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1.
A carbon nanotube paste electrode modified in situ with Triton X 100 was developed for the individual and simultaneous determination of acetaminophen (ACOP), aspirin (ASA) and caffeine (CF). The electrochemical behavior of these three molecules was investigated employing cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), chronocoulometry (CC) and adsorptive stripping differential pulse voltammetry (AdSDPV). Kramers-Kronig transformation implied that the resulting impedance data were validated and were of very good quality. These studies revealed that the oxidation of ACOP, ASA and CF is facilitated at an in situ surfactant-modified multiwalled carbon nanotube paste electrode (ISSM-CNT-PE). After optimization of analytical conditions employing this electrode at pH 7.0 in phosphate buffer (0.1 M), the peak currents for the three molecules were found to vary linearly with their concentrations in the range of 2.91 × 10−7-6.27 × 10−5 M with detection limits of 2.58 × 10−8, 8.47 × 10−8 and 8.83 × 10−8 M for ACOP, ASA and CF respectively using AdSDPV. The prepared modified electrode showed several advantages, such as a simple preparation method, high sensitivity, very low detection limits and excellent reproducibility. Furthermore, the proposed method was employed for the simultaneous determination of ACOP, ASA and CF in pharmaceutical formulations, urine and blood serum samples and the obtained results were found to be satisfactory.  相似文献   

2.
A multi-walled carbon nanotubes (MWCNTs) modified carbon ionic liquid electrode (CILE) was fabricated and used to investigate the electrochemical behavior of guanosine. CILE was prepared by mixing hydrophilic ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIMBF4), graphite powder and liquid paraffin together. The fabricated MWCNTs/CILE showed great electrocatalytic ability to the oxidation of guanosine and an irreversible oxidation peak appeared at 1.067 V (vs. SCE) with improved peak current. The electrochemical behavior of guanosine on the MWCNTs/CILE was carefully studied by cyclic voltammetry and the electrochemical parameters such as the charge transfer coefficient (α) and the electrode reaction standard rate constant (ks) were calculated with the result as 0.66 and 2.94 × 10−4 s−1, respectively. By using differential pulse voltammetry (DPV) as the detection method, a linear relationship was obtained between the oxidation peak current and the guanosine concentration in the range from 1.0 × 10−7 to 4.0 × 10−5 mol/L with the detection limit as 7.8 × 10−8 mol/L (3σ). The common coexisting substances showed no interferences to the guanosine detection and the modified electrode showed good ability to distinguish the electrochemical response of guanosine and adenosine.  相似文献   

3.
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   

4.
Cytochrome c/DNA modified electrode was achieved by coating calf thymus DNA onto the surface of glassy carbon electrode firstly, then immobilizing cytochrome c on it by multi-cyclic voltammetric method and characterized by the electrochemical impedance. The electrochemical behavior of cytochrome c on DNA modified electrode was explored and showed a quasi-reversible electrochemical redox behavior with a formal potential of 0.045 ± 0.010 V (versus Ag/AgCl) in 0.10 M, pH 5.0, acetate buffer solution. The peak currents were linearly with the scan rate in the range of 20-200 mV/s. Cytochrome c/DNA modified electrode exhibited elegant catalytic activity for the electrochemical reduction of NO. The catalytic current is linear to the nitric oxide concentration in the range of 6.0 × 10−7 to 8.0 × 10−6 M and the detection limit was 1.0 × 10−7 M (three times the ratio of signal to noise, S/N = 3).  相似文献   

5.
A cetyltrimethyl ammonium bromide modified carbon paste electrode (CTAB/CPE) was developed in this work based on the surface modification method. The improved electrochemical response of K4Fe(CN)6 at this electrode indicated that CTAB could change the surface property of carbon paste electrodes (CPEs), which was demonstrated by the electrochemical impedance spectroscopy (EIS). In 0.1 mM [Fe(CN)6]3−/4−, a low exchange current (i0) of 2.72×10−7 A at bare CPE was observed while that at CTAB/CPE was 6.79×10−5 A. The effect of CTAB concentration on the electrode quality revealed that CTAB formed a compact monolayer on the electrode surface with high density of positive charges directed outside the electrode. This electrode showed strong accumulation ability toward Fe(CN)64− and can also accumulate Co(phen)32+ by the adsorption of the organic ligands in the hydrophobic area of the monolayer. The electrode was applied to the immobilization of DNA, which was characterized by the isotherm adsorption of Co(phen)32+.  相似文献   

6.
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   

7.
An electrochemical biosensor was constructed based on the immobilization of myoglobin (Mb) in a composite film of Nafion and hydrophobic ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF6) for a modified carbon paste electrode (CPE). Direct electrochemistry of Mb in the Nafion-BMIMPF6/CPE was achieved, confirmed by the appearance of a pair of well-defined redox peaks. The results indicate that Nafion-BMIMPF6 composite film provided a suitable microenvironment to realize direct electron transfer between Mb and the electrode. The cathodic and anodic peak potentials were located at −0.351 V and −0.263 V (vs. SCE), with the apparent formal potential (Ep) of −0.307 V, which was characteristic of Mb Fe(III)/Fe(II) redox couples. The electrochemical behavior of Mb in the composite film was a surface-controlled quasi-reversible electrode process with one electron transfer and one proton transportation when the scan rate was smaller than 200 mV/s. Mb-modified electrode showed excellent electrocatalytic activity towards the reduction of trichloroacetic acid (TCA) in a linear concentration range from 2.0 × 10−4 mol/L to 1.1 × 10−2 mol/L and with a detection limit of 1.6 × 10−5 mol/L (3σ). The proposed method would be valuable for the construction of a third-generation biosensor with cheap reagents and a simple procedure.  相似文献   

8.
The antimony film carbon paste electrode (SbF-CPE) was prepared in situ on the carbon paste substrate electrode as a “mercury-free” electrochemical sensor. Its aptitude for measuring some selected trace heavy metals has been demonstrated in combination with square-wave anodic stripping voltammetry in non-deaerated model solutions of 0.01 M hydrochloric acid with pH 2. Some important operational parameters, such as deposition potential, deposition time, and concentration of antimony ions were optimized, and the electroanalytical performance of the SbF-CPE was critically compared with both bismuth film carbon paste electrode (BiF-CPE) and mercury film carbon paste electrode (MF-CPE) using Cd(II) and Pb(II) as test metal ions. In comparison with BiF-CPE and MF-CPE, the SbF-CPE exhibited superior electroanalytical performance in more acidic medium (pH 2) associated with favorably low hydrogen evolution, improved stripping response for Cd(II), and moreover, stripping signals corresponding to Cd(II) and Pb(II) at the SbF-CPE were slightly narrower than those observed at bismuth and mercury counterparts. In addition, the comparison with antimony film electrode prepared at the glassy carbon substrate electrode displayed higher stripping current response recorded at the SbF-CPE. The newly developed sensor revealed highly linear behavior in the examined concentration range from 5 to 50 μg L−1, with limits of detection (3σ) of 0.8 μg L−1 for Cd(II), and 0.2 μg L−1 for Pb(II) in connection with 120 s deposition step, offering good reproducibility of ±3.8% for Cd(II), and ±1.2% for Pb(II) (30 μg L−1, n = 10). Preliminary experiments disclosed that SbF-CPE and MF-CPE exhibit comparable performance for measuring trace concentration levels of Zn(II) in acidic medium with pH 2, whereas its detection with BiF-CPE was practically impossible. Finally, the practical applicability of SbF-CPE was demonstrated via measuring Cd(II) and Pb(II) in a real water sample.  相似文献   

9.
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   

10.
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   

11.
A promethazine (PMZ) molecularly imprinted polymer (MIP) and a non-imprinted polymer (NIP) were synthesized by two different formulations of methacrylic acid-ethylene glycol dimethacrylate (MAA-EGDMA) and vinyl benzene-divinyl benzene (VB-DVB). Then, the MIPs were used to modify the carbon paste electrode (CP). The response difference between MIP-CP and NIP-CP electrodes, containing VB-DVB polymer, was higher than that for MIP-CP and NIP-CP modified with polymer of MAA-EGDMA, indicating the lower nonselective surface adsorption property of the VB-DVB based MIP. The MIP, incorporated in the carbon paste electrode, functioned as selectively recognition element and pre-concentrator agent for PMZ determination. The prepared electrode was used for PMZ measurement by the three steps procedure including analyte extraction in the electrode, electrode washing and electrochemical measurement of PMZ. It was shown that the electrode washing, after PMZ extraction, led to enhanced selectivity. Square wave voltammetry (SWV) for PMZ determination by proposed electrode was proved to be better than that of differential pulse voltammetry. Some parameters, effective on the electrode response, were optimized and then a calibration curve was plotted. Two dynamic linear range of 7 × 10−9 to 4 × 10−7 and 4 × 10−7 to 7 × 10−6 mol L−1 were obtained. The detection limit of the method was calculated equal to 3.2 × 10−9 mol L−1. This method was used successful for PMZ determination in blood serum sample.  相似文献   

12.
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   

13.
Nano-γ-Al2O3 is dispersed onto the glass carbon electrode (GCE) by polishing. This nanostructured modified GCE exhibits a great enhancement to the redox responses of 3-nitrobenzaldehyde thiosemicarbazone (3-NBT). In comparison with bare GCE, 3-NBT gives a more sensitive voltammetric response because of the nanoparticle’s unique properties. The lowest detectable concentration (3σ) of 3-NBT is estimated to be 1.18 × 10−6 M (accumulation for 4 min). The linear relationship between peak current and concentration of 3-NBT holds in the range 1.0 × 10−5 M to 1.0 × 10−4 M (r = 0.9981). The electrochemical properties of 3-NBT on this modified electrode have been investigated with various electrochemical methods. The results indicate that the transference of one electron and one proton involves electrode radical reaction processes I and II, respectively. The coverage value (Γ) of 1.62 × 10−9 mol cm−2 was calculated and the electrochemical parameters, diffusion coefficient D (2.54 × 10−3 cm2 s−1, 2.03 × 10−3 cm2 s−1) and reaction rate constant ks (5.9573 s−1, 7.15 × 10−2 cm s−1) were obtained for quasi-reversible system I and irreversible system II, respectively.  相似文献   

14.
Bismuth-powder modified carbon paste electrode (Bi-CPE) is presented as an attractive “mercury-free” sensor applicable in electrochemical striping analysis of selected heavy metals. The electrode paste was prepared as a mixture of finely powdered metallic bismuth together with graphite powder and silicon oil. The Bi-CPE was characterized in nondeaerated solutions containing Cd(II) and Pb(II) at the μg/L level in conjunction with square-wave anodic stripping voltammetry. The electrode exhibited well-defined and separated stripping signals for both metals accompanied with a low background contribution, and a reproducibility of 5.6 and 6.0% (n = 12) for 20 μg/L Cd(II) and Pb(II), respectively. The Bi-CPE exhibited superior performance in comparison to the bare carbon paste electrode (CPE) and the bismuth paste electrode (BiPE) and surprisingly, yielded a higher response than the in situ prepared bismuth-film carbon paste electrode. The electrode displayed excellent linear behavior in the examined concentration range from 10 to 100 μg/L Cd(II) + Pb(II) (R2 = 0.998 for both), with limits of detection of 1.2 μg/L for Cd(II) and 0.9 μg/L for Pb(II). The electroanalytical performance of Bi-CPE was successfully tested in a real sample of tap water spiked with Cd(II) and Pb(II).  相似文献   

15.
A sensitive and novel DNA electrochemical biosensor for the detection of the transgenic plants gene fragment by electrochemical impedance spectroscopy (EIS) was presented. The well-dispersed carboxylic group-functionalized single-walled carbon nanotubes (SWNTs) were dripped onto the carbon paste electrode (CPE) surface firstly, and poly-l-lysine films (pLys) were subsequently electropolymerized by cyclic voltammetry (CV) to prepare pLys/SWNTs/CPE. The morphology of pLys/SWNTs films was examined using a field emission scanning electron microscope (SEM). The pLys/SWNTs films modified electrode exhibited very good conductivity. DNA probes were easily immobilized on the poly-l-lysine films via electrostatic adsorption. The hybridization events were monitored with electrochemical impedance spectroscopy using [Fe(CN)6]3−/4− as indicator. The PAT gene fragment from phosphinothricin acetyltransferase gene was detected by this DNA electrochemical sensor. The dynamic detection range of this sensor to the PAT gene fragment was from 1.0 × 10−12 to 1.0 × 10−7 mol/L. A detection limit of 3.1 × 10−13 mol/L could be estimated. The PCR amplification of NOS gene from the sample of a kind of transgenic modified bean was also detected satisfactorily by EIS.  相似文献   

16.
Here we investigated the analytical performances of the bismuth-modified zeolite doped carbon paste electrode (BiF-ZDCPE) for trace Cd and Pb analysis. The characteristics of bismuth-modified electrodes were improved greatly via addition of synthetic zeolite into carbon paste. To obtain high reproducibility and sensitivity, optimum experimental conditions for bismuth deposition were studied. Voltammetric responses of the BiF-ZDCPEs prepared with different ratios of zeolite, carbon powder, and silicone, were examined under same conditions. The in situ plated (zeolite/graphite powder/silicone, 10/190/80 w/w) BiF-ZDCPEs exhibited the most sensitive response to Cd and Pb in 0.10 M acetate buffer (pH 4.5). The detection limits of the modified electrode were 0.08 μg L−1 for Cd(II) and 0.10 μg L−1 for Pb(II) based on three times the standard deviation of the baseline with a preconcentration time of 120 s under optimal conditions, respectively. The modified electrode showed well linear response to both Cd(II) and Pb(II) over the concentration range from 1.0 to 20.0 μg L−1. The BiF-ZDCPEs were successfully applied to the determination of Cd(II) and Pb(II) in real samples, and the results were in agreement with those of atomic absorption spectroscopy (AAS).  相似文献   

17.
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   

18.
Stable Nafion-Au colloids were immobilized on a glassy carbon electrode (GCE) for detection of β-agonist clenbuterol by electroanalysis. The Au colloids were prepared by a one-step electrodeposition onto GCE, with obvious electrocatalytic activity present. The negatively charged Nafion film was an efficient barrier to negatively charged interfering compounds, resulting in accumulation of positively charged clenbuterol at the Nafion film. The electrochemical characters of the electrode during various modified steps in a redox probe system of K4[Fe(CN)6]/K3[Fe(CN)6] were confirmed by cyclic voltammetry (CV) and AC-impedance. In Britton-Robinson (B-R) buffer solution (pH = 2.0) and the potential range of −0.2 to 1.2 V, the Nafion-Au colloid modified electrode, compared to a bare GCE, exhibits obvious electrocatalytic activity towards the redox of clenbuterol by greatly enhancing the peak current with a linear calibration curve from 8.0 × 10−7 to 1.0 × 10−5 mol/L and a detection limit of (1.0 × 10−7 mol/L) (R = 0.996). The modified electrode shows high sensitivity, selectivity and reproducibility. The recovery for detecting clenbuterol (∼10−6 mol/L) in human serum is up to 98.19%.  相似文献   

19.
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   

20.
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   

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