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1.
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.  相似文献   

2.
A dopamine polymer film was electrogenerated on the bare gold template from a 5 × 10−3 M dopamine solution in phosphate buffer at pH 7 and next subjected to overoxidation in 0.1 M sodium hydroxide solution. The overoxidized dopamine polymer film obtained shows good permeability to cationic species and was used for quantitative determination of dopamine. A linear relationship between dopamine concentration and current response was obtained in the range of 1 × 10−6 M to 6 × 10−4 M with the detection limit 2 × 10−7 M. The results have shown that using the overoxidized dopamine film it is possible to perform electrochemical analysis of dopamine without interference of ascorbic and uric acids, which is the major limitation in dopamine determination. The modified electrode shows good selectivity, sensitivity, reproducibility and high stability.  相似文献   

3.
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 Cm = 3sb1/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.  相似文献   

4.
The development of a simple and efficient method to 2-(2-nitrophenyl)-1H-benzimidazole (NB) electrochemical determination using a polymer film coated chemically modified electrode is described. A glassy carbon (GC) electrode was modified employing an electro-polymerized film of 1-naphtylamine (1-NAP) followed by an over-oxidation treatment in 0.2 M sodium hydroxide solution (poly-1-NAPox electrode).The electrochemical behaviour of NB at the poly-1-NAPox electrode was investigated in a mixture of 10% ethanol + 90% buffer solution (pH 2) by cyclic voltammetry (CV) and square-wave voltammetry (SWV). The experimental results suggested that the poly-1-NAPox electrode had a good effect on NB electrochemical response because it avoided the electrode surface fouling as a consequence of the adsorption of NB reduction products, which was found when a bare GC electrode was employed as the working electrode. The NB cathodic current was dependent on the polymeric film over-oxidation degree (α).NB could be determined in the range from 2 × 10−6 to 5 × 10−5 M. The NB detection and quantification limits were 5 × 10−7 and 1.7 × 10−6 M, respectively. The percent relative standard deviation of the peak current to 10-replicated measurement using 1.2 × 10−5 M NB solution was 1.4%. The method showed to be rapid, simple and with a good sensitivity.  相似文献   

5.
A novel electrode material was obtained at an aluminum electrode (Al) by a simple electroless method including two consecutive procedures: (i) the electroless deposition of metallic palladium on the Al electrode surface from PdCl2 + 25% ammonia solution and (ii) the chemical transformation of deposited palladium to the palladium hexacyanoferrate (PdHCF) films in a solution containing 0.5 M K3[Fe(CN)6]. The modified Al electrode demonstrated a well-behaved redox couple due to the redox reaction of the PdHCF film. The PdHCF film showed an excellent electrocatalytic activity toward the oxidation of dopamine (DA). The effect of solution pH on the voltammetric response of DA has been investigated. A linear calibration graph was obtained over the DA concentration range 2-51 mM. The rate constant k and transfer coefficient α for the catalytic reaction and the diffusion coefficient of DA in the solution D, were found to be 4.67 × 102 M−1 s−1, 0.63 and 2.5 × 10−6 cm2 s−1, respectively. The interference of ascorbic acid was investigated and greatly reduced using a thin film of Nafion on the modified electrode. The modified electrode indicated reproducible behavior and a high level stability during electrochemical experiments, making it particularly suitable for the analytical purposes.  相似文献   

6.
Poly(o-aminophenol) (POAP) was formed by successive cyclic voltammetry in monomer solution in the presence of sodium dodecyl sulfate (SDS) on the surface of a carbon paste electrode. The electrochemical behavior of the SDS-POAP carbon paste electrode has been investigated by cyclic voltammetry in 0.5 M HClO4 and 5 mM K4[Fe(CN)6]/0.1 M KCl solutions as the supporting electrolyte and model system, respectively. Ni(II) ions were incorporated into the electrode by immersion of the polymeric modified electrode having amine groups in 0.1 M Ni(II) ion solution. Cyclic voltammetric and chronoamperometric experiments were used for the electrochemical study of this modified electrode. A good redox behavior of the Ni(III)/Ni(II) couple at the surface of electrode can be observed. The electrocatalytic oxidations of methanol and ethylene glycol (EG) at the surface of the Ni/SDS-POAP electrode were studied in a 0.1 M NaOH solution. Compared to bare carbon paste and POAP-modified carbon paste electrodes, the SDS-POAP electrode significantly enhanced the catalytic efficiency of Ni ions for methanol oxidation. Finally, using a chronoamperometric method, the catalytic rate constants (k) for methanol and ethylene glycol were found to be 2.04 × 105 and 1.05 × 107 cm3 mol−1 s−1, respectively.  相似文献   

7.
A novel electro-active material was successfully prepared with Fe(CN)63− ions loaded by electrostatic interaction onto the layer of poly(allylamine) hydrochloride (PAH), which was first assembled on prepared poly(sodium 4-styrenesulfonate) (PSS)-doped porous calcium carbonate (CaCO3) microspheres. Further, an electrochemical sensor for use in ascorbic acid (AA) detection was constructed with the use of the above electro-active materials embedded into a chitosan (CS) sol-gel matrix as an electron mediator. The electrocatalytic oxidation of AA by ferricyanide was observed at the potential of 0.27 V, which was negative-shifted compared with that by direct electrochemical oxidation of AA on a glassy carbon electrode. The experimental parameters, including the pH value of testing solution and the applied potential for detection of AA, were optimized. The current electrochemical sensor not only exhibited a good reproducibility and storage stability, but also showed a fast amperometric response to AA in a linear range (1.0 × 10−6 to 2.143 × 10−3 M), a low detection limit (7.0 × 10−7 M), a fast response time (<6 s), and a high sensitivity (−4.5127 μA mM−1).  相似文献   

8.
Copper chloride modified copper (CCMC) electrode was prepared as a new electrode. For the preparation of the modified electrode, the polished copper electrode was placed in 0.1 M CuCl2 solution for 20 s. In this step, a layer of copper (I) chloride was formed at the surface of copper electrode. Then, the electrode was placed in 0.1 M NaOH and the electrode potential was cycled between −250 and 1000 mV (vs. SCE) at a scan rate of 50 mV s−1 for 5 cycles in a cyclic voltammetry regime until a featureless voltammogram was obtained. Surface physical characteristics of the modified electrode were studied by scanning electron micrographs (SEM). Results showed that considerable amounts of microcrystals have been formed on the copper surface during the modification. Surface elemental analysis of electrode were performed by energy dispersive X-ray (EDX) technique. The results showed that in addition to copper and chloride elements, there is also oxygen at the surface of CCMC electrode. This indicates that a layer of (ClCu)2O was formed at the surface of the modified electrode. The electrocatalytic activity of the modified electrode for the oxidation of methanol, in aqueous basic solution was studied by using cyclic voltammetry. Results showed that, copper chloride modified electrode can improve the activity of Cu towards the oxidation of this small organic molecule, showing the possibility of attaining good electrocatalytic anodes for fuel cells. The modified electrode shows a stable and linear response in the concentration range of 5 × 10−3 to 8 × 10−2 M with a correlation coefficient of 0.9958.  相似文献   

9.
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.  相似文献   

10.
A multiwall carbon nanotubes (MWNTs)-chitosan modified glassy carbon electrode (GCE) exhibits attractive ability for highly sensitive cathodic stripping voltammetric measurements of bromide (Br). In pH 1.8 H2SO4 solution, a substantial increase in the stripping peak current of Br (compared to bare GCE and chitosan modified GCE) is observed using MWNTs-chitosan modified electrode. Operational parameters were optimized and the electrochemical behaviors of Br were studied by different electrochemical methods. The kinetics parameters were measured, the number of electron transfer (n) was 1 and the transfer coefficient (α) is 0.17. A wide linear calibration range (3.6 × 10−7-1.4 × 10−5 g mL−1) was achieved, with a detection limit of 9.6 × 10−8 g mL−1. The mechanism of electrode reaction was fully discussed.  相似文献   

11.
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.  相似文献   

12.
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, kh′, 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.  相似文献   

13.
A carbon paste electrode (CPE) modified with thionine immobilized on multi-walled carbon nanotube (MWCNT), was prepared for simultaneous determination of ascorbic acid (AA) and acetaminophen (AC) in the presence of isoniazid (INZ). The electrochemical response characteristics of the modified electrode toward AA, AC and INZ were investigated by cyclic and differential pulse voltammetry (CV and DPV). The results showed an efficient catalytic role for the electro-oxidation of AA and AC, leading to a remarkable peak resolution (∼303 mV) for two compounds. On the other hand, the presence of INZ, which is considered as important drug interference for AC, does not affect the voltammetric responses of these pharmaceuticals. The mechanism of the modified electrode was analyzed by monitoring the CVs at various potential sweep rates and pHs of the buffer solutions. Under the optimum conditions, the calibration curves for AA, AC and INZ were obtained in the range of 1 × 10−6 to 1 × 10−4 M, 1 × 10−7 to 1 × 10−4 M and 1 × 10−6 to 1 × 10−4 M, respectively. The prepared modified electrode shows several advantages such as simple preparation method, high sensitivity, long-time stability, ease of preparation and regeneration of the electrode surface by simple polishing and excellent reproducibility. The proposed method was applied to determination of AA, AC and INZ in commercial drugs and in plasma samples and the obtained results were satisfactory.  相似文献   

14.
A sulfate-selective electrode based on surfactant modified zeolite (SMZ) particles into carbon paste has been proposed (SMZ-CPE). The electrode was fully characterized in terms of composition, response time, ionic strength range, thermal stability and usable pH range. The electrode containing 10% of the SMZ was exhibited linear response range to sulfate species in the range of 2.0 × 10−6-3.1 × 10−3 M with detection limit of 2.0 × 10−6 M and Nernstian slope of 29.8 ± 0.8 mV per decade of sulfate concentration. The electrode response remains constant in the pH range of 4-10 and in the presence of 1 × 10−4-2 × 10−3 M NaNO3. The response of the electrode reaches equilibrium within several second after immersing the electrode in sulfate solution. A successful application of sulfate determination sulfate in real sample of a pharmaceutical zinc sulfate capsule, using direct potentiometry, is presented. The electrode was also used for potentiometric titration of sulfate. The validation of the obtained results in each case was proved by statistical methods.  相似文献   

15.
The catalytic oxidation of dopamine (DA) at a LiTCNE (lithium tetracyanoethylenide) film modified electrode is studied by electrochemical approaches. The immobilization of LiTCNE was performed by a polymer (poly-l-lysine) to prepare this modified electrode and its application for dopamine (DA) determination is described in detail. The modified electrode showed a high activity for the electrooxidation of dopamine (DA) at Ep = 0.20 V versus SCE. The modified electrode presented a wide linear response range for DA from 0.01 up to 10 μmol l−1 by differential pulse voltammetry (DPV) with a detection limit of 0.5 nmol l−1. The repeatability of the proposed sensor evaluated in term of relative standard deviation was 3.2% for n = 10. The sensor was applied for the determination of dopamine in pharmaceutical formulations and the average recovery for these samples was 101.9 (±0.1)%.  相似文献   

16.
Jinhua Chen 《Electrochimica acta》2007,52(13):4457-4462
The electrochemiluminescent behavior of lucigenin on a single-wall carbon nanotube/DMF film-modified glassy carbon electrode was studied in this paper. Comparing with the bare glassy carbon electrode, the electrochemiluminescent of lucigenin at modified electrode is more stable and without tedious procedure for clean-up the surface of modified electrode. It has been found that ascorbic acid could enhance the electrochemiluminescent intensity of lucigenin greatly at this modified electrode. Based on which, a new sensitive and simple electrochemiluminescent method for determination of ascorbic acid could be developed. The condition for the determination of ascorbic acid was optimized. Under the optimized condition, the enhanced electrochemiluminescent intensity versus ascorbic acid concentration was linear in the range of 1.0 × 10−8 to 4.0 × 10−6 mol/L with a detection limit of 2.0 × 10−10 mol/L, and the relative standard derivation for 1.0 × 10−7 mol/L ascorbic acid was 3.8% (n = 8). The possible mechanism was also discussed.  相似文献   

17.
Voltammetric behavior of folic acid at plain carbon paste electrode and electrode modified with calixarenes has been studied. Two peaks for irreversible oxidation were observed. Out of the three calixarenes chosen for modification of the electrodes, p-tert-butyl-calix[6]arene modified electrode (CME-6) was found to have better sensitivity for folic acid. Chronocoulometric and differential pulse voltammetric studies reveal that folic acid can assemble at CME-6 to form a monolayer whose electron transfer rate is 0.00273 s−1 with 2-electron/2-proton transfer for the peak at +0.71 V against SCE. An adsorption equilibrium constant of 5 × 103 l/mol for maximum surface coverage of 2.89 × 10−10 mol/cm2 was obtained. The current is found to be rectilinear with concentration by differential pulse voltammetry. However, linearity in the lower range of concentration 8.79 × 10−12 M to 1.93 × 10−9 M with correlation coefficient of 0.9920 was achieved by adsorptive stripping voltammetry. The limit of detection obtained was found to be 1.24 × 10−12 M. This method was used for the determination of folic acid in a variety of samples, viz. serum, asparagus, spinach, oranges and multivitamin preparations.  相似文献   

18.
Tetraoctylammonium bromide stabilized gold nanoparticles (TOAB-AuNPs) attached to 1,6-hexanedithiol (HDT) modified Au electrode was used for the simultaneous determination of paracetamol (PA) and ascorbic acid (AA) at physiological pH. The attachment of TOAB-AuNPs on HDT modified Au surface was confirmed by attenuated total reflectance (ATR)-FT-IR spectroscopy and atomic force microscope (AFM). The ATR-FT-IR spectrum of TOAB-AuNPs attached to the HDT monolayer showed a characteristic stretching modes corresponding to -CH2 and -CH3 of TOAB, confirming the immobilization of AuNPs with surface-protecting TOAB ions on the surface of the AuNPs after being attached to HDT modified Au electrode. AFM image showed that the immobilized AuNPs were spherical in shape and densely packed to a film of ca. 7 nm thickness. Interestingly, TOAB-AuNPs modified electrode shifted the oxidation potential of PA towards less positive potential by 70 mV and enhanced its oxidation current twice when compared to bare Au electrode. In addition, the AuNPs modified electrode separated the oxidation potentials of AA and PA by 210 mV, whereas bare Au electrode failed to resolve them. The amperometry current of PA was increased linearly from 1.50 × 10−7 to 1.34 × 10−5 M with a correlation coefficient of 0.9981 and the lowest detection limit was found to be 2.6 nM (S/N = 3). The present method was successfully used to determine the concentration of PA in human blood plasma and commercial drugs.  相似文献   

19.
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).  相似文献   

20.
A glassy carbon electrode modified with CeO2 nanoparticles was constructed and was characterized by electrochemical impedance spectrum (EIS) and cyclic voltammetry (CV). The resulting CeO2 nanoparticles modified glassy carbon electrode (CeO2 NP/GC electrode) was used to detect uric acid (UA) and ascorbic acid (AA) simultaneously in mixture. This modified electrode exhibits potent and persistent electron-mediating behavior followed by well-separated oxidation peaks towards UA and AA with activation overpotential. For UA and AA in mixture, one can well separate from the other with a potential difference of 273 mV, which was large enough to allow the determination of one in presence of the other. The DPV peak currents obtained in mixture increased linearly on the UA and AA in the range of 5.0 × 10−6 to 1.0 × 10−3 mol/L and 1.0 × 10−6 to 5.0 × 10−4 mol/L, with the detection limit (signal-to-noise ratio was 3) for UA and AA were 2.0 × 10−7 and 5.0 × 10−6 mol/L, respectively. The proposed method showed excellent selectivity and stability, and the determination of UA and AA simultaneously in serum was satisfactory.  相似文献   

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