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1.
A stable suspension of ordered mesoporous carbon (OMC) was obtained by dispersing OMC in a solution of Nafion. By coating the suspension onto glassy carbon (GC) electrode, cyclic voltammetry was used to evaluate the electrochemical behaviors of Nafion-OMC-modified GC (Nafion-OMC/GC) electrode in 0.1 mmol L−1 hexaammineruthenium(III) chloride (Ru(NH3)6Cl3)/0.1 mol L−1 KCl solution, where Nafion-OMC/GC electrode shows a faster electron transfer rate as compared with OMC/GC, Nafion/GC and GC electrodes. Due to the unique properties of Nafion-OMC, an obvious decrease in the overvoltage of the epinephrine (EP) oxidation (ca. 100 mV at pH 4.1 and 115 mV at pH 7.0) as well as a dramatic increase in the peak current (12 times at pH 4.1 and 6 times at pH 7.0) was observed at Nafion-OMC/GC electrode compared to that seen at GC electrode. By combining the advantages of OMC with those of Nafion, the anodic peak of EP and that of ascorbic acid (AA) were separated successfully (by ca. 144-270 mV) in the pH range of 2.0-10.0, which may make Nafion-OMC/GC electrode potential for selective determination of EP in the presence of AA at a broad pH range. As an EP sensor, the EP amperometric response at Nafion-OMC/GC electrode in pH 7.0 PBS is extremely stable, with 99% of the initial activity remaining (compared to 32% at GC surface) after 120 min stirring of 0.20 mmol L−1 EP. And Nafion-OMC/GC electrode can be used to readily detect the physiological concentration of EP at pH 7.0. These make Nafion-OMC/GC electrode potential candidates for stable and efficient electrochemical sensor for the detection of EP. The solubilization of OMC by Nafion may provide a route to more precise manipulation, and functionalization for the construction of OMC-based sensors, as well as allowing OMC to be introduced to biologically relevant systems.  相似文献   

2.
The potential application of hybrid ZSM-5/Al-MCM-41 zeolitic-mesostructured materials as supports of metallocene polymerization catalysts has been investigated and compared with the behaviour of standard mesoporous Al-MCM-41 and microporous ZSM-5 samples. Hybrid zeolitic-mesostructured solids were prepared from zeolite seeds obtained with different Si/Al molar ratios (15, 30 and 60), which were assembled around cetyltrimethylammonium bromide (CTAB) micelles to obtain hybrid materials having a combination of both zeolitic and mesostructured features. (nBuCp)2ZrCl2/MAO catalytic system was impregnated onto the above mentioned solid supports and tested in ethylene polymerization at 70 °C and 5 bar of ethylene pressure. Supports and heterogeneous catalysts were characterized by X-ray powder diffraction, nitrogen adsorption-desorption isotherms at 77 K, transmission electron microscopy, 27Al-MAS-NMR, ICP-atomic emission spectroscopy and UV-vis spectroscopy.Catalysts supported over hybrid ZSM-5/Al-MCM-41 (Si/Al = 30-60) exhibited the best catalytic activity followed by those supported on Al-MCM-41 (Si/Al = 30-60). However, catalyst supported on ZSM-5 gave lower polymerization activity because of its microporous structure with narrower pores and lower textural properties than hybrid and mesoporous materials.Although higher acid site population shown by hybrid materials could contribute to the stabilization of the metallocene system on the support, in this case their better catalytic performance is mainly ascribed to the larger textural properties.  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.
A CuGeO3 nanowire modified glassy carbon electrode was fabricated and characterized by scanning electron microscopy. The results of electrochemical impedance spectroscopy reveal that electron transfer through nanowire film is facile compared with that of bare glassy carbon electrode. The modified electrode exhibited a novel electrocatalytic behavior to the electrochemical reactions of l-cysteine in neutral solution, which was not reported previously. Two pairs of semi-reversible electrochemical peaks were observed and assigned to the processes of oxidation/reduction and adsorption/desorption of cysteine at the modified electrode, respectively. The electrochemical response of cysteine is poor in alkaline condition and is enhanced greatly in acidic solution, suggesting that hydrogen ions participate in the electrochemical oxidation process of cysteine. The intensities of two anodic peaks varied linearly with the concentration of cysteine in the range of 1 × 10−6 to 1 × 10−3 mol L−1, which make it possible to sensitive detection of cysteine with the CuGeO3 nanowire modified electrode. Furthermore, the modified electrode exhibited good reproducibility and stability.  相似文献   

5.
A novel uracil covalently grafted carbon paste electrode (Ura/CPE) based on electro-deposition of uracil on CPE was prepared for the quantitative determination of nevirapine. The records of electrochemical impedance spectroscopy (EIS) and cyclic voltammograms (CV) in K3Fe(CN)6/K4Fe(CN)6 solution illustrated that uracil grafted on CPE efficiently decreased the charge transfer resistance value of electrode and improved the electron transfer kinetic between analyte and electrode. The electrochemical properties of Ura/CPE towards the oxidation of nevirapine were investigated by cyclic voltammetry and differential pulse voltammetry (DPV) in 0.1 M NaOH. The effects of pH and scan rates on the oxidation of nevirapine were studied. The results indicated the participation of the same protons and electrons in the oxidation of nevirapine, and the electrochemical reaction of nevirapine on Ura/CPE is an adsorption-controlled process. Under optimized conditions, the linearity between the oxidation peak current and nevirapine concentration was obtained in the range of 0.1–70.0 μM with detection limit of 0.05 μM and the sensitivity of 2.073 μA mM?1 cm?2 (S/N = 3). The proposed method was also successfully applied to detect the concentration of nevirapine in human serum samples.  相似文献   

6.
The simultaneous voltammetric determination of dihydroxybenzene isomers was investigated using cyclic and differential pulse voltammetries at the amino-functionalized SBA-15 mesoporous silica-modified carbon paste electrode (NH2-SBA15/CPE) in phosphate buffer solution (pH 6.0). The NH2-SBA15/CPE showed a larger peak current and higher selectivity for the dihydroxybenzene isomers in comparison with the bare carbon paste electrode (CPE) and SBA-15 mesoporous silica-modified carbon paste electrode (SBA15/CPE). The oxidation peak potential difference between hydroquinone (HQ) and catechol (CC) was 115 mV and was 396 mV between catechol and resorcinol (RC). This indicated that catechol, resorcinol and hydroquinone could be identified entirely at the NH2-SBA15/CPE. Under the optimized conditions, the amperometric currents were linear over ranges from the following: 0.8–160 μmol L−1 for hydroquinone, 1.0–140 μmol L−1 for catechol and 2.0–160 μmol L−1 for resorcinol. The detection limits were 0.3, 0.5 and 0.8 μmol L−1, respectively. The proposed electrode can be applied to the simultaneous determination of dihydroxybenzene isomers in mixtures without previous chemical or physical separations.  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.
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   

9.
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   

10.
Ionic liquid, 1-heptyl-3-methylimidazolium hexafluorophosphate (HMIMPF6), has been used to fabricate two new electrodes, carbon ionic liquid electrode (CILE) and ionic liquid modified carbon paste electrode (IL/CPE), using graphite powder mixed with HMIMPF6 or the mixture of HMIMPF6/paraffin liquid as the binder, respectively. The electrochemical behaviors of hydroquinone at the CILE, the IL/CPE and the CPE were investigated in phosphate buffer solution. At all these electrodes, hydroquinone showed a pair of redox peaks. The order of the current response and the standard rate constant of hydroquinone at these electrodes were as follows: CILE > IL/CPE > CPE, while the peak-to-peak potential separation was in an opposite sequence: CILE < IL/CPE < CPE. The results show the superiority of CILE to IL/CPE and CPE, and IL/CPE to CPE in terms of promoting electron transfer, improving reversibility and enhancing sensitivity. The CILE was chosen as working electrode to determine hydroquinone by differential pulse voltammetry, which can be used for sensitive, simple and rapid determination of hydroquinone in medicated skin cosmetic cream.  相似文献   

11.
A novel poly rutin (Ru) modified paraffin-impregnated graphite electrode (WGE) was fabricated by electrochemical method. The field emission scanning electron microscope (FE-SEM), infrared spectra (IR), in situ UV-spectroelectrochemical and electrochemical techniques proved the immobilization of rutin on WGE. Ru undergoes electrochemical oxidation in two ways related to the two catechol hydroxyl groups and the other two hydroxyl groups; the former not only carries out a two-electron two-proton reversible reaction, but also produces unstable phenoxy radicals which readily polymerize to strongly adhere to WGE surface companying Ru monomer embeded and adsorbed in the film (Ru/WGE). The Ru/WGE displayed strong catalytic function for the oxidation of adrenalin (EP), serotonin (5-HT), and ascorbic acid (AA) and resolved the overlap voltammetric response of EP and AA into two well-defined voltammetric peaks of about 172 mV with DPV. A linear response in the range of 3.0-90.0 μM with detection limit (s/n = 3) of 8.0 × 10−7 M for EP was obtained in coexistence of AA (0.01 mM).  相似文献   

12.
Nanodiamond (ND) powder electrodes were fabricated and the electrochemical properties were investigated in the solution containing nitrite in this article. This electrode exhibits substantial catalytic ability toward the oxidation of nitrite anions. The electrochemical oxidation mechanism of nitrite on the ND powder electrode is discussed. The oxidation of NaNO2 is a two-electron transfer process. The electrode reaction rate constant k is estimated to be 2.013 × 10−4 cm/s and (1 − α)nα is 0.1643. The peak current increases linearly with the rising of the concentration of NaNO2.  相似文献   

13.
Protoporphyrin IX (PPIX) was immobilized on Au surfaces for the electrochemical oxidation of dopamine (DA) and epinephrine (EP). Two procedures for the immobilization were employed. One class of modified electrodes was prepared by immobilizing the PPIX into polypyrrole (PPy) films synthesized by anodic electropolymerization. The other procedure involved the immobilization of PPIX on an electrode modified by a 11-mercaptoundecanoic acid (MUA) self-assembled monolayer (SAM). The modified surfaces were characterized by cyclic voltammetry (CV).The efficiency of these modified surfaces for the electrochemical oxidation of DA and EP was investigated and compared. The peak potential for the oxidation of each analyte at the different electrode surfaces was determined by square-wave voltammetry (SWV).The dependence of the sensitivity of the electrodes for the detection of the catecholamines on the applied potential was also measured. The SAM-based electrodes showed better selectivity for detecting DA in the potential range between 0.2 and 0.4 V versus Pt (QRE). However, higher sensitivity and linearity were observed for the film-based electrodes.  相似文献   

14.
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   

15.
A carbon-paste electrode (CPE) chemically modified with the cobalt(II)-4-methylsalophen (CoMSal) as a Schiff base complex was used as a highly sensitive and fairly selective electrochemical sensor for simultaneous determination of minor mounts of ascorbic acid (AA) and cysteine. This modified electrode shows very efficient electrocatalytic activity for anodic oxidation of both AA and cysteine via substantially decreasing of anodic overpotentials for both compounds. The mechanism of electrochemical oxidation of both AA and cysteine using CoMSal-modified electrode was thoroughly investigated by cyclic voltammetry and polarization studies. Results of cyclic voltammetry (CV) and differential pulse voltammetry (DPV) using this modified electrode show two well-resolved anodic waves for the oxidation of AA and cysteine, which makes it possible for simultaneous determination of both compounds. A linear range of 1 × 10−4 to 5 × 10−7 M for cysteine in a constant concentration of 1 × 10−4 M AA in buffered solution (as a background electrolyte) was obtained from DPV measurements using this electrode. The linear range, which is obtained for AA in the presence of 1 × 10−4 M cysteine, was in the range of 1 × 10−4 to 1 × 10−6 M. The modified electrode has good reproducibility (RSD ≤ 2.5%), low detection limit (sub-micromolar) and high sensitivity for the detection of both AA and cysteine with a very high stability in its voltammetric response. Differential pulse voltammetry using the modified electrode exhibited a reasonable recovery for a relatively wide concentration range of cysteine spiked to a synthetic human serum sample.  相似文献   

16.
A novel electrode material was obtained at an aluminum electrode (Al) by a simple electroless method including two consecutive procedures: (i) the electroless deposition of metallic palladium on the Al electrode surface from PdCl2 + 25% ammonia solution and (ii) the chemical transformation of deposited palladium to the palladium hexacyanoferrate (PdHCF) films in a solution containing 0.5 M K3[Fe(CN)6]. The modified Al electrode demonstrated a well-behaved redox couple due to the redox reaction of the PdHCF film. The PdHCF film showed an excellent electrocatalytic activity toward the oxidation of dopamine (DA). The effect of solution pH on the voltammetric response of DA has been investigated. A linear calibration graph was obtained over the DA concentration range 2-51 mM. The rate constant k and transfer coefficient α for the catalytic reaction and the diffusion coefficient of DA in the solution D, were found to be 4.67 × 102 M−1 s−1, 0.63 and 2.5 × 10−6 cm2 s−1, respectively. The interference of ascorbic acid was investigated and greatly reduced using a thin film of Nafion on the modified electrode. The modified electrode indicated reproducible behavior and a high level stability during electrochemical experiments, making it particularly suitable for the analytical purposes.  相似文献   

17.
The electrochemistry of bisoprolol fumarate (BF) has been investigated by differential pulse voltammetry at a single-wall carbon nanotubes (SWNTs) modified glassy carbon electrode (GCE). The prepared electrode showed an excellent electrocatalytic activity towards the oxidation of BF leading to a marked improvement in sensitivity as compared to bare glassy carbon electrode where electrochemical activity for the analyte cannot be observed. The SWNTs-modified GCE exhibited a sharp anodic peak at a potential of ∼950 mV for the oxidation of BF. Under optimum conditions linear calibration curve was obtained over the BF concentration range 0.01-0.1 mM in 0.5 M phosphate buffer solution (pH 7.2) with a correlation coefficient of 0.9789 and detection limit of 8.27 × 10−7 M. The modified electrode has been applied for the drug determination in human urine with no prior extraction and in commercial tablets. The proposed method has also been validated.  相似文献   

18.
This work reports the electrocatalytic activity of 2,3,5,6-tetrachloro-1,4-benzoquinone (TCBQ)/multi-walled carbon nanotubes (MWCNT) immobilized on an edge plane pyrolytic graphite electrode for nicotinamide adenine dinucleotide (NADH) oxidation. Scanning electron microscopy (SEM) and energy dispersive X-ray spectrometry (EDS) were used to confirms the presence of chloro after the nanotube modification with 2,3,5,6-tetrachloro-1,4-benzoquinone. The surface charge transfer constant, ks, and the charge transfer coefficient for the modified electrode, α, were estimated as 98.5 (±0.6) s−1 and 0.5, respectively. With this modified electrode the oxidation potential of the NADH was shifted about 300 mV toward a less positive value, presenting a peak current much higher than those measured on an unmodified edge plane pyrolytic graphite electrode (EPPG). Cyclic voltammetry and rotating disk electrode (RDE) experiments indicated that the NADH oxidation reaction involves 2 electrons and a heterogenous rate constant (kobs) of 3.1 × 105 mol−1 l s−1. The detection limit, repeatability, long-term stability, time of response and linear response range were also investigated.  相似文献   

19.
The electrochemical behavior of bisphenol A (BPA) was investigated on Mg-Al layered double hydroxide (LDH) modified glassy carbon electrode (GCE) by cyclic voltammetry (CV), differential pulse voltammetry (DPV), linear sweep voltammetry (LSV) and chronocoulometry (CC). The cyclic voltammogram of BPA on the modified electrode exhibited a well defined anodic peak at 0.454 V in 0.1 M pH 8.0 phosphate buffer solution (PBS). The experimental parameters were optimized and the kinetic parameters were investigated. The probable oxidation mechanism was proposed. Under the optimized conditions, the oxidation peak current was proportional to BPA concentration in the range from 1 × 10−8 to 1.05 × 10−6 M with the correlation coefficient of 0.9959. The detection limit was 5.0 × 10−9 M (S/N = 3). The fabricated electrode showed good reproducibility, stability and anti-interference. The proposed method was successfully applied to determine BPA in plastic products and the results were satisfactory.  相似文献   

20.
[PFeW11O39]4− (PFeW11) supported on the surface of 3-aminopropyl(triethoxy)silane modified silica gel was synthesized and used as a bulk modifier to fabricate a renewable three-dimensional chemically modified electrode. The electrochemical behavior of the modified electrode was investigated. Cyclic voltammetry studies showed that the PFeW11 on the electrode surface sustained the same electrochemical properties as that of the PFeW11 in solution. The preparation of chemically modified electrode is simple and quiet reproducible using inexpensive material. The modified electrode had high electrocatalytic activity toward H2O2 reduction and it was successfully applied as an electrochemical detector to monitor H2O2 in flow injection analysis (FIA). The electrocatalytic peak current was found to be linear with the H2O2 concentration in the range 10-200 μmol L−1 with a correlation coefficient of 0.998 and a detection limit (3σ) of 7.4 μmol L−1 H2O2. The electrode has the remarkable advantage of surface renewal owing to bulk modification, as well as simple preparation, good mechanical and chemical stability and reproducibility.  相似文献   

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