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1.
A stable modified glassy carbon electrode based on the poly 3-(5-chloro-2-hydroxyphenylazo)-4,5-dihydroxynaphthalene-2,7-disulfonic acid (CDDA) film was prepared by electrochemical polymerization technique to investigate its electrochemical behavior by cyclic voltammetry. The properties of the electrodeposited films, during preparation under different conditions, and their stability were examined. The homogeneous rate constant, ks, for the electron transfer between CDDA and glassy carbon electrode was calculated as 5.25(±0.20) × 102 cm s−1. The modified electrode showed electrocatalytic activity toward ascorbic acid (AA), dopamine (DA), and uric acid (UA) oxidation in a buffer solution (pH 4.0) with a diminution of their overpotential of about 0.12, 0.35, and 0.50 V for AA, DA, and UA, respectively. An increase could also be observed in their peak currents. The modified glassy carbon electrode was applied to the electrocatalytic oxidation of DA, AA, and UA, which resolved the overlapping of the anodic peaks of DA, AA, and UA into three well-defined voltammetric peaks in differential pulse voltammetry (DPV). This modified electrode was quite effective not only for detecting DA, AA, and UA, but also for simultaneous determination of these species in a mixture. The separation of the oxidation peak potentials for ascorbic acid–dopamine and dopamine–uric acid were about 0.16 V and 0.17 V, respectively. The final DPV peaks potential of AA, DA and UA were 0.28, 0.44, and 0.61 V, respectively. The calibration curves for DA, AA, and UA were linear for a wide range of concentrations of each species including 5.0–240 μmol L−1 AA, 5.0–280 μmol L−1 DA, and 0.1–18.0 μmol L−1 UA. Detection limits of 1.43 μmol L−1 AA, 0.29 μmol L−1 DA and 0.016 μmol L−1 UA were observed at pH 4. Interference studies showed that the modified electrode exhibits excellent selectivity toward AA, DA, and UA.  相似文献   

2.
A novel and reliable electrochemical sensor based on PbO2-carbon nanotubes-room temperature ionic liquid (i.e., 1-butyl-3-methylimidazolium hexafluorophosphate, BMIMPF6) composite film modified glassy carbon electrode (GCE) (PbO2–MWNT–RTIL/GCE) was proposed for simultaneous and individual determination of guanine and adenine. The guanine and adenine oxidation responses were monitored by differential pulse voltammetric (DPV) measurement. Compared with the bare electrode, the PbO2–MWNT–RTIL/GCE not only significantly enhanced the oxidation peak currents of guanine and adenine, but also lowered their oxidation overpotentials, suggesting that the synergistic effect of PbO2, MWNT and RTIL could dramatically improve the determining sensitivity of guanine and adenine. The PbO2–MWNT–RTIL/GCE showed good stability, high accumulation efficiency and enhanced electrocatalytic ability for the detection of guanine and adenine. Besides, the modified electrode also exhibited good behaviors in the simultaneous detection of adenine and guanine with the peak separation of 0.29 V in 0.1 M pH 7.0 phosphate buffer solution (PBS). Under the optimal conditions, the detection limit for individual determination of guanine and adenine was 6.0 × 10−9 M and 3.0 × 10−8 M (S/N = 3), respectively. The proposed method for the measurements of guanine and adenine in herring sperm DNA was successfully applied with satisfactory results.  相似文献   

3.
In this paper, a multiwall carbon nanotube/Nafion composite modified glassy carbon electrode (MWNT/Nafion/GCE) was used as a voltammetric sensor to determine 8-hydroxyquinoline (8-HQ) in cosmetic. This voltammetric sensor exhibited strong catalytic effect toward the oxidation of 8-HQ and caused an anodic peak at 0.97 V in HAc-NaAc buffer solution (0.2 M, pH 3.6). Under the optimized condition, the anodic peak current was linear with the concentration of 8-HQ in the range of 2 × 10−8 M–1.0 × 10−5 M. The detection limit was 9 × 10−9 M. The practical application of MWNT/Nafion/GCE was carried out for determining 8-HQ in cosmetic sample with satisfactory results. The electrode reaction mechanism was studied by cyclic voltammetry and UV–vis spectra.  相似文献   

4.
Cyclic voltammetric investigation of calcium dobesilate (CD) in aqueous acid media was carried out by using an ordered mesoporous carbon-modified pyrolytic graphite electrode (OMC/PGE). A pair of well-defined redox peaks of CD was observed at the OMC/PGE, showing its good elelctrochemial response towards CD. The anodic current is linear with CD concentration in the range of 1.0 × 10−7–1.3 × 10−3 mol L−1, with a detection limit of 4.0 × 10−8 mol L−1. Meanwhile, the proposed electrode can avoid some interference coexisting with CD, such as uric acid, serotonin, and ascorbic acid. The proposed method can be potentially applied for selective electrochemical sensing of CD in physiological condition.  相似文献   

5.
A novel electrochemical sol–gel imprinted sensor for sensitive and convenient determination of thymidine was developed. Thin film of molecularly imprinted sol–gel polymers with specific binding sites for thymidine was cast on carbon electrode by electrochemical deposition. Multi-walled carbon nanotubes (MWCNTs) were introduced for the enhancement of electronic transmission and sensitivity. The morphology and performance of the imprinted film was characterized by scanning electron microscopy (SEM), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), differential pulse voltammetry (DPV) and amperometric measurements (it) in detail. The results showed that the imprinted film exhibited high selectivity toward thymidine. The linear range is over the range from 2 to 22 μmol L−1, and the linear regression equation for thymidine is I = 0.867C + 0.232 with the detection limit of 1.6 × 10−9 mol L−1(S/N = 3). The imprinted sensor was successfully employed to detect thymidine in some zidovudine-tablet samples.  相似文献   

6.
With ordered mesoporous carbon (OMC) as the modifier, a voltammetric sensor for folic acid (FA) was constructed on a glassy carbon electrode (GCE). Due to the good characteristics of OMC, FA exhibited an enhanced electrochemical response and lower reduction potential in the neutral solution. In addition, the experimental parameters such as pH values, accumulation time and potential were optimized. Using the differential pulse voltammetry (DPV) measurement, the peak current was found to be linear with FA concentration in the range from 5.0 × 10−10 to 1.0 × 10−7 M with a lower detection limit of 6.0 × 10−11 M (S/N = 3). Also, in real samples analysis, the as-prepared sensor successfully gives satisfying results.  相似文献   

7.
A functionalized carbon nanotubes paste electrode modified with cross-linked chitosan for the determination of trace amounts of cadmium(II) and mercury(II) by linear anodic stripping voltammetry is described. Under optimal experimental conditions, the peak current was linear in the Cd(II) concentration range from 5.9 × 10−8 to 1.5 × 10−6 mol L−1 with a detection limit of 9.8 × 10−9 mol L−1 and, for Hg(II) from 6.7 × 10−9 to 8.3 × 10−8 mol L−1with a detection limit of 2.4 × 10−9 mol L−1. The proposed method was successfully applied for the determination of Hg(II) in natural and industrial wastewater samples, and Cd(II) in sediments, human urine, natural, and industrial wastewater samples.  相似文献   

8.
Trace chromium(VI) determination plays an important role since it is carcinogenic agent and toxic pollutant. For this purpose a direct method is developed using differential pulse polarography, DPP. When selenite was added into solutions of some ions such as copper(II), lead(II), cadmium(II), zinc(II), and chromium(VI) their DP polarographic peak decreased. This kind of interference will cause large errors in the determinations, its elimination is very important. The interference between selenite and Cr(VI) ions could be eliminated in B-R (Britton-Robbinson) buffer at pH 8.5. In this work the effect of components present in buffer has been investigated and it was found that phosphate and borate eliminated the formation of Cr–Se intermetallic compound formation. While it was possible to determine 1 × 10−5 M Cr(VI) in the presence of 100 times more selenite as (1.0 ± 0.1) × 10−5 M, in borate medium, it was possible to determine (1.0 ± 0.05) × 10−5 M in phosphate medium. In the presence of selenite detection limit (S/N = 3) was 9.0 × 10−8 M Cr(VI) by using either phosphate or borate This method was applied to Gerede river water, after oxidation all Cr(III) present into Cr(VI).  相似文献   

9.
A novel modified carbon-paste electrode was employed for the simultaneous determination of dopamine (DA) and ascorbic acid (AA) with good selectivity and high sensitivity. Silver nanoparticle and carbon nanotube modified carbon-paste electrode (Ag/CNT–CPE) displayed excellent electrochemical catalytic activities towards dopamine (DA) and ascorbic acid (AA). The oxidation overpotentials of DA and AA were decreased significantly compared with those obtained at the bare CPE. Differential pulse voltammetry was used for the simultaneous determination of DA and AA. The peak separation between DA and AA was 67 mV. The calibration curves for DA and AA were obtained in the range of 8.0 × 10−7–6.4 × 10−5 M and 3.0 × 10−5–2.0 × 10−3 M, respectively. The lowest detection limits (S/N = 3) were 3.0 × 10−7 M and 1.2 × 10−5 M for DA and AA, respectively. Method was applied to the determination of DA and AA in real samples.  相似文献   

10.
Functionalized poly N,N-dimethylaniline film was prepared by adsorption of ferrocyanide onto the polymer forming at the surface of carbon paste electrode (CPE) in aqueous solution. The electrocatalytic ability of poly N,N-dimethylaniline/ferrocyanide film modified carbon paste electrode (PDMA/FMCPE) was demonstrated by oxidation of l-cysteine. Cyclic voltammetry and chronoamperometry techniques were used to investigate this ability. In the optimum pH (6.00), the electrocatalytic ability about 480 mV and the catalytic reaction rate constant, (kh), can be seen 3.08 × 103 M−1 s−1. The catalytic oxidation peak current determined by cyclic voltammetry method was linearly dependent on the l-cysteine concentration and the linearity range obtained was 8.00 × 10−5 –2.25 × 10−3 M. Detection limit of this method was determined as 6.17 × 10−5 M (2σ). At a fixed potential under hydrodynamic conditions (stirred solution), the calibration plot was linear over the l-cysteine concentration range 7.40 × 10−6 M–1.38 × 10−4 M. The detection limit of the method was 6.38 × 10−6 M (2σ).  相似文献   

11.
When a nitrobenzene (NB) phase came in quiescent contact with a water phase, water droplets were formed spontaneously near the oil|water interfaces (K. Aoki, M. Li, J. Chen, T. Nishiumi, Electrochem. Commn. 11 (2009) 239). We reported here quantitative data of the NB-droplets by use of UV-absorbance, dynamic light scattering (DLS) and voltammetry with a help of ferrocene. The supernatant separated spontaneously from the oil–water mixture contained 15.5 mmol dm−3 evaluated by UV spectra, whereas the centrifuged supernatant did 9.3 mM. The difference suggested the presence of NB-droplets, the diameter of which ranged 0.15–0.5 μm obtained by DLS. Ferrocene was dissolved deliberately in the aqueous solution and the NB solution up to saturation. The voltammograms in the ultrasonicated supernatant exhibited diffusion-controlled redox peaks of ferrocene, which should be supplied from both dissolved ferrocene and ferrocene-dissolved NB droplets. The former was 1/3.6 times of the latter by the comparison with the current of ferrocene-saturated aqueous solution. Applying the expression for the diffusion-controlled peak current of a big particle, we estimated the number concentration of NB droplet to be 1.1 × 1014 dm−3. This value is equivalent to the average distance, = 2.1 μm, between neighboring two droplets, corresponding to the diffusional traveling time, L2/= 1.3 s, which would be long enough for collision of droplets to stabilize the emulsions.  相似文献   

12.
This work compares the electroactivity of a conventional carbon-paste electrodes and screen-printed carbon electrodes. Potentiometric sensors responsive to sildenafil citrate (SILC) drug (the active component of Viagra) are described, characterized, compared and used for drug assessment. The proposed carbon paste electrode is fully characterized in terms of plasticizer type, response time, life span, soaking time, titrant, pH and temperature. The electrodes exhibited linear response with a Nernstian slope of 58.20 ± 1 and 58.82 ± 0.5 mV decade−1 for SILC in the concentration range from 1.0 × 10−7 to 1.0 × 10−2 and 5.30 × 10−7 to 1.0 × 10−2 mol L−1 with good reproducibility for CPE and SPE, respectively. Both CPE and SPE could be used in the pH range 3.0–5.0 and the isothermal coefficient is found to be 0.98 and 0.85 mV/°C, respectively. The limit of detection was found to be 9.0 × 10−8 and 3.5 × 10−7 mol L−1 for CPE and SPE, respectively. They were applied to potentiometric determination of SILC in pure state and pharmaceutical preparation under batch conditions. The CPE and SPE sensors display good selectivity for SILC drug over large number of inorganic cations, sugars and amino acids commonly used in drug formulations. The CPE and SPE show high selectivity for the drug under investigation. The results obtained using the fabricated CPE is compared with those obtained by SPE for spiked pharmaceutical samples.  相似文献   

13.
Nafion® 211 differs from previous versions of Nafion in that the membrane is cast from a dispersion rather than being melt-extruded. As such, the water sorption properties are different, as is the rate of increase in water content with temperature. Kinetic and mass-transport parameters for dispersion-cast Nafion® 211 were determined using solid-state electrochemistry in the temperature range 30–70 °C, 100% relative humidity, and 30 psi oxygen pressure. Exchange current densities, Tafel slopes, and transfer coefficients for ORR in Nafion® 211, are similar to those observed in Nafion® 117; mass-transport parameters are not. At 30 °C and 100% RH oxygen solubility and the diffusion coefficient is determined to be 1.16 × 10−5 mol cm−3 and 1.13 × 10−6 cm2 s−1, respectively. Oxygen permeability at 30 °C (1.28 × 10−11 mol cm−1 s−1) is lower than in Nafion® 117 (5.31 × 10−11 mol cm−1 s−1) by factor of 4, while at T > 60 °C the permeability of Nafion® 211 increases significantly to values higher than Nafion® 117, and is correlated with the increase in water content and hydration number (λ) with temperature.  相似文献   

14.
The functionalized carbon nanotube electrode was fabricated by electrodeposition of 1,2-naphthoquinone-4-sulfonic acid sodium (Nq) on single-wall carbon nanotube (SWNT) modified glassy carbon electrode (GCE). This electrode was characterized by scanning electron microscopy (SEM) and the results showed that Nq can rapidly and effectively be deposited on the surface of SWNT film with high stability. The electrochemical properties of functionalized SWNT/GCE with Nq (SWNT–Nq/GCE) were studied using cyclic voltammetry, double step potential chronoamperometry and differential pulse voltammetry methods. The results indicated that SWNT could improve the electrochemical behavior of Nq and greatly enhances its redox peak currents. The SWNT–Nq/GCE exhibited a pair of well-defined redox peaks. The experimental results also demonstrated that the Nq deposited species on SWNT could catalyze cysteamine oxidation and SWNT–Nq exhibited a high performance with lowering the overpotential by more than 710 mV. The effect of pH value, number of scans and Nq concentration were investigated on the electrochemical behavior of cysteamine. The selectivity of the reaction has been assessed with no interference from tyrosine, lysine, methionine, tryptophan, alanine and glutathione. The presented method has highly selectivity for voltammetric detection of cysteamine in the dynamic range from 5.0 × 10−6 M to 2.7 × 10−4 M and with a detection of limit (3σ) 3.0 × 10−6 M.  相似文献   

15.
Voltammetric and electrochemical impedance spectroscopic (EIS) studies of generation one poly(propylene imine) (G1 PPI) dendrimer as an electroactive and catalytic nanomaterials both in solution and as an electrode modifier based on a simple one step electrodeposition method is presented. The G1 PPI exhibited a reversible one electron redox behaviour at E0′ ca 210 mV in phosphate buffer pH 7.2 with diffusion coefficient and Warburg coefficient of 7.5 × 10−10 cm2 s−1 and 8.87 × 10−4 Ω s−1/2 respectively. Cyclic voltammetric electrodeposition of a monolayer of G1 PPI on glassy carbon electrode was carried out between −100 mV and 1100 mV for 10 cycles. The nanoelectrode was electroactive in PBS at E0′ ca 220 mV. Kinetic profiles such as time constant (4.64 × 10−5 s rad−1), exchange current (1.55 × 10−4 A) and heterogeneous rate constant (4.52 × 10−3 cm s−1) obtained from EIS showed that the dendrimer layer catalysed the redox reaction of Fe2+/3+ in [Fe(CN)6]3−/4− redox probe.  相似文献   

16.
The flow cell proposed previously for the rapid and coulometric determination of cations based on the electrochemical ion transfer at the aqueous|organic solution interface was improved to be applicable to the determination of anions. The developed cell was composed of a porous poly(tetrafluoroethylene) tube (1.0 mm in inner diameter), a copper wire (0.8 mm in diameter) inserted into the tube, a platinum wire placed outside the tube, an organic solution into which the tube was immersed and a reference electrode in the organic solution. The aqueous solution containing a species of interest was flowed through the narrow gap between the tube and the copper wire. A potential difference was applied at the aqueous|organic solution interface by using the copper wire and the reference electrode in the organic solution in order to realize the ion transfer at the interface, and the current due to the interfacial ion transfer was detected by the copper and platinum wires. The developed cell was evaluated adopting the transfer of an anion such as perchlorate, picrate or alkylsulphonates from the aqueous solution to 1,2-dichloroethane (used as the organic solution), and demonstrated that the anions of 10−4 mol dm−3 level could be determined with coefficients of variations better than 0.2% (n = 5). The applicability of the developed cell to the flow injection analysis of anions was also discussed.  相似文献   

17.
Polypyrrole hexafluorosilicate, PPYSiF6, and polypyrrole hexafluoroaluminate, PPYAlF6, were found to follow the mixed 2DI–3DI kinetic model of electrodeposition in the potentials range (+0.80 V, +0.60 V) and (+0.95 V, +0.55 V) vs. SCE, respectively. The potentiostatic depositions of polypyrrole were performed on polycrystalline gold and on the single layer or bilayer polypyrrole films. Only in the case of the third layer deposition of PPYSiF6 (on PPYSiF6) at +0.6 V, the experimental current was found to fit better with the 2DP–3DI model. For electrodeposition of PPYAlF6 on gold, a slightly better quality fitting with 2DP–3DP or 2DP–3DI kinetic models was observed only for some samples synthesized at 0.55 V. In general, contribution of the 2D structure in the polypyrrole deposits was observed to decrease with an increase of the polarization potential. Conclusions of the mathematical analysis of the current–time functions are in accordance with a texture of the outer surface of the polymer layers visible in SEM micrographs. The apparent rate constants of the lateral and outward growths of polypyrrole increase with potentials in (+0.55, +0.80) V range. Under assumption of the classical electrochemical kinetics law, the anodic transfer coefficients were found lower than 0.5. Values of the outward growth rate constant were of the order of 10−8–10−10 mol/(s cm2); being approximately one order of magnitude higher for polypyrrole hexafluorosilicate than for polypyrrole hexafluoroaluminate. The lateral growth rates of PPYAlF6 on gold were found to depend on the electrodeposition potential more significantly than the outward growth rate. An increase in the growth rates with the potential was observed to diminish/vanish at E > +0.80 V, probably due to concurrent degradation processes of polypyrrole chains. The analysis of the deposition currents was done under conditions of the masking double layer currents that were characterized by the relaxation times of the order of seconds or longer.  相似文献   

18.
Fe-modified zeolites (ferrierite and MFI) were prepared by four impregnation methods followed by calcination and tested as catalysts in oxidative dehydrogenation of ethane by nitrous oxide at 350 °C. The Fe cationic and Fe oxidic species were identified by combination of UV–Vis spectroscopy and voltammetry. Monomeric or dimeric Fe ions have only UV absorption bands and some of them evolve voltammetrically identifiable [Fe(OH)x](3−x)+ ions in contact with acetic acid-sodium acetate buffer. Fe oxide nanoclusters characterised by UV band at about 28,000 cm−1 are not detected by voltammetry under chosen conditions because they are situated inside the zeolite channels. Amorphous, nanocrystalline, and crystalline Fe(III) oxides were distinguished sensitively by their specific voltammetric reduction peaks at potentials −0.1 to −0.8 V/SCE in acetate buffer (pH 4.7) and by phase-specific electron pair transitions responsible for Vis absorption band centred at 17,500–21,000 cm−1. The proposed method to differentiation between these ferric oxides is novel in materials analysis and solid state speciation. The monomeric and dimeric ferric ions are active in oxidative dehydrogenation of ethane to ethene with selectivity about 40–60% under used conditions, while Fe oxide nanoclusters are too active and over-oxidise ethane and/or ethene to C, CO and CO2. Oppositely to general expectations, ferric oxides are indifferent in the catalytic reaction and do not decrease reaction selectivity.  相似文献   

19.
Direct reduction of Lindane (1R,2r,3S,4R,5r,6S-hexachlorocyclohexane, 1) at carbon cathodes in dimethylformamide (DMF) containing 0.10 M tetra-n-butylammonium tetrafluoroborate (TBABF4) has been explored by means of cyclic voltammetry and controlled-potential (bulk) electrolysis. Cyclic voltammograms for reduction of 1 at a glassy carbon electrode exhibit two cathodic peaks at −1.40 V and −2.10 V as well as an anodic peak at −1.93 V; the first cathodic peak is attributed to reduction of 1 itself, whereas the second cathodic peak is due to reduction of chlorobenzene that is derived from 1. Controlled-potential (bulk) electrolyses conducted with reticulated vitreous carbon electrodes held at −1.70 or −2.20 V reveal that reduction of 1 is essentially a six-electron process that affords benzene as major product (80–100% yield) along with small amounts of chlorobenzene (3–10% yield). To account for these products, a mechanism is proposed that is supported by the results of theoretical computations based on density functional theory.  相似文献   

20.
The electrochemical behaviors of magnolol have been studied at glassy carbon electrode using cyclic voltammetry, linear sweep voltammetry and chronocoulometry. Moreover, its interaction with DNA was investigated in solution by electrochemical methods and ultraviolet–visible spectroscopy. The experiment results indicated that the electrochemical oxidation of magnolol was an irreversible process with one proton and one electron transfer. The electron transfer coefficient (α) was calculated to be 0.441 ± 0.001. At the scan rate from 100 mV/s to 450 mV/s, the electrode process was controlled by the adsorption step and at the range of 600–950 mV/s the electrochemical oxidation was diffusion controlled process. The corresponding electrochemical rate constant (ks) was 0.0760 ± 0.0001 s−1. Through chronocoulometry experiment, the diffusion coefficient (D) and the surface concentration (Γ) were obtained as (3.76 ± 0.01) × 10−7 cm2/s and (2.98 ± 0.01) × 10−10 mol/cm2. In addition, the interaction of magnolol and DNA was ascribed to be electrostatic interaction and the calculated association constant (β) and Hill coefficient (m) were 1.14 × 105 M−1 and 0.973. At last a sensitive and convenient electrochemical method was proposed for the determination of magnolol.  相似文献   

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