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1.
This paper describes the electrocatalytic oxidation of ascorbic acid (AA) in phosphate buffer solution by the immobilized citrate capped gold nanoparticles (AuNPs) on 1,6-hexanedithiol (HDT) modified Au electrode. X-ray photoelectron spectrum (XPS) of HDT suggests that it forms a monolayer on Au surface through one of the two SH groups and the other SH group is pointing away from the electrode surface. The free SH groups of HDT were used to covalently attach colloidal AuNPs. The covalent attachment of AuNPs on HDT monolayer was confirmed from the observed characteristic carboxylate ion stretching modes of citrate attached with AuNPs in the infra-red reflection absorption spectrum (IRRAS) in addition to a higher reductive desorption charges obtained for AuNPs immobilized on HDT modified Au (Au/HDT/AuNPs) electrode in 0.1 M KOH when compared to HDT modified Au (Au/HDT) electrode. The electron transfer reaction of [Fe(CN)6]4−/3− was markedly hindered at the HDT modified Au (Au/HDT) electrode while it was restored with a peak separation of 74 mV after the immobilization of AuNPs on Au/HDT (Au/HDT/AuNPs) electrode indicating a good electronic communication between the immobilized AuNPs and the underlying bulk Au electrode through a HDT monolayer. The Cottrell slope obtained from the potential-step chronoamperometric measurements for the reduction of ferricyanide at Au/HDT/AuNPs was higher than that of bare Au electrode indicating the increased effective surface area of AuNPs modified electrode. The Au/HDT/AuNPs electrode exhibits excellent electrocatalytic activity towards the oxidation of ascorbic acid (AA) by enhancing the oxidation peak current to more than two times with a 210 mV negative shift in the oxidation potential when compared to a bare Au electrode. The standard heterogeneous electron transfer rate constant (ks) calculated for AA oxidation at Au/HDT/AuNPs electrode was 5.4 × 10−3 cm s−1. The oxidation peak of AA at Au/HDT/AuNPs electrode was highly stable upon repeated potential cycling. Linear calibration plot was obtained for AA over the concentration range of 1–110 μM with a correlation coefficient of 0.9950. The detection limit of AA was found to be 1 μM. The common physiological interferents such as glucose, oxalate ions and urea do not show any interference within the detection limit of AA. The selectivity of the AuNPs modified electrode was illustrated by the determination of AA in the presence of uric acid.  相似文献   

2.
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   

3.
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   

4.
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.  相似文献   

5.
A gold electrode surface was modified using a dinuclear copper complex [CuII2 (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.  相似文献   

6.
P. Kannan 《Electrochimica acta》2010,55(10):3497-265
This paper describes the highly sensitive electrochemical determination of nitric oxide (NO) using the fused spherical gold nanoparticles (FAuNPs) modified ITO electrode. The FAuNPs were self-assembled on a (3-mercaptopropyl)-trimethoxysilane (MPTS) sol-gel film, which was preassembled on ITO electrode. The attachment of FAuNPs on MPTS sol-gel film was confirmed by UV-vis absorption spectroscopy, atomic force microscopy (AFM) and cyclic voltammetry (CV). The AFM image shows that the AuNPs retain their fused morphology after immobilized on MPTS sol-gel film. The FAuNPs modified ITO electrode shows an excellent electrocatalytic activity towards the oxidation of NO. Using FAuNPs modified electrode, the detection of 12 nM NO was achieved for the first time by amperometry method. Further, the current response was increased linearly with increasing NO concentration in the range of 1.2 × 10−8 to 7 × 10−4 M and the detection limit was found to be 3.1 × 10−10 M (S/N = 3). The FAuNPs modified ITO electrode displays an excellent selectivity towards the determination of 12 nM NO even in the presence of 1000-fold excess common interfering agents.  相似文献   

7.
A sensitive and selective electrochemical sensor was fabricated via the drop-casting of carbon nanoparticles (CNPs) suspension onto a glassy carbon electrode (GCE). The application of this sensor was investigated in simultaneous determination of acetaminophen (ACE) and tramadol (TRA) drugs in pharmaceutical dosage form and ACE determination in human plasma. In order to study the electrochemical behaviors of the drugs, cyclic and differential pulse voltammetric studies of ACE and TRA were carried out at the surfaces of the modified GCE (MGCE) and the bare GCE. The dependence of peak currents and potentials on pH, concentration and the potential scan rate were investigated for these compounds at the surface of MGCE. Atomic force microscopy (AFM) was used for the characterization of the film modifier and its morphology on the surface of GCE. The results of the electrochemical investigations showed that CNPs, via a thin layer model based on the diffusion within a porous layer, enhanced the electroactive surface area and caused a remarkable increase in the peak currents. The thin layer of the modifier showed a catalytic effect and accelerated the rate of the electron transfer process. Application of the MGCE resulted in a sensitivity enhancement and a considerable decrease in the anodic overpotential, leading to negative shifts in peak potentials. An optimum electrochemical response was obtained for the sensor in the buffered solution of pH 7.0 and using 2 μL CNPs suspension cast on the surface of GCE. Using differential pulse voltammetry, the prepared sensor showed good sensitivity and selectivity for the determination of ACE and TRA in wide linear ranges of 0.1-100 and 10-1000 μM, respectively. The resulted detection limits for ACE and TRA was 0.05 and 1 μM, respectively. The CNPs modified GCE was successfully applied for ACE and TRA determinations in pharmaceutical dosage forms and also for the determination of ACE in human plasma.  相似文献   

8.
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.  相似文献   

9.
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   

10.
Gold nanoparticle-functionalized carbon nanotubes (AuNP-CNT) have been prepared by a novel self-assembly method. The new material has been characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD) and utilized for constructing AuNP-CNT-modified pyrolytic graphite electrode (AuNP-CNT/PGE) to investigate the electrochemical behavior of L-dopa in neutral phosphate buffer solution. Compared to bare PG electrode, AuNP-CNT/PGE shows novel properties towards the electrochemical redox of L-dopa in phosphate buffer solution at pH 7.0. The oxidation potential of L-dopa shows a significant decrease at the AuNP-CNT/PGE. The oxidation current of L-dopa is about 5-fold higher than that of the unmodified PGE. Using differential pulse voltammetry (DPV) method, the oxidation current is well linear with L-dopa concentration in the range of 0.1-150 μM, with a detection limit of about 50 nM (S/N = 3). The proposed electrode can also effectively avoid the interference of ascorbic acid and uric acid, making the proposed sensor suitable for the accurate determination of L-dopa in both pharmaceutical preparations and human body fluids.  相似文献   

11.
A new voltammetric method for a direct determination of gold nanoparticles, based on adsorption and electrochemical detection of colloidal gold, is described. In this protocol, the absorption of gold nanoparticles onto the rough surface of graphite-epoxy composite electrode is followed by their electrochemical oxidation in 0.1 M HCl medium at a potential of +1.25 V. The resulting tetrachloroaurate ions generated near the electrode surface are detected by differential pulse voltammetry (DPV). The DPV response is linear in the range from 4.7 × 108 to 4.7 × 1011 nanoparticles cm−3 with a limit of detection of 1.8 × 108 gold nanoparticles cm−3. The surface characteristics of the composite electrode are investigated and the parameters that affect the complete analytical detection process of gold nanoparticles are optimized.  相似文献   

12.
Different shapes (nanosphere or nanorod) of gold nanoparticles (Au-NPs) were synthesized with and without ultrasonic irradiation in the presence of citric acid. Spherical-shaped and rod-shaped Au-NPs showed different surface plasmon resonance (SPR) absorption bands. The Au-NPs with different shapes were immobilized on a monolayer of 3-aminopropyltriethoxysilane (APS) coated on an indium-tin oxide (ITO) electrode. The potential dependence of the SPR band of different shaped Au-NPs in an aqueous solution was explored. The SPR band and intensity changes of the Au-NPs were found to depend on the applied potential. The spherical-shaped and rod-shaped Au-NPs showed different SPR absorption behaviors when potential was applied. These behavior changes were interpreted as the result of the potential-induced changes of the local dielectric environment around the nanoparticles due to molecular absorption/desorption and the charging/discharging of the particles.  相似文献   

13.
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.  相似文献   

14.
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.  相似文献   

15.
A novel two-step method was employed to synthesize gold nanoparticles dispersed on boron-doped diamond (BDD) electrode. It consisted of sputter deposition at ambient temperature of maximum 15 equivalent monolayers of gold, followed by a heat treatment in air at 600 °C. Gold nanoparticles with an average diameter between 7 and 30 nm could be prepared by this method on polycrystalline BDD film electrode. The obtained Au/BDD composite electrode appeared stable under conditions of electrochemical characterization performed using ferri-/ferrocyanide and benzoquinone/hydroquinone redox couples in acidic medium. The electrochemical behavior of Au/BDD was compared to that of bulk Au and BDD electrodes. Finally, the Au/BDD composite electrode was regarded as an array of Au microelectrodes dispersed on BDD substrate.  相似文献   

16.
Citrate-stabilized gold nanoparticles (Au-NPs) of a nearly spherical shape with four different diameters (3.7, 11.0, 21.7, and 40.8 nm) were immobilized on a 4-aminobutylsiloxane monolayer-modified indium-tin oxide (ITO) electrode. From the results of coulometric measurements using potential step sequences, the number of electrons per particle to be transferred to attain a new equilibrium state after applying a potential step was found to increase in proportion to the square of the diameter. The double layer integral capacitance of the Au-NP surface per unit area in the potential range from −0.4 to 0.6 V (Ag/AgCl/sat’d KCl) is ca. 70 μF cm−2, being independent of the particle size. The differential capacitance of the Au-NP surface is a function of the potential with a maximum at 0.32 V, while the function is again independent of the particle size. The kinetics of the charging was discussed using the analysis of the potential step transient current. The potential-dependent shift of the plasmon absorption band obtained by constant-potential and potential-modulated transmission-absorption spectroscopic measurements revealed that a smaller Au-NP exhibits a greater blue-shift of the plasmon band when applying more negative potentials, being in line with the Mie-Drude theory.  相似文献   

17.
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   

18.
5-Hydroxytryptophan (5-HTP) was covalently grafted on the surface of glassy carbon electrodes (GCEs) using cyclic voltammetric method in a phosphate buffer solution. The prepared electrode, denoded as 5-HTP/GCE, was characterized by X-ray photoelectron spectroscopy, cyclic voltammetry and differential pulse voltammetry (DPV). Tryptophan grafted GCE (TRP/GCE) and 5-hydroxytryptamine grafted GCE (5-HTP/GCE) were also prepared by the same method for comparison. It was found that the electrocatalytic activities toward the oxidation of uric acid (UA) and ascorbic acid (AA) was in the order of 5-HT/GCE > 5-HTP/GCE > TRP/GCE for UA oxidation and 5-HT/GCE = 5-HTP/GCE > TRP/GCE for AA oxidation. However, the CV current sensitivity was estimated as 4:2:1 for 5-HTP/GCE:5-HT/GCE:TRP/GCE. The DPV peaks for UA and AA oxidation appeared at 0.07 V and 0.34 V versus SCE, respectively, allowing simultaneous determination in mixtures. A linearly response in the range of: 5.0 × 10−7 to 1.1 × 10−5 M with the detection limit (s/n = 3) of 2.8 × 10−7 M for UA determination, and a linear response in the range of: 5.0 × 10−6 to 1.0 × 10−4 M with the detection limit of 4.2 × 10−6 M for AA determination were obtained. This electrode was used for UA and AA determinations in human urine samples satisfactorily.  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.
The comparison of assembly structure and property of mercaptopropionic acid (MPA) self-assembled monolayers (SAMs) on gold nanoparticle modified electrode (nanogold electrode) with that on planar gold electrode was studied by cyclic voltammetry (CV). The electron transfer of through the MPA SAMs and Cu underpotential deposition (UPD) on MPA-covered electrode indicated that MPA molecules assemblied on the planar gold electrode could form a very compact layer, which could surpass the electron transfer K3Fe(CN)6 greatly, whereas on the surface on the nanogold, which curvature make the compact packing loose. The reductive desorption in 0.5 M KOH and oxidative desorption in phosphate buffer solution (PBS) (pH 6.8) showed that gold nanoparticles could enhance the Au-S bond and stabilize the MPA molecules.  相似文献   

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