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1.
Poly(o-aminobenzoic acid) (o-ABA) film is deposited on glassy-carbon electrode (GCE) by electropolymerization in pH 7.0 phosphate buffer solution (PBS). Electrochemical behavior of modified electrode is investigated by electrochemical impedance spectroscopy (EIS), different pulse voltammetry (DPV), and cyclic voltammetry (CV). The results indicate that there is a greater resistance during the electron transfer process in poly(o-ABA) film than in bare GCE for the redox of [Fe(CN)6]3−/[Fe(CN)6]4−. Further research indicates that epinephrine (EP) can be strongly absorbed on the surface of the poly(o-ABA) film-modified electrode. The modified electrode shows an excellent electrocatalytical activity on EP oxidation. The EP cathodic peak potential shifts negatively with a slope of −53.5 mV/pH, indicating that equal amounts of proton and electron are involved in the electrode reaction process. In pH 7.0 PBS, the peak current of EP and the concentration has a linear relationship from 0 to 65 μM by amperometric current-time curve. __________ From Elektrokhimiya, Vol. 41, No. 9, 2005, pp. 1059–1065. Original English Text Copyright ? 2005 by Cheng, Jin, Zhang. The text was submitted by the authors in English.  相似文献   

2.
4-Aminobenzoic acid (4-ABA) was covalently grafted on a glassy carbon electrode (GCE) during an electrochemical oxidation process in 0.1 M KCl aqueous solution. The modified electrode was applied to sense paracetamol (PCT) at serials of simulated physiologic conditions, compared to the bare electrode. The results showed that the modified electrode possessed better stability, reusability, and longevity than the bare GCE at room to physiologic temperatures. This indicated that 4-ABA/GCE can be used as the electrochemical sensing platform of PCT at the physiologic condition.  相似文献   

3.
A novel and sensitive electrochemical DNA biosensor has been developed for the detection of DNA hybridization. The biosensor was proposed by using copper(II) complex of Luteolin C30H18CuO12 (CuL2) as an electroactive indicator based on silver nanoparticles and multi-walled carbon nanotubes (Ag/MWCNTs) modified glassy carbon electrode (GCE). In this method, the 4-aminobenzoic acid (4-ABA) and Ag nanoparticles were covalently grafted on MWCNTs to form Ag/4-ABA/MWCNTs. The proposed method dramatically increased DNA attachment quantity and complementary ssDNA detection sensitivity for its large surface area and good charge-transport characteristics. DNA hybridization detection was performed using CuL2 as an electroactive indicator. The CuL2 was synthesized and characterized using elemental analysis (EA) and IR spectroscopy. Cyclic voltammetry (CV) and fluorescence spectroscopy were used to investigate the interaction between CuL2 and ds-oligonucleotides (dsDNA). It was revealed that CuL2 presented high electrochemical activity on GCE, and it could be intercalated into the double helices of dsDNA. The target ssDNA of the human hepatitis B virus (HBV) was quantified in a linear range from 3.23 × 10−12 to 5.31 × 10−9 M (r = 0.9983). A detection limit of 6.46 × 10−13 M (3σ, n = 11) was achieved.  相似文献   

4.
A new approach for a simple electrochemical detection of PAT gene fragment is described. Poly(2,6-pyridinedicarboxylic acid) (PDC) modified glassy carbon electrode (GCE) was prepared by potential scan electropolymerization in an aqueous solution. Mg2 ions were incorporated by immer-sion of the modified electrode in 0.5 mol/L aqueous solution of MgCl2 to complete the preparation of a generic "activated" electrode ready for binding the probe DNA. The ssDNA was linked to the conduct-ing polymer by forming a bidentate complex between the carboxyl groups on the polymer and the phosphate groups of DNA via Mg2 . DNA immobilization and hybridization were characterized with dif-ferential pulse voltammetry (DPV) by using methylene blue (MB) as indicator and electrochemical im-pedance spectroscopy (EIS). The EIS was of higher sensitivity for DNA detection as compared with voltammetric methods in our strategy. The electron transfer resistance (Ret) of the electrode surface in EIS in [Fe(CN)6]3-/4- solution increased after the immobilization of the DNA probe on the Mg/PDC/GCE electrode. The hybridization of the DNA probe with complementary DNA (cDNA) made Ret increase further. The difference between the Ret at ssDNA/Mg/PDC/GCE and that at hybridization DNA modified electrode (dsDNA/Mg/PDC/GCE) was applied to determine the specific sequence related to the target PAT gene with the dynamic range comprised between 1.0 × 10-9 and 1.0 × 10_5 mol/L. A detection limit of 3.4 × 10-10 mol/L of oligonucleotides can be estimated.  相似文献   

5.
S. Ashok Kumar 《Talanta》2007,72(2):831-838
The adsorption processes and electrochemical behavior of 4-nitroaniline (4-NA) adsorbed onto glassy carbon electrodes (GCE) have been investigated in aqueous 0.1 M nitric acid (HNO3) electrolyte solutions using cyclic voltammetry (CV). 4-NA adsorbs onto GCE surfaces, and upon potential cycling past −0.2 V, is transformed into the arylhydroxylamine (ArHA) derivative which exhibits a well-behaved pH dependent redox couple centered at 0.32 V at pH 1.5. It is noted as arylhydroxylamine modified glassy carbon electrodes (HAGCE). This modified electrode can be readily used as an immobilization matrix to entrap proteins and enzymes. In our studies, myoglobin (Mb) was used as a model protein for investigation. A pair of well-defined reversible redox peaks of Mb (Fe(III)-Fe(II)) was obtained at the Mb/arylhydroxylamine modified glassy carbon electrode (Mb/HAGC) by direct electron transfer between the protein and the GCE. The formal potential (E0), the apparent coverage (Γ*) and the electron-transfer rate constant (ks) were calculated as −0.317 V, 8.26 × 10−12 mol/cm2 and 51 ± 5 s−1, respectively. Dramatically enhanced biocatalytic activity was exemplified at the Mb/HAGC electrode by the reduction of hydrogen peroxide (H2O2), trichloroacetic acid (TCA) and oxygen (O2). The Mb/arylhydroxylamine film was also characterized by UV-visible spectroscopy (UV-vis), scanning electron microscope (SEM) indicating excellent stability and good biocompatibility of the protein in the arylhydroxylamine modified electrode. This new Mb/HAGC electrode exhibited rapid electrochemical response (2 s) for H2O2 and had good stability in physiological condition, showing the potential applicability of the films in the preparation of third generation biosensors or bioreactors based on direct electrochemistry of the proteins.  相似文献   

6.
Cyclic voltammetry (CV), double-potential step chronocoulometry (DPSCC), and electrochemical impedance spectroscopy (EIS) techniques have been performed to study the effects of abrasive particles on the electrochemical reaction of adrenaline at glassy carbon electrode (GCE) and platinum electrode in 0.5 mol/L H2SO4 solution. For the electrochemical reaction of adrenaline, it was shown that abrasive particles have a more marked electrocatalytic effect at GCE compared to that at platinum electrode. The electrocatalytic effect of SiC coated GCE is more obvious comparing to that of Al2O3 coated GCE. With the coarse degree of the abrasive paper increasing, the peak current (i p) increases significantly and the peak-to-peak potential separation (ΔE p) changes a little at the pretreated GCE. The electron transfer process of adrenaline at the different pretreated GCE is controlled by the diffusion in this system.  相似文献   

7.
A graphene, chitosan and Fe3O4 nanoparticles (nano-Fe3O4) modified glassy carbon electrode (graphene-chitosan/nano-Fe3O4/GCE) was fabricated. The modified electrode was characterized by scanning electron microscope and electrochemical impedance spectroscopy. The electrochemical oxidation behavior of guanosine was investigated in pH 7.0 phosphate buffer solution by cyclic voltammetry and differential pulse voltammetry. The experimental results indicated that the modified electrode exhibited an electrocatalytic and adsorptive activities towards the oxidation of guanosine. The transfer electron number (n), transfer proton number (m) and electrochemically effective surface area (A) were calculated. Under the optimized conditions, the oxidation peak current was proportional to guanosine concentration in the range of 2.0 × 10−6 to 3.5 × 10−4 mol L−1 with the correlation coefficient of 0.9939 and the detection limit of 7.5 × 10−7 mol L−1 (S/N = 3). Moreover, the modified electrode showed good ability to discriminate the electrochemical oxidation response of guanosine, guanine and adenosine. The proposed method was further applied to determine guanosine in spiked urine samples and traditional Chinese medicines with satisfactory results.  相似文献   

8.
The electrochemical behavior of electrochemical deposition of Au nanoparticles onto a glassy carbon electrode (GCE) and its application for the electrocatalytic electrogenerated chemiluminescence (ECL) of Ru(bpy)32+ in an aqueous solution without coreaction are investigated in this report. The modification of GCE by Au nanoparticles results in excellent catalysis of the ECL of Ru(bpy)32+. The effects of various factors, such as potential scan range, the presence of nitrogen and oxygen, and the scan rate on Ru(bpy)32+. ECL peaks, were systematically studied. This article has provided insight into the design of an Au-nanoparticle-modified electrode for ECL, analytical and catalytic applications. Published in Russian in Elektrokhimiya, 2008, Vol. 44, No. 9, pp. 1127–1132. The text was submitted by the authors in English.  相似文献   

9.
Hui Yao  Nan Li  Jun-Jie Zhu 《Talanta》2007,71(2):550-554
Direct electrochemical and electrocatalytic behavior of hemoglobin (Hb) immobilized on glass carbon electrode (GCE) containing gelatine (Gel) films was investigated. The characteristics of Hb/Gel film modified GC electrode were performed by using SEM microscopy, UV-vis spectroscopy and electrochemical methods. The immobilized Hb showed a couple of quasi-reversible redox peak with a formal potential of −0.38 V (versus SCE) in 0.1 M pH 7.0 PBS. The formal potential changed linearly from pH 4.03 to 8.41 with a slope value of −52.0 mV pH−1, which suggested that a proton transfer was accompanied with each electron transfer (ET) in the electrochemical reaction. The Hb/gelatine/GCE displayed a rapid amperometric response to the reduction of H2O2 and nitrite.  相似文献   

10.
The electrochemical oxidation of sulfite catalyzed by acetylferrocene (AFc) at a glassy carbon electrode (GCE) in 0.2 M NaClO4 aqueous solution has been studied by cyclic voltammetry. Although sulfite itself showed a sluggish electrochemical response at the GCE, the response could be enhanced greatly by using AFc as a mediator, which enables a sensitive determination of the substrate (sulfite). The reaction rate constant for catalytic oxidation was evaluated as (7.02 ± 0.05) × 104 M ?1 s?1 by chronoamperometry. Experimental conditions that maximize the current efficiency of the electrocatalytic oxidation, such as the pH and both the catalyst (AFc) and substrate (sulfite) concentrations, were also investigated. The electrochemical kinetics of electrocatalytic oxidation of sulfite by AFc has been studied by cyclic voltammetry. In the presence of 5 × 10?4 M AFc, the oxidation current is proportional to the sulfite concentration and the calibration plot was linear over the concentration range 2 × 10?4–2.4 × 10?3 M . This result can be applied in the determination of real samples. Copyright © 2005 John Wiley & Sons, Ltd.  相似文献   

11.
The direct and selective detection of ascorbate at conventional carbon or metal electrodes is difficult due to its large overpotential and fouling by oxidation products. Electrode modification by electrochemical reduction of diazonium salts of different aryl derivatives is useful for catalytic, analytical and biotechnological applications. A monolayer of o-aminophenol (o-AP) was grafted on a glassy carbon electrode (GCE) via the electrochemical reduction of its in situ prepared diazonium salts in aqueous solution. The o-aminophenol confined surface was characterized by cyclic voltammetry. The grafted film demonstrated an excellent electrocatalytic activity towards the oxidation of ascorbate in phosphate buffer of pH 7.0 shifting the overpotential from +462 to +263 mV versus Ag/AgCl. Cyclic voltammetry and d.c. amperometric measurements were carried out for the quantitative determination of ascorbate and uric acid. The catalytic oxidation peak current was linearly dependent on the ascorbate concentration and a linear calibration curve was obtained using d.c. amperometry in the range of 2-20 μM of ascorbate with a correlation coefficient 0.9998, and limit of detection 0.3 μM. The effect of H2O2 on the electrocatalytic oxidation of ascorbate at o-aminophenol modified GC electrode has been studied, the half-life time and rate constant was estimated as 270 s, and 2.57 × 10−3 s−1, respectively. The catalytically selective electrode was applied to the simultaneous detection of ascorbate and uric acid, and used for their determination in real urine samples. This o-AP/GCE showed high stability with time, and was used as a simple and precise amperometric sensor for the selective determination of ascorbate.  相似文献   

12.
Phytic acid (PA) with its unique structure was attached to a glassy carbon electrode (GCE) to form PA/GCE modified electrode which was characterized by electrochemical impedance. The electrochemical behavior of cytochrome c (Cyt c) on the PA/GCE modified electrode was explored by cyclic voltammetry and differential pulse voltammetry. The Cyt c displayed a quasi-reversible redox process on PA modified electrode pH 7.0 phosphate buffer solution with a formal potential (E 0′) of 57 mV (versus Ag/AgCl). The peak currents were linearly related to the square root of the scan rate in the range of 20–120 mV·s?1. The electron transfer rate constant was determined to be 12.5 s?1. The PA/GCE modified electrode was applied to the determination of Cyt c, in the range of 5?×?10?6 to 3?×?10?4 M, the currents increase linearly to the Cyt c concentration with a correlation coefficient 0.9981. The detection limit was 1?×?10?6 M (signal/noise?=?3).  相似文献   

13.
《Electroanalysis》2017,29(10):2224-2231
The morphology and structure of as‐prepared aluminum silicon carbide (Al4SiC4) were characterized using X‐ray diffraction (XRD) patterns, scanning electron microscope (SEM), transmission electron microscopy (TEM) and UV‐vis spectra. The Al4SiC4 nanoparticles modified glassy carbon electrode (GCE) was further investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Based on this, this kind of new electrode was used for the detection of trace Cu2+ by square wave anodic stripping voltammetry (SWASV) for the first time. The electrochemical parameters influencing on deposition and stripping of metal ions, such as supporting electrolytes, pH value, deposition potential and deposition time, were also optimized. The results showed that the Al4SiC4 modified GCE exhibited excellent stripping response of Cu2+ and the stripping peaks response increased linearly with increasing concentration of Cu2+ in the ranges of 400 to 2200 nM. Under the optimized conditions the favorable sensitivity of the Al4SiC4 modified GCE toward trace Cu2+ was 1.49 μA μM−1 and the limit of detection (S/N=3) was estimated to be 2.76 nM. More importantly, Al4SiC4 modified GCE had an excellent stability and negligible interference from other coexisting metal ions in the electrochemical determination of Cu2+.  相似文献   

14.
A new electrode was developed by one-step potentiostatic electrodeposition (at ?2.0 V for 20 s) of Au/SiO2 nanoparticles on a glassy carbon electrode. The resulting electrode (nano-Au/SiO2/GCE) was characterized by scanning electronic microscopy, X-ray photoelectron spectroscopy and electrochemical techniques. The electrochemical behavior of dihydronicotinamide adenine dinucleotide (NADH) at the nano-Au/SiO2/GCE were thoroughly investigated. Compared to the unmodified electrode, the overpotential decreased by about 300 mV, and the current response significantly increased. These changes indicated that the modified electrode showed excellent catalytic activity in the oxidation of NADH. A linear relationship was obtained in the NADH concentration range from 1.0?×?10?6 to 1.0?×?10?4 mol?L?1. In addition, amperometric sensing of ethanol at the nano-Au/SiO2/GCE in combination with alcohol dehydrogenase and nicotinamide adenine dinucleotide was successfully demonstrated. A wide linear response was also found for ethanol in the range from 5.0?×?10?5 to 1.0?×?10?3 mol?L?1 and 1.0?×?10?3 to 1.0?×?10?2 mol?L?1, respectively. The method was successfully applied to determine ethanol in beer and biological samples.  相似文献   

15.
We show that the addition of white dextrin during the electrochemical deposition of platinum nanostructures (nano-Pt) on a glassy carbon electrode (GCE) results in an electrochemically active surface that is much larger than that of platinum microparticles prepared by the same procedure but in the absence of dextrin. The nano-Pt deposits are characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy, and electrochemical methods. The SEM images reveal deposits composed of mainly nanoparticles and short nanorods. The GCE was applied as a novel and cost-effective catalyst for methanol oxidation. The use of nano-Pt improves the electrocatalytic activity and the stability of the electrodes.
Figure
(A) SEM image of the Pt nanostructures. (B) Electrochemical responses of the Pt nanostructures (solid line) and Pt microparticles (line) in 1.4 M CH3OH + 0.5 M H2SO4 solution at υ?=?50 mV s?1. Novel Pt nanostructures were electrodeposited at the surface of glassy carbon electrode in the presence of white dextrin as an additive, which exhibit high electrocatalytic activity towards methanol oxidation due to their highly electrochemically active surface area.  相似文献   

16.
Co3O4/graphene oxide (GO) nanocomposites were successfully prepared by a depositing‐decomposition method. The as‐prepared samples were characterized by scanning electron microscopy (SEM) and Raman spectroscopy. Cyclic voltammetry (CV) was used to evaluate the electrochemical response of a glass carbon electrode (GCE) modified with Co3O4/GO nanocomposite towards glucose. Compared with the Co3O4/GCE, the Co3O4/GO/GCE exihibits higher electrocatalytic activity due to the synergistic effects of electrocatalytic ability of Co3O4 and large surface of GO. The Co3O4/GO/GCE was applied for glucose detection in alkaline solution. The linear current response range of glucose on Co3O4/GO/GCE covered the range from 9 × 10?5 to 6.03 × 10?3 M, with a detection limit of 5.2 × 10?7 M (S/N = 3).  相似文献   

17.
Different organic molecules were covalently grafted on glassy carbon electrodes (GCEs) by an electrochemical reduction or potentiostatic process of several in situ-generated diazonium cations in acidic aqueous solution containing NaNO2. The cyclic voltammetry implemented in 0.1?M KCl aqueous solution containing 5?mM Fe(CN) 6 3? or Ru(NH3) 6 3+ confirmed the blocking properties of the modified GCEs. The electrochemical impedance spectroscopy (EIS) performed in 0.1?M KCl aqueous solution containing 5?mM Fe(CN) 6 3?/4? was used to measure the surface coverage of the modifiers on GCE; the results showed that the modified layers on GCEs are very compact. The linear sweep voltammetry (LSV) was employed to investigate the electrochemical sensing properties of the bare and modified GCEs toward paracetamol (PCT) in sulfuric acid solution of pH?1.02, and the corresponding calibration plots were obtained, respectively. The results indicated there is an oxidation peak of PCT in the linear sweep voltammograms on the bare and modified GCEs with the active terminal groups such as ?OPO3H2, ?SO3H, ?COOH, and so on, but do not appear on GCEs modified with the inert terminal groups such as ?NO2 and ?Br. These imply that the GCEs modified with the active terminal groups display an electrochemical behavior like bulk GCE; however, those with the inert terminal groups present an electrochemical behavior like microelectrode. The varying electrochemical sensitivity of all the electrodes toward PCT was explained according to electronegativity and pK a of the terminal groups of the modifiers on the electrodes and hydrogen bond between the modifiers and PCT. Apparent standard rate constants of PCT oxidation reaction on the bare and modified GCEs were obtained from the Laviron’s approach.  相似文献   

18.
The mixed‐valent nickel hexacyanoferrate (NiHCF) and poly(3,4‐ethylenedioxythiophene) (PEDOT) hybrid film (NiHCF‐PEDOT) was prepared on a glassy carbon electrode (GCE) by multiple scan cyclic voltammetry. The films were characterized using atomic force microscopy, field emission scanning electron microscopy, energy dispersive spectroscopy, X‐ray diffraction, and electrochemical impedance spectroscopy (AC impedance). The advantages of these films were demonstrated for the detection of ascorbic acid (AA) using cyclic voltammetry and amperometric techniques. The electrocatalytic oxidation of AA at different electrode surfaces, such as the bare GCE, the NiHCF/GCE, and the NiHCF‐PEDOT/GCE modified electrodes, was determined in phosphate buffer solution (pH 7). The AA electrochemical sensor exhibited a linear response from 5×10−6 to 1.5×10−4 M (R2=0.9973) and from 1.55×10−4 to 3×10−4 M (R2=0.9983), detection limit=1×10−6 M, with a fast response time (3 s) for AA determination. In addition, the NiHCF‐PEDOT/GCE was advantageous in terms of its simple preparation, specificity, stability and reproducibility.  相似文献   

19.
A modified glassy carbon electrode was prepared by depositing a composite of polymer and mediator on a glassy carbon electrode (GCE). The mediator, flavin adenine dinucleotide (FAD) and the polymer, poly(3,4-ethylenedioxythiophene) (PEDOT) were electrochemically deposited as a composite on the GCE by applying cyclic voltammetry (CV). This modified electrode is hereafter designated as GCE/PEDOT/FAD. FAD was found to significantly enhance the growth of PEDOT. Electrochemical quartz crystal microbalance (EQCM) analysis was performed to study the mass changes in the electrode during the electrodeposition of PEDOT, with and without the addition of FAD. The optimal cycle number for preparing the modified electrode was determined to be 9, and the corresponding surface coverage of FAD (ΓFAD) was ca. 5.11 × 10−10 mol cm−2. The amperometric detection of iodate was performed in a 100 mM buffer solution (pH 1.5). The GCE/PEDOT/FAD showed a sensitivity of 0.78 μA μM−1 cm−2, a linear range of 4–140 μM, and a limit of detection of 0.16 μM for iodate. The interference effects of 250-fold Na+, Mg2+, Ca2+, Zn2+, Fe2+, Cl, NO3, I, SO42− and SO32−, with reference to the concentration of iodate were negligible. The long-term stability of GCE/PEDOT/FAD was also investigated. The GCE/PEDOT/FAD electrode retained 82% of its initial amperometric response to iodate after 7 days. The GCE/PEDOT/FAD was also applied to determine iodate in a commercial salt.  相似文献   

20.
A novel electrochemical biosensor, DNA/hemin/nafion–graphene/GCE, was constructed for the analysis of the benzo(a)pyrene PAH, which can produce DNA damage induced by a benzo(a)pyrene (BaP) enzyme-catalytic product. This biosensor was assembled layer-by-layer, and was characterized with the use of cyclic voltammetry, electrochemical impedance spectroscopy (EIS) and atomic force microscopy. Ultimately, it was demonstrated that the hemin/nafion–graphene/GCE was a viable platform for the immobilization of DNA. This DNA biosensor was treated separately in benzo(a)pyrene, hydrogen peroxide (H2O2) and in their mixture, respectively, and differential pulse voltammetry (DPV) analysis showed that an oxidation peak was apparent after the electrode was immersed in H2O2. Such experiments indicated that in the presence of H2O2, hemin could mimic cytochrome P450 to metabolize benzo(a)pyrene, and a voltammogram of its metabolite was recorded. The DNA damage induced by this metabolite was also detected by electrochemical impedance and ultraviolet spectroscopy. Finally, a novel, indirect DPV analytical method for BaP in aqueous solution was developed based on the linear metabolite versus BaP concentration plot; this method provided a new, indirect, quantitative estimate of DNA damage.  相似文献   

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