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1.
A sensitive and simplified voltammetric method is developed for the determination of trace amounts of vanadium(V) by adsorptive anodic stripping voltammetry using an acetylene black (AB) paste electrode. The method is based on the preconcentration of the V(V)–alizarin violet (AV) complex at open circuit while stirring the solution for 90 s in 0.15 mol dm−3 hexamethylenetetraamine–hydrochloric acid buffer (pH 4.4), the adsorbed complex is then oxidized, producing a response with a peak potential of 564 mV when scanning linearly from 0 to 1000 mV. For voltammetric determination of V(V), the parameters influencing the peak current have been optimized. Under the selected conditions, the peak current and concentration of V(V) accorded with linear relationship in the range of 8.0 × 10−10 mol dm−3–1.0 × 10−7 mol dm−3 (cAV = 2.0 × 10−6 mol dm−3) and 1.0 × 10−7 mol dm−3–8.0 × 10−6 mol dm−3 (cAV = 2.0 × 10−5 mol dm−3), the detection limit (three times signal to noise) was estimated to be 6.0 × 10−10 mol dm−3 for 90 s accumulation. The relative standard deviation (RSD) is 1.9% and 2.3% for V(V) concentrations of 1.0 × 10−7 mol dm−3 and 1.0 × 10−8 mol dm−3 respectively. Finally, this proposed method was successfully applied to the determination of V(V) in natural water samples.  相似文献   

2.
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   

3.
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   

4.
In the present paper, the use of a gold electrode modified by 2-(2,3-dihydroxy phenyl)-1,3-dithiane self-assembled monolayer (DPDSAM) for the determination of epinephrine (EP) and uric acid (UA) was described. Initially, cyclic voltammetry was used to investigate the redox properties of this modified electrode at various scan rates. The apparent charge transfer rate constant, ks, and transfer coefficient, α, were calculated. Next, the mediated oxidation of EP at the modified electrode was described. At the optimum pH of 8.0, the oxidation of EP occurs at a potential about 155 mV less positive than that of an unmodified gold electrode. The values of electron transfer coefficients (α = 0.356), catalytic rate constant (k = 1.624 × 104 M−1 s−1) and diffusion coefficient (D = 1.04 × 10−6 cm2 s−1) were calculated for EP, using electrochemical approaches. Based on differential pulse voltammetry, the oxidation of EP exhibited a dynamic range between 0.7 and 500.0 μM and a detection limit (3σ) of 0.51 μM. Furthermore, simultaneous determination of EP and UA at the modified electrode was described. Finally, this method was used for the determination of EP in EP ampoule.  相似文献   

5.
The renewable mercury film electrode, applied for the determination of tungsten(VI) ultra traces using differential pulse catalytic adsorptive cathodic stripping voltammetry (DPCAdSV) with presence of catechol as a ligand and chlorate(V) is presented. The calibration graph obtained for W(VI) is linear from 0.025 nM (4.5 ng L−1) to 130 nM (23.9 μg L−1) for a preconcentration time of 30 s, with correlation coefficient of 0.9989. For the renewable mercury electrode (Hg(Ag)FE) with a surface area of 4.4 mm2 the detection limit for a preconcentration time of 60 s is as low as 0.2 ng L−1. The repeatability of the method at a concentration level of the analyte as low as 0.09 μg L−1, expressed as RSD is 3.1% (n = 5). The proposed method was successfully applied and validated by studying the certified reference material CTA-VTL-2 and simultaneously recovery of W(VI) from spiked water samples.  相似文献   

6.
The cyclic renewable mercury film silver based electrode (Hg(Ag)FE), applied for the determination of vanadium(V) traces using differential pulse adsorptive cathodic stripping voltammetry (DP AdCSV) with presence of chloranilic acid as a ligand is presented. The calibration graph obtained for V(V) is linear from 0.25 nM (12.7 ng L−1) to 150 nM (7.6 μg L−1) for a preconcentration time of 20 s, with correlation coefficient of 0.9992. For a Hg(Ag)FE with a surface area of 6.6 mm2 the detection limit for a preconcentration time of 90 s is as low as 0.5 ng L−1. The repeatability of the method at a concentration level of the analyte as low as 1.3 μg L−1, expressed as RSD is 2.1% (n = 5). The proposed method was successfully applied and validated by studying the certified reference materials TMRAIN-95, SPS-SW1, SPS-SW2 and simultaneously recovery of V(V) from spiked water samples.  相似文献   

7.
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   

8.
A scanning electrochemical microscope (SECM) in the feedback and generation-collection modes was used to investigate the regeneration of photoexcited dye cations at the semiconductor/electrolyte interface in a dye-sensitized solar cell (DSSC) based on ZnO/D149. An effective dye regeneration rate constant kox of 9.55 × 107 cm9/2 mol−3/2 s−1 was obtained from feedback mode experiments at different wavelengths and light intensities on ZnO/D149 electrodes. Illuminated regions of the dye-sensitized electrodes could be differentiated from non-illuminated regions by local imaging in SECM generation-collection experiments with I- as redox mediator. We also report SECM feedback measurements on non-illuminated dye-sensitized electrodes to investigate the electron transfer kinetics of dissolved redox couples at the underlying FTO substrate.  相似文献   

9.
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   

10.
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   

11.
The electrochemical behaviors of dimethyl ether (CH3–O–CH3, DME), which is a promising fuel for the fuel cell, on Pt(1 0 0) electrode in 0.5 M H2SO4 solution have been investigated in detail by electrochemical and in situ infrared (IR) measurements. As the potential is swept from 0.05 V (vs. RHE) to positive direction at 50 mV s−1, the dehydrogenation peak of DME is observed around 0.33 V to generate a reaction intermediate and is further converted to carbon monoxide (CO) in more positive potential region. The main peak for DME bulk oxidation locates around 0.80 and 0.72 V in the positive- and negative-going potential sweep, respectively. The positions of these peaks strongly depend on the scan rate. The in situ IR observations show that (CH3OCH2–)ad is an intermediate for the first dehydrogenation step of DME on Pt(1 0 0) surface and can serve as a precursor of the subsequent intermediate of adsorbed CO (COad). Cyclic voltammograms of Pt high index single crystal planes Pt(hkl) show that the direct oxidation of DME is suppressed by decreasing the (1 0 0) terrace width. Based on these results, a possible reaction mechanism for DME electro-oxidation on the platinum single crystal electrode surface is proposed.  相似文献   

12.
This research in finding a cheap and efficient catalyst for electrooxidation of formaldehyde give us an attempt to make and examine the behavior of poly(N-methylaniline)/nickel modified carbon paste electrode (Ni/P(NMA)/MCPE) in absence and presence of formaldehyde. This involves in situ electropolymerization of N-methylaniline at carbon paste electrode, which is following to the incorporation of Ni(II) to polymeric layer by immersion of modified electrode in 1.0 M nickel sulphate solution. The electrocatalytic oxidation of formaldehyde was studied by cyclic voltammetry and chronoamperometry methods. The effects of scan rate and formaldehyde concentration on the electrocatalytic oxidation of formaldehyde were also investigated at the surface of Ni/P(NMA)/MCPE. The diffusion coefficient (D = 14.1 × 10−5 cm2 s−1), and some kinetic parameters such as the transfer coefficient (α = 0.45) and also second-order rate constant (k = 8.96 × 10−4 cm3 mol−1 s−1) of formaldehyde were calculated.  相似文献   

13.
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   

14.
Here, we report a simple and extremely effective method to modify a glassy carbon (GC) electrode with carbon nanotubes (CNTs) and [Mn(CH3COO)(CH3OH)2(pyterpy)]ClO4, (pyterpy = 4′-(4-pyridyl)-2,2′:6′,2′′-terpyridine) complex. The kinetics of the reaction between, the terpyridine manganese(II) complex, mediator and hydrazine has been characterized using cyclic voltammetry and rotating disk electrode voltammetry. The catalytic currents were proportional to the concentration of hydrazine giving rise to calibration curves characterized by two linear segments. The linear segment over the concentration range of 1.00 × 10−3–1.05 mM could be used with analytical purposes to determination of hydrazine with a detection limit of 0.50 μM and a sensitivity of 0.038 μA/μM. The heterogeneous rate constant, k′ for the oxidation of hydrazine at the surface of the modified electrode was determined by rotating disk electrode voltammetry using the Koutecky–Levich plot. The transfer coefficient (α) for electrocatalytic oxidation of hydrazine and the diffusion coefficient of this substance under the experimental conditions were also investigated. The resulting modified electrode retains its initial response for at least one month if stored dry in air.  相似文献   

15.
Electrochemistry of cytochrome c (cyt c) at biomimetic phospholipid layers was studied in a phosphate buffer solution, which were formed with dilauroyl phosphatidic acid (DLPA, C12:0), dipalmitoyl phosphatidic acid (DPPA, C16:0), distearoyl phosphatidic acid (DSPA, C18:0), and palmitoyl–oleoyl phosphatidic acid (POPA, C16:0–18:1). The lipid-layers formed firstly at the air/water interface were immediately transferred onto the electrode surface using the Langmuir–Blodgett (LB) technique. The electrochemical properties of cyt c at the lipid covered electrodes depended on the orientation, number of layers of phospholipids, tail (or head) group down, and vice versa. Atomic force microscopy (AFM) images of cyt c adsorbed on the POPA monolayer (showing the head group diameter of POPA to be ca. 0.7 nm) formed on highly oriented pyrolytic graphite (HOPG) displayed uniform surface morphology of lipid layer and clumps of aggregated cyt c molecules with a minimum size corresponding to four cyt c molecules. The heterogeneous electron transfer rate constants, k0 values, of cyt c were determined to be 1.02 × 10−3, 0.98 × 10−3, and 0.67 × 10−3 cm/s for the lipid monolayer in the tail down orientation (X-type) of POPA, DLPA, and DPPA, and 0.67 × 10−3 and 0.50 × 10−3 cm/s for the head down orientation (Z-type) of POPA and DLPA monolayers, respectively.  相似文献   

16.
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   

17.

Objective

To develop polymeric hydrogel delivery systems for iontophorseis transfer of large molecules across buccal (porcine) mucosa.

Methods

Three hydrogels (PVA, HPMC and PVA/HPMC) were prepared as stable gels (7 mm diameter/1.5 mm thick). Quantitative (8 and 36 h) assessment of porcine buccal mucosa and the three hydrogel delivery systems, using a diffusion cell in vitro model, was carried out by UV/vis spectroscopy with three model agents (3 and 10 kDa dextrans and 12 kDa parvalbumin). Passive and iontophoresis parameters were obtained. Experimental and theoretical data were compared.

Results

Iontophoresis (30 min, 1–8 h) significantly enhanced the delivery of all model agents across four single systems (hydrogels and buccal mucosa) and three sandwich systems (hydrogels on top of buccal mucosa), as confirmed by time lag factor/enhancement ratio (TLF/ER) data. The diffusion coefficients of model agents across buccal mucosa (×10−13 m2 s−1) were ∼100 times lower than across single hydrogels (2.97–4.80 × 10−11 m2 s−1). Solubility values of all agents across hydrogels were similar, but lower across buccal mucosa. Permeability of parvalbumin was highest across PVA, and for both dextrans across PVA/HPMC. In sandwich systems TLFs were similar for all hydrogels, but significantly lower, and ERs significantly higher, than tissue alone. Experimental and theoretical TLF data were in reasonable agreement.

Significance

The in vitro data show that iontophoresis enhanced the delivery of large molecules across polymeric hydrogel systems and buccal mucosa. This creates the opportunity of new approaches to drug delivery and opens pathways to further research for delivering therapeutic agents topically and systemically.  相似文献   

18.
The phase-boundary potential between the moderately hydrophobic ionic liquid and a low ionic strength aqueous solution is demonstrated to be stable and constant with the standard deviation of 0.4 mV down to 20 μmol kg−1 HBr, LiBr, and KBr solutions, for three ionic liquids that consist of either N-methyl-N-octylpyrrolidinium, N-heptyl-N-methylpyrrolidinium, or N-hexyl-N-methylpyrrolidinium and a common anion species, bis(pentafluoroethanesulfonyl)amide. This stability is promising for accurate measurements of pH of low ionic strength samples and reliable estimates of single ion activities in general. The phase-boundary potential deviates from the value determined by the partition of the ionic liquid in further dilute aqueous solutions. The magnitude of the deviation ranges from 3 to 11 mV at 5 μmol kg−1 MBr (M is H+, Li+, or K+). The solubility of these ionic liquids in water is 0.2 mmol dm−3 at most at 25 °C, which is another advantage of ionic liquid salt bridge in electroanalytical chemistry.  相似文献   

19.
A sensitive and selective method for determination of dopamine (DA) using multi-wall carbon nanotube (MWCNT)-poly(3,5-dihydroxy benzoic acid) [poly(DBA)] modified electrode is developed. The modified electrode shows excellent electrocatalytic activity toward the oxidation of dopamine in phosphate buffer solutions at pH 7.4. Using cyclic voltammetry, the linear range of 1 × 10−7–7.0 × 10−5 M in the interference of 500 μM ascorbic acid (AA) and the detection limit of 1.0 × 10−8 M were estimated for the measurement of DA in pH 7.4 phosphate buffer solutions. The value of DA current retained 98.36% of the initial response current after the modified electrode exposed to the air for one week. The interference studies showed that the modified electrode excludes effectively large excess of AA. The kinetic characteristics of the transfer of DA demonstrated that the electron propagation between DA and electrode was accelerated at MWCNT-poly(DBA) modified electrode. The work provided a valid and simple approach to selectively detect dopamine in the presence of AA in physiological environment.  相似文献   

20.
Amperometric gas sensor of arsine was developed using gold-modified diamond electrodes as the working electrodes. The detection method was conducted in high concentration of H2SO4. The reaction was declared based on two oxidation steps, involving oxidation of As3− to As0 at mild potential in strong acid, followed by electrochemical oxidation of As0 to As3+ at gold-based electrodes. Linear calibration curve was observed in the concentration range of 5–50 ppb (r2 = 0.985) with detection limit of ∼4.43 ppb (S/N = 3). Current decreasing of measurement was found ∼5.5% for 5 measurements. However, better stability was observed after the 5th measurement, indicated that the sensor could be applied for long time measurement. Investigation to several possible interference gasses, i.e. SO2, H2S, NO, NO2, CO, O3 and H2 indicated no significant interference of the gas to arsine measurements.  相似文献   

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