LSV and DPV methods, respectively. The detection limits (2σ) were determined as 3.38 × 10⁻⁵ M and 1.34 × 10⁻⁵ M of ascorbic acid and 3.86 × 10⁻⁵ M and 1.51 × 10⁻⁵ M of dopamine by CV and DPV methods.     

Simultaneous determination of ascorbic acid, dopamine and uric acid by use of a MWCNT modified carbon-ceramic electrode and differential pulse voltammetry

Multi walled carbon nanotube modified carbon-ceramic electrode (MWCNT/CCE) was employed for the simultaneous determination of ascorbic acid (AA), dopamine (DA) and uric acid (UA). The MWCNT/CCE displayed very good electrochemical catalytic activities with respect to CCE. The oxidation over-potentials of AA, DA and UA decreased dramatically, and their oxidation peak currents increased significantly at MWCNT/CCE compared to those obtained at the bare CCE. Differential pulse voltammetry was used for the simultaneous determination of AA, DA and UA in their ternary mixture. The peak separation between AA and DA, and DA and UA was large up to 205 and 160 mV, respectively. The calibration curves for AA, DA and UA were obtained in the range of 15.00-800.00, 0.50-100.00, and 0.55-90.00 μM, respectively. The detection limits (S/N = 3) were 7.71, 0.31, and 0.42 μM for AA, DA and UA, respectively.The present method was applied to the determination of AA, DA and UA in human serum and some commercial pharmaceutical samples, using standard adding method and the results were quite promising.     

Fabrication of Fc-SWNTs modified glassy carbon electrode for selective and sensitive determination of dopamine in the presence of AA and UA

The electrochemistry of dopamine (DA) was investigated by cyclic voltammetry (CV) and differential pulse voltammograms (DPV) at a glassy carbon electrode modified by the hybridization adducts of Fc-SWNTs. The electro-oxidation of DA could be catalyzed by Fc/Fc⁺ couple as a mediator and had a higher electrochemical response due to the unique carbon surface of carbon nanotubes. The anodic peaks of DA, ascorbic acid (AA) and uric acid (UA) in their mixture can be well separated by the prepared electrode. Under optimum conditions linear calibration graphs were obtained over the DA concentration range 5.0 × 10⁻⁶ to 3.0 × 10⁻⁵ M with a correlation coefficient of 0.9998 and a detection limit of 5.0 × 10⁻⁸ M based on the equation C_m = 3s_b1/m. The modified electrode has been successfully applied for the assay of DA in human blood serum. This work provides a simple and easy approach to selectively detect DA in the presence of AA and UA.     

Highly sensitive and simultaneous determination of hydroquinone and catechol at poly(thionine) modified glassy carbon electrode

A simple and highly sensitive electrochemical method for the simultaneous and quantitative detection of hydroquinone (HQ) and catechol (CT) was developed, based on a poly(thionine)-modified glassy carbon electrode (GCE). The modified electrode showed excellent electrocatalytic activity and reversibility towards the oxidation of both HQ and CT in 0.1 M phosphate buffer solution (PBS, pH 7.0). The peak-to-peak separations (ΔE_p) between oxidation and reduction waves in CV were decreased significantly from 262 and 204 mV at the bare GCE, to 63 and 56 mV, respectively for HQ and CT at the poly(thionine) modified GCE. Furthermore, the redox responses from the mixture of HQ and CT were easily resolved in both CV and DPV due to a difference in the catalytic activity of the modified GCE to each component. The peak potential separation of ca. 0.1 V was large enough for the simultaneous determination of HQ and CT electrochemically. The oxidation peak currents of HQ and CT were linear over the range from 1 to 120 μM in the presence of 100 and 200 μM of HQ and CT, respectively. The modified electrode showed very high sensitivity of 1.8 and 1.2 μA μM⁻¹ cm⁻² for HQ and CT, respectively. The detection limits (S/N = 3) for HQ and CT were 30 and 25 nM, respectively. The developed sensor was successfully examined for real sample analysis with tap water and revealed stable and reliable recovery data.     

Voltammetric studies of a novel bicopper complex modified glassy carbon electrode for the simultaneous determination of dopamine and ascorbic acid

A novel modified glassy carbon electrode (GCE) with a binuclear copper complex was fabricated using a cyclic voltammetric method in phosphate buffer solution. This modified electrode shows very efficient electrocatalytic activity for anodic oxidation of both dopamine (DA) and ascorbic acid (AA) via substantial decrease in anodic overpotentials for both compounds. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) using this modified electrode show two well-resolved anodic waves for the oxidation of DA and AA in mixed solution, which makes it possible for simultaneous determination of both compounds. Linear analytical curves were obtained in the ranges 2.0–120.0 μM and 5.0–160.0 μM for DA and AA concentrations by using DPV methods, respectively. The detection limits were 1.4 × 10⁻⁶ M of DA and 2.8 × 10⁻⁶ M of AA. This electrode was used for AA and DA determinations in medicine and foodstuff samples with satisfactory results.     

Enhanced electrochemical response in oxidative differential pulse voltammetry of dopamine in the presence of ascorbic acid at carboxyl-terminated boron-doped diamond electrodes

The differential pulse voltammetric (DPV) peak for dopamine (DA) oxidation was found to be highly amplified by the addition of ascorbic acid (AA) when carboxyl-terminated boron-doped diamond (BDD) electrodes were used as the working electrode. The DP voltammogram for a solution containing DA and AA obtained using a 4-pentenoic acid-modified BDD (4PA-BDD) electrode showed well-separated oxidation peaks for DA and AA at 0.4 and 0.6 V vs. Ag/AgCl, respectively. In addition, as the DA concentration increased at constant AA concentration, a simultaneous increase in the DA peak current density and decrease in the AA peak current density were observed. The slope of the calibration curve for the [DA] range of 1-10 μM in the presence of AA (500 μM) was seven times larger than that obtained in the absence of AA. Such an enhancement was found to be more efficient at 4PA-BDD than at oxidized-BDD, partly due to simple electrostatic effects and partly due to suppression of the polymerization of DA oxidation products by the terminal carboxyl groups. The enhanced detection method using a carboxyl-terminated BDD electrode should be an effective analytical tool, especially for determining low concentrations of DA in the presence of high concentrations of AA.     

Development of a biomimetic chitosan film-coated gold electrode for determination of dopamine in the presence of ascorbic acid and uric acid

A gold electrode surface was modified using a dinuclear copper complex [Cu^II₂ (Ldtb)(μ-OCH₃)](BPh₄) and then coated with a chitosan film. This biomimetic polymer film-coated electrode was employed to eliminate the interference from ascorbic acid and uric acid in the sensitive and selective determination of dopamine. The optimized conditions obtained for the biomimetic electrode were 0.1 M phosphate buffer solution (pH 8.0), complex concentration of 2.0 × 10⁻⁴ M, 0.1% of chitosan and 0.25% of glyoxal. Under the optimum conditions, the calibration curve was linear in the concentration range of 4.99 × 10⁻⁷ to 1.92 × 10⁻⁵ M, and detection and quantification limits were 3.57 × 10⁻⁷ M and 1.07 × 10⁻⁶ M, respectively. The recovery study gave values of 95.2-102.6%. The lifetime of this biomimetic sensor showed apparent loss of activity after 70 determinations. The results obtained with the modified electrode for dopamine quantification in the injection solution matrix were in good agreement with those of the pharmacopoeia method.     

Synthesis and characterization of layered Nb2C MXene/ZnS nanocomposites for highly selective electrochemical sensing of dopamine

MXenes, due to their exceptional properties, are tagged as materials of future in the field of two dimensional (2D) materials. Niobium carbide (Nb₂C) is an important member of MXene family having vast application in the field of lithium ion batteries and supercapacitors. However, its applications in the field of sensing have not been explored yet. This research work reports the synthesis and application of Nb₂C/ZnS nanocomposite for the sensing of dopamine (DA) for the first time. The etching of Nb₂C from parent MAX phase (Nb₂AlC) was performed at 55 °C. The application of Nb₂C electrode for the electrochemical sensing of DA was employed through differential pulse voltammetry (DPV). Zinc sulphide (ZnS) nanoparticles were synthesized hydrothermally to enhance the electrochemical properties of Nb₂C. The characterization of these prepared samples was done with the help XRD, SEM, EDS, and of FTIR spectroscopy. The MXene-ZnS nanocomposite modified glassy carbon electrode (GCE) proved to be a very effective electrode material to detect dopamine electrochemically with a wide linear detection range of 0.09–0.82 mM, a very low detection limit of 1.39 μM and excellent sensitivity of 12.1 μAμM^-1. The modified glassy carbon electrode also proved to be exceptionally selective towards dopamine in the presence of interfering agents like ascorbic acid, citric acid and glucose.     

Simultaneous determination of acetaminophen and dopamine using SWCNT modified carbon–ceramic electrode by differential pulse voltammetry

A highly sensitive method was investigated for the simultaneous determination of acetaminophen (AC) and dopamine (DA) using single wall carbon nanotubes modified carbon–ceramic electrode (SWCNT/CCE). The SWCNT/CCE displayed excellent electrochemical catalytic activities towards the oxidation of AC and DA. Under optimized experimental conditions in differential pulse voltammetry technique, AC and DA gave linear response over the ranges 0.2–100.0 μM (R² = 0.996) and 0.4–150.0 μM (R² = 0.999), respectively. The detection limits (S/N = 3) were found to be 0.12 μM for AC and 0.22 μM for DA. The present method was applied to the determination of AC and DA in some commercial pharmaceutical samples.     

Voltammetric studies of a cobalt(II)-4-methylsalophen modified carbon-paste electrode and its application for the simultaneous determination of cysteine and ascorbic acid

A carbon-paste electrode (CPE) chemically modified with the cobalt(II)-4-methylsalophen (CoMSal) as a Schiff base complex was used as a highly sensitive and fairly selective electrochemical sensor for simultaneous determination of minor mounts of ascorbic acid (AA) and cysteine. This modified electrode shows very efficient electrocatalytic activity for anodic oxidation of both AA and cysteine via substantially decreasing of anodic overpotentials for both compounds. The mechanism of electrochemical oxidation of both AA and cysteine using CoMSal-modified electrode was thoroughly investigated by cyclic voltammetry and polarization studies. Results of cyclic voltammetry (CV) and differential pulse voltammetry (DPV) using this modified electrode show two well-resolved anodic waves for the oxidation of AA and cysteine, which makes it possible for simultaneous determination of both compounds. A linear range of 1 × 10⁻⁴ to 5 × 10⁻⁷ M for cysteine in a constant concentration of 1 × 10⁻⁴ M AA in buffered solution (as a background electrolyte) was obtained from DPV measurements using this electrode. The linear range, which is obtained for AA in the presence of 1 × 10⁻⁴ M cysteine, was in the range of 1 × 10⁻⁴ to 1 × 10⁻⁶ M. The modified electrode has good reproducibility (RSD ≤ 2.5%), low detection limit (sub-micromolar) and high sensitivity for the detection of both AA and cysteine with a very high stability in its voltammetric response. Differential pulse voltammetry using the modified electrode exhibited a reasonable recovery for a relatively wide concentration range of cysteine spiked to a synthetic human serum sample.     

Simultaneous voltammetric determination of ascorbic acid, dopamine and uric acid by methylene blue adsorbed on a phosphorylated zirconia-silica composite electrode

This paper describes the preparation, characterization and application of a composite electrode based on methylene blue adsorption to phosphorylated zirconia-silica mixed oxide particles prepared by a sol-gel process. This electrode electrocatalytically oxidizes ascorbic acid (AA), dopamine (DA) and uric acid (UA), allowing their simultaneous voltammetric detection. Well-defined and -separated oxidation peaks were observed by differential pulse voltammetry in a 0.35 mol l⁻¹ Tris-HCl buffer solution (pH 7.4) containing 0.5 mol l⁻¹ KCl. The anodic peak currents observed at −74, 94 and 181 mV increased with increasing concentrations of AA, DA and UA, respectively. Linear calibration plots were obtained over the range of 100-1600 μmol l⁻¹ for ascorbic acid, 6-100 μmol l⁻¹ for dopamine and 22-350 μmol l⁻¹ for uric acid with detection limits of 8.3 ± 0.1, 1.7 ± 0.1 and 3.7 ± 0.2 μmol l⁻¹, respectively. DA and UA concentrations could also be determined under conditions of excess AA (1 mmol l⁻¹).     

Electrochemical characterization of poly(eriochrome black T) modified glassy carbon electrode and its application to simultaneous determination of dopamine, ascorbic acid and uric acid

A polymerized film of eriochrome black T (EBT) was prepared on the surface of a glassy carbon (GC) electrode in alkaline solution by cyclic voltammetry (CV). The redox response of the poly(EBT) film at the GC electrode appeared in a couple of redox peak in 0.1 M hydrochloride and the pH dependent peak potential was −55.1 mV/pH which was close to the Nernst behavior. The poly(EBT) film-coated GC electrode exhibited excellent electrocatalytic activity towards the oxidations of dopamine (DA), ascorbic acid (AA) and uric acid (UA) in 0.05 mM phosphate buffer solution (pH 4.0) and lowered the overpotential for oxidation of DA. The polymer film modified GC electrode conspicuously enhanced the redox currents of DA, AA and UA, and could sensitively and separately determine DA at its low concentration (0.1 μM) in the presence of 4000 and 700 times higher concentrations of AA and UA, respectively. The separations of anodic peak potentials of DA-AA and UA-DA reached 210 mV and 170 mV, respectively, by cyclic voltammetry. Using differential pulse voltammetry, the calibration curves for DA, AA and UA were obtained over the range of 0.1-200 μM, 0.15-1 mM and 10-130 μM, respectively. With good selectivity and sensitivity, the present method provides a simple method for selective detection of DA, AA and UA in biological samples.     

Simultaneous detection of ascorbic acid, uric acid and homovanillic acid at copper modified electrode

The copper was deposited on glassy carbon (GC) and indium tin oxide (ITO) electrodes by electrochemical method. The copper structures on electrode were characterized by atomic force microscope, X-ray diffractometeric pattern and differential pulse voltammetric studies. Optimal conditions for uniform growth of copper structures on the electrode were established. Voltammetric sensor was fabricated using the copper deposited GC electrode for the simultaneous detection and determination of uric acid (UA) and homovanillic acid (HVA) in the presence of excess concentrations of ascorbic acid (AA). The voltammetric signals due to AA and UA oxidation were well separated with a potential difference of 400 mV and AA did not interfere with the measurement of UA and HVA at the GC/Cu electrode. Linear calibration curves were obtained in the concentration range 1-40 μM for AA and 20-50 μM for UA at physiological pH and a detection limit of 10 nM of UA in the presence of 10-fold excess concentrations of AA was achieved. The simultaneous detection of submicromolar concentrations of AA, UA and HVA was achieved at the GC/Cu electrode. The practical utility of the present GC/Cu modified electrode was demonstrated by measuring the AA content in Vitamin C tablet, UA content in human urine and blood serum samples with satisfactory results.     

Selective and sensitive detection of dopamine in the presence of ascorbic acid by molecular sieve/ionic liquids composite electrode

A simple, sensitive, and reliable method based on a molecular sieve/ionic liquids composite electrode has been successfully developed for selective determination of dopamine (DA). The electrochemical behavior of dopamine (DA) at the modified electrode was investigated by cyclic voltammetry (CV) and square wave voltammetry (SWV). The influence of experimental parameters including pH of solution, amount of modifier, accumulation potential and time on the response of DA was investigated. At the optimum conditions, the peak current of DA was linear with the concentration of DA in the wide range of 5.0 × 10⁻⁸ mol L⁻¹ to 8 × 10⁻⁴ mol L⁻¹, with the correlation coefficient of 0.9982. The detection limit was 1.0 × 10⁻⁸ mol L⁻¹ (S/N = 3) in the presence of 0.2 mM ascorbic acid (AA). The interference studies showed that the modified electrode had excellent selectivity. What's more, the modified electrode also exhibited good reproducibility and stability for determination of DA, and could be applied to determine human serum samples.     

Application of thionine-nafion supported on multi-walled carbon nanotube for preparation of a modified electrode in simultaneous voltammetric detection of dopamine and ascorbic acid

A modified carbon-paste electrode (CPE) is prepared by incorporating thionine-nafion supported on multi-walled carbon nanotube (MWCNT). The electrochemical behavior of dopamine (DA) and ascorbic acid (AA) on the surface of the modified electrode is investigated by cyclic voltammetry (CV). The results show that thionine effectively immobilized in the matrix of the paste by using an appropriate mixture of nafion/MWCNT under the ultrasonic condition. On the other hand, presence of nafion enhances the stability of the thionine supported by MWCNT in the composite electrode and improves the reproducibility of the surface of the modified electrode under renewing process by polishing. The results of cyclic and differential pulse voltammetric investigations show that the modified electrode possesses an efficient electrocatalytic activity for the electrochemical oxidation of DA and AA and a peak potential separation nearly 379 mV is resulted for two compounds. The prepared modified electrode does not show any considerable response toward the electro-oxidation of sulfhydryl compounds, such as, cysteine, penicillamine and glutathione, revealing a good selectivity for voltammetric response to AA and DA in clinical and pharmaceutical preparations. The effective electrocatalytic property, excellent peak resolution and ability for masking the voltammetric responses of the other biologically reducing agents, make the modified electrode suitable for simultaneous and sensitive voltammetric detection of sub-micromolar amounts of AA and DA.     

Application of silica gel as an effective modifier for the voltammetric determination of dopamine in the presence of ascorbic acid and uric acid

Amorphous silica gel modified carbon paste electrode (CPE) offers substantial improvements in voltammetric sensitivity and selectivity towards determination of dopamine (DA). Cyclic voltammetry of Fe(CN)₆^3−/4− as a negatively charged probe revealed that the surface of the silica gel modified carbon paste electrode had a high density of negative charge at pH 8.0. Therefore, the modified electrode adsorbed DA (pK_a = 8.9) and enhanced its voltammetric response while repulsed ascorbic acid (AA) (pK_a = 4.2) and uric acid (UA) (pK_a = 5.4) and inhibited their interfering effects. The influence of various experimental parameters including percent of silica gel in the CPE, pH of solution, and accumulation time and potentials, on the voltammetric response of DA was investigated. At the optimum conditions, the analytical curve was linear for dopamine concentrations from 2.0 × 10⁻⁷ to 1.0 × 10⁻⁶ mol L⁻¹ and 2.0 × 10⁻⁶ to 1.5 × 10⁻⁴ mol L⁻¹ with a detection limit (3σ) of 4.8 × 10⁻⁸ mol L⁻¹. The prepared electrode was used for determination of DA spiked into DA injection and human serum samples, and very good recovery results were obtained over a wide concentration range of DA.     

Preparation of polypyrrole/ferrocyanide films modified carbon paste electrode and its application on the electrocatalytic determination of ascorbic acid

Functionalized polypyrrole film were prepared by incorporation of (Fe(CN)₆)⁴⁻ as doping anion, during the electropolymerization of pyrrole onto a carbon paste electrode (CPE) in aqueous solution by using potentiostatic method. The electrochemical behavior of the (Fe(CN)₆)³⁻/(Fe(CN)₆)⁴⁻ redox couple in polypyrrole was studied by cyclic voltammetry and double step potential chronoamperometry methods. In this study, an obvious surface redox reaction was observed and dependence of this reaction on the solution pH was illustrated. The electrocatalytic ability of polypyrrole/ferrocyanide films modified carbon paste electrode (Ppy/FCNMCPEs) was demonstrated by oxidation of ascorbic acid. It has been found that under optimum condition (pH 7.00), the oxidation of ascorbic acid at the surface of such electrode occurs at a potential about 540 mV less positive than unmodified carbon paste electrode. The kinetic parameters such as electron transfer coefficient, α and catalytic reaction rate constant, k_h′, were also determined by using various electrochemical approaches.The catalytic oxidation peak current showed a linear dependent on the ascorbic acid concentration and a linear calibration curve was obtained in the range of 4.5×10⁻⁴ to 9.62×10⁻³ M of ascorbic acid with a correlation coefficient of 0.9999. The detection limit (2σ) was determined as 5.82×10⁻⁵ M.     

The electrochemical synthesis of polyaniline/polysulfone composite films and electrocatalytic activity for ascorbic acid oxidation

Polyaniline (PANI)/polysulfone (PSF) composite films with asymmetric porous structure were successfully prepared by electropolymerization. The back face (in contact with the electrode) of the freestanding composite film is green while the outer face is white. The chemical component and the morphology of the surfaces were characterized by FTIR spectra and scanning electron microscopy, respectively. It was shown that replicate films gave reproducible voltammetry in 0.5 M H₂SO₄. The influence of the electrolyte and the acidic concentration on the redox peak currents of polyaniline were investigated in detail. The composite film electrode showed good electrocatalytic activity for ascorbic acid, which the anodic overpotential was evidently reduced compared with that obtained at bare Pt electrode. The diffusion coefficient of ascorbic acid was 1.38 × 10⁻⁶ cm² s⁻¹.