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1.
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, ks, 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.  相似文献   

2.
A novel electrochemical sensor for the selective and sensitive detection of dopamine (DA) in presence of large excess of ascorbic acid (AA) and uric acid (UA) at physiological pH was developed by the bulk modification of carbon paste electrode (CPE) with biocompatible graphite oxide (GO). Very small quantity of GO in carbon paste matrix imparted selectivity through electrostatic interactions. The modifier was characterized using infrared spectroscopy and powder X-ray diffraction. Large peak separation, good sensitivity and stability allow this modified electrode to analyze DA individually and simultaneously along with AA and UA. Applying differential pulse technique, DA could be detected even in the presence of 1000 fold excess of AA and UA. A linear dynamic range of 0.07–70 μM with detection limit of 1.5 × 10−8 M was obtained for DA. None of the bulk modified electrodes reported in the literature have shown such a low detection limit at the physiological pH. The practical application of the modified electrode was demonstrated by spiking the human blood serum and cerebral fluid with dopamine and the results obtained were satisfactory.  相似文献   

3.
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.  相似文献   

4.
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.  相似文献   

5.
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.  相似文献   

6.
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, ks, 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.  相似文献   

7.
Short time immobilization of densely packed tetraoctylammonium bromide (TOAB) stabilized gold nanoparticles (AuNPs) were established on a Au electrode modified with a self-assembled monolayer (SAM) of 1,6-hexanedithiol (HDT) or 1,4-benzenedimethanethiol (BDMT). The quartz crystal microbalance experiment showed densely packed TOAB–AuNPs single layer formation on both SAMs was achieved within 20 min. AFM images demonstrated that the immobilized TOAB–AuNPs on the SAMs were densely packed and the AuNPs film thickness was 6–7 nm. The electronic communication between the immobilized AuNPs and the underlying bulk electrode was confirmed by cyclic voltammetry and electroreflectance spectroscopy. A reversible electron transfer reaction was observed for both [Fe(CN)6]4−/3− and [Ru(NH3)6]2+/3+ at TOAB–AuNPs immobilized on HDT (Au/HDT/AuNPs) and BDMT (Au/BDMT/AuNPs) modified electrodes. The electroreflectance spectra show a red-shifted strong positive-going plasmon resonance bands at 551 nm and 584 nm, respectively, for the Au/BDMT/AuNPs and Au/HDT/AuNPs electrodes. The observed reversible redox response for the solution redox species and red-shifted plasmon resonance bands for the immobilized AuNPs again indicated that the AuNPs were immobilized on the SAMs in a densely packed manner. An advantage of TOAB–AuNPs modified electrode prepared by short time immersion over citrate-stabilized AuNPs modified electrode was demonstrated by the enhanced oxidation of ascorbic acid (AA) at these electrodes. The oxidation of AA was shifted to 90 mV less positive potential with higher oxidation current at TOAB–AuNPs modified electrode when compared to citrate-stabilized AuNPs modified electrode.  相似文献   

8.
Gold nanofilm, with a nanoporous morphology, was found to have the unique property to catalyze the oxidization of ascorbic acid (AA) and dopamine (DA), resulting in the improved electrochemical behavior of the two species and a negative shift of the oxidization potential of AA for about 300 mV. The catalytic oxidization of gold nanofilm to AA is mainly ascribed to its high surface energy, while the enhanced electron transfer ability of DA on the gold nanofilm is attributed to the strong interaction between DA and the electrode surface. Based on the peak separation of DA and AA, selective detection of DA was achieved on the gold nanofilm modified electrode. Differential pulse voltammetry (DPV) techniques and cyclic voltammetry (CV) were used to investigate the electrochemical behavior of AA and DA on the surface of the electrode. Afterwards, the obtained gold nanofilm was applied in selective detection of dopamine (DA) in the presence of ascorbic acid (AA) at near neutral pH by DPV in the optimized conditions. The linear range for DA was 1.5–27.5 μM. The electrode also shows good stability during detection.  相似文献   

9.
This work describes the electrochemical behavior of lead pentacyanonitrosylferrate (PbPCNF) film immobilized on the surface of carbon-ceramic electrode (CCE) and its electrocatalytic activity toward the reduction of hydrogen peroxide in acidic medium. The electrode was prepared by electroless derivatization of Pb-doped carbon-ceramic electrode surface to the redox active PbPCNF solid film, in the presence of sodium pentacyanonitrosylferrate, Na2[Fe(CN)5NO], (PCNF). The morphology and the composition of the PbPCNF-modified CCE were characterized by scanning electron microscopy (SEM), energy-dispersive X-ray (EDX), and Fourier transform infrared (FTIR) techniques. Various experimental parameters influencing the electrochemical behavior of the modified electrode were optimized by varying the supporting electrolyte, potential scan rates and solution pH. The modified electrode showed an excellent electrocatalytic behavior toward the reduction of hydrogen peroxide in 0.5 M KNO3 at pH 4. The sensor exhibited a good linear response for H2O2 concentration over the range 0.5–58.75 μM with a detection limit of 0.4 μM (S/N = 3). The interferences of dopamine (DA), uric acid (UA), and ascorbic acid (AA) were negligible in the determination of H2O2. The proposed sensor showed good stability, reproducibility and outstanding for long-term use.  相似文献   

10.
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.  相似文献   

11.
This research in finding a cheap and efficient catalyst for electrooxidation of formaldehyde give us an attempt to make and examine the behavior of poly(N-methylaniline)/nickel modified carbon paste electrode (Ni/P(NMA)/MCPE) in absence and presence of formaldehyde. This involves in situ electropolymerization of N-methylaniline at carbon paste electrode, which is following to the incorporation of Ni(II) to polymeric layer by immersion of modified electrode in 1.0 M nickel sulphate solution. The electrocatalytic oxidation of formaldehyde was studied by cyclic voltammetry and chronoamperometry methods. The effects of scan rate and formaldehyde concentration on the electrocatalytic oxidation of formaldehyde were also investigated at the surface of Ni/P(NMA)/MCPE. The diffusion coefficient (D = 14.1 × 10−5 cm2 s−1), and some kinetic parameters such as the transfer coefficient (α = 0.45) and also second-order rate constant (k = 8.96 × 10−4 cm3 mol−1 s−1) of formaldehyde were calculated.  相似文献   

12.
Sheets consisted of entire single-walled carbon nanotubes (SWNTs) were used as the working electrode for electrochemical measurement of ethidium bromide by covering a glassy carbon electrode (GCE) using the SWNT-sheet. This SWNT-sheet based electrode exhibited a fast electron transfer process on the electrode surface via the cyclic voltammetry with K4Fe(CN)6 as electrochemical probes. This SWNT-sheet based electrode showed also a high sensitivity toward ethidium bromide, a typically harmful, aromatic backboned chemical. The SWNT-sheet based electrode was capable of accumulating ethidium bromide to a higher concentration and therefore was capable of detecting ethidium bromide with a detection limit of 1.0 × 10−8 M.  相似文献   

13.
The electrochemical study of a tetrabromo-p-benzoquinone modified carbon paste electrode (TBQ-MCPE), as well as its efficiency for electrocatalytic oxidation of ascorbic acid, dopamine and uric acid, is described. Cyclic voltammetry was used to investigate the redox properties of this modified electrode at various solution pH values and at various scan rates. Three linear segments were found with slope values of ?58.4 mV/pH, ?28.1 mV/pH and 0.0 mV/pH in the pH range 2.0–7.1, pH 7.1–9.0 and pH 9.0–11.0, respectively. The apparent charge transfer rate constant, ks, and transfer coefficient, α, for electron transfer between TBQ and CPE were calculated as 3.79 ± 0.10 s?1 and 0.55, respectively. The electrode was also employed to study the electrocatalytic oxidation of AA, using cyclic voltammetry, chronoamperometry and differential pulse voltammetry as diagnostic techniques. It has been found that the oxidation of AA at the surface of TBQ-MCPE occurs at a potential of about 430 mV less positive than that of an unmodified CPE. The diffusion coefficient of AA was also estimated using chronoamperometry. The kinetic parameters such as the electron transfer coefficient, α, and heterogeneous rate constant, kh, for oxidation of AA at the TBQ-MCPE surface was determined using cyclic voltammetry. Differential pulse voltammetry (DPV) exhibits two linear dynamic ranges and a detection limit of 0.62 μM for AA. In DPV, the TBQ-MCPE could separate the oxidation peak potentials of AA, DA and UA present in the same solution, though at the unmodified CPE the peak potentials were indistinguishable. This modified electrode was quite effective not only to detect AA, DA and UA, but also in simultaneous determination of each component concentration in the mixture.  相似文献   

14.
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.  相似文献   

15.
In this work, m-toluidine is electropolymerized at the surface of carbon paste electrode using consecutive cyclic voltammetry in 20 mM monomer aqueous solution in the presence of 6 mM cetyltrimethyl ammonium bromide (CTAB) as surfactant. Then transition metal of nickel is incorporated into the polymer by electrodepositing of Ni (II) from 1.5 M NiSO4 acidic solution using chronoamperometry technique (−1.0 V versus Ag|AgCl|KCl (3 M) for 15 min). In alkaline medium (i.e. NaOH 0.1 M) a good redox behavior of Ni (III)/Ni (II) couple at the surface of Ni/poly (m-toluidine) modified carbon paste electrode (Ni/PMT/MCPE) in the absence and presence of CTAB (Ni/CTAB-PMT/MCPE) can be observed. Electrocatalytic oxidation of methanol has been studied on Ni/PMT/MCPE and Ni/CTAB-PMT/MCPE. The results show that CTAB significantly enhances the catalytic efficiency of nickel particles on the oxidation of methanol in aqueous alkaline media. Moreover, the effects of various parameters such as concentration of CTAB, concentration of methanol, electrodepositing time, film thickness and monomer concentration on the electrooxidation of methanol as well as long-term stability of the Ni/CTAB-PMT/MCPE have also been investigated. This polymeric modified electrode can oxidize the methanol with high current density (over 40 mA cm−2).  相似文献   

16.
Growth of flower-like Au nanocrystals at room temperature on a conducting support and electroanalysis of biomolecules are described. The Au nanocrystals are grown by seed-mediated growth approach using electrochemically deposited Au nanoseeds (nAuS) without any template or surfactants. The flower-like nanocrystals (nAuF) have the size ranging from 75 to 350 nm. XRD profile of nAuF reveals the existence of (1 1 1), (2 0 0) and (3 1 1) planes, corresponding to the face centered cubic lattice of Au. The nAuF on the electrode surface have significantly large surface area of 0.354 ± 0.02 cm2. The electroanalysis of biomolecules such as ascorbic acid (AA), dehydroascorbic acid (DHA), dopamine (DA) and reduced nicotinamide adenine dinucleotide (NADH) is performed using nAuF electrode. The nanocrystals on the electrode facilitate the oxidation of these bioanalytes; decrease in the overpotential and enhancement in the peak current is observed. Unlike the bulk Au electrode, nAuF electrode displays unique inverted ‘V’ shape voltammogram for NADH and DHA. Oxidation of AA occurs in two steps and two voltammetric peaks are obtained for AA in neutral and alkaline pH. Increase in the peak current and decrease in peak-to-peak separation with respect to the unmodified electrode are obtained for DA on nAuF electrode. The nAuF electrode shows high sensitivity, stability and linear response for a wide concentration range towards these analytes. The high sensitivity is ascribed to the ensemble behavior of the nAuF electrode.  相似文献   

17.
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 E0′ 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 E0′ 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 Fe2+/3+ in [Fe(CN)6]3−/4− redox probe.  相似文献   

18.
After reviewing relevant equations for the calculation of exchange current density, a new equation is derived for hydrogen electrode reactions to correct for the influences of the hydrogen concentration change in the vicinity to the electrode surface. This equation is able to describe the polarization curve shape in the small polarization region as well as to calculate the exchange current (density). The abilities of this equation are demonstrated by the data obtained with a Pt rotating disk electrode in 0.1 mol l−1 KOH solution. The exchange current density at 298 K under 1 atmosphere hydrogen pressure is found to be 0.103 mA cm−2 with an apparent activation energy of 33.5 kJ mol−1. At a constant temperature, the exchange current is found to be proportional to the square root of the hydrogen partial pressure in the solution.  相似文献   

19.
The functionalized carbon nanotube electrode was fabricated by electrodeposition of 1,2-naphthoquinone-4-sulfonic acid sodium (Nq) on single-wall carbon nanotube (SWNT) modified glassy carbon electrode (GCE). This electrode was characterized by scanning electron microscopy (SEM) and the results showed that Nq can rapidly and effectively be deposited on the surface of SWNT film with high stability. The electrochemical properties of functionalized SWNT/GCE with Nq (SWNT–Nq/GCE) were studied using cyclic voltammetry, double step potential chronoamperometry and differential pulse voltammetry methods. The results indicated that SWNT could improve the electrochemical behavior of Nq and greatly enhances its redox peak currents. The SWNT–Nq/GCE exhibited a pair of well-defined redox peaks. The experimental results also demonstrated that the Nq deposited species on SWNT could catalyze cysteamine oxidation and SWNT–Nq exhibited a high performance with lowering the overpotential by more than 710 mV. The effect of pH value, number of scans and Nq concentration were investigated on the electrochemical behavior of cysteamine. The selectivity of the reaction has been assessed with no interference from tyrosine, lysine, methionine, tryptophan, alanine and glutathione. The presented method has highly selectivity for voltammetric detection of cysteamine in the dynamic range from 5.0 × 10−6 M to 2.7 × 10−4 M and with a detection of limit (3σ) 3.0 × 10−6 M.  相似文献   

20.
Time-differentiation of the frequency response observed with electrochemical quartz crystal microbalance (EQCM) was applied for the analysis of the electrode processes for the Au electro-dissolution and deposition in acidic aqueous solution containing free chloride ion (Cl). Evaluation for the values of the apparent equivalent molar mass per second proved the generation of the Au(I) species during the oxidation and reduction reactions of Au electrode in the presence of Cl at a level of 10 mM, which has not been reported so far. It was found that the electron-transfer reactions composed of Au(0), Au(I) and Au(III) species are participated in the overall Au electro-dissolution and deposition reactions in the applied potential range from −0.10 to 1.50 V (vs. Ag/AgCl).  相似文献   

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