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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.
Haemoglobin (Hb) modified electrochemical devices have been prepared by Hb encapsulation in silica sol–gel films (SiO2), which were generated by electro-assisted deposition onto pyrolitic graphite electrodes (PGEs). The stability and electrocatalytic activity of Hb entrapped into SiO2 network was substantially enhanced in the presence of cationic surfactant (CTAB) and Au nanoparticles (Au-NPs). The composition of sol–gel synthesis medium, i.e., molar ratio of silica precursor to water, contents of Hb, CTAB and Au-NPs, as well as the conditions of electrogeneration had a great influence on the electrocatalytic activity of Hb on PGE surface. The electrochemical response of the PGE modified with the composite SiO2–Hb–CTAB–Au-NPs film was found to vary linearly with the concentration of dissolved oxygen in solution and this was exploited to determine this analyte in the tap water with detection limit 0.12 mg L−1. The electrocatalytic current of dissolved oxygen was also found to decrease in the presence of the antivirus drug––amino derivative of adamantane (rimantadine)––which opens the way to the determination of this drug with detection limit 0.3 mg L−1 using PGE modified with SiO2–Hb–CTAB–Au-NPs nanocomposite film.  相似文献   

3.
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   

4.
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   

5.
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   

6.
The electro-oxidation mechanism of trace amounts of sodium hypochlorite (<4.0 mg Cl dm−3) in an aqueous medium has been studied by employing the potential sweep method and double-potential step chronocoulometry. These methods confirmed the occurrence of the competition reaction of the Faradaic-based hypochlorite and the non-Faradaic-based formation of platinum oxide. In the hypochlorite-free solution, the amount of platinum oxide formed during the non-Faradaic reaction was approximately 1.3 pmol cm−2; however, with an increase in the amount of sodium hypochlorite, the amount of platinum oxide gradually decreased to approximately 0.2 pmol cm−2. The results of this study suggest that the electro-oxidation of trace amounts of hypochlorite, particularly amounts less than 1.0 mg Cl dm−3, is strongly inhibited by the initial formation of platinum oxide in a non-Faradaic reaction.  相似文献   

7.

Objectives

This work is concerned with the study of the sorption and desorption process of water, ethanol or ethanol/water solution 50% (v/v) or 75% (v/v) by the dental resins prepared by light curing of Bis-GMA, Bis-EMA, UDMA, TEGDMA or D3MA.

Methods

A thin resin disc is placed in a bath of time to obtain the sorption curve mt = f(t). Then the liquid is desorbed until a constant mass for the disc is reached and the desorption curve is recorded. These experimental curves help in the determination of the sorbed/desorbed liquid amount at equilibrium, the percentage of the extracted mass of unreacted monomer known as “solubility”, and the sorption/desorption diffusion coefficient which expresses correspondingly the rate of the liquid sorption/desorption.

Results

The highest liquid uptake by dental resins was 13.3 wt% ethanol for Bis-GMA-resin, 12.0 wt% ethanol for UDMA-resin, 10.10 wt% ethanol/water solution for TEGDMA-resin, 7.34 wt% ethanol for D3MA-resin and 6.61 wt% ethanol for Bis-EMA-resin. The diffusion coefficient for all resins was higher in water than in ethanol/water solution or ethanol. Bis-GMA-resin showed the highest diffusion coefficient (11.01 × 10−8 cm2 s−1) followed by Bis-EMA-resin (7.43 × 10−8 cm2 s−1), UDMA-resin (6.88 × 10−8 cm2 s−1), D3MA-resin (6.22 × 10−8 cm2 s−1) and finally by TEGDMA-resin (1.52 × 10−8 cm2 s−1).

Significance

All studied dental resins, except TEGDMA-resin, absorbed higher amount of pure ethanol than water or ethanol water solution. TEGDMA-resin absorbed higher amount of ethanol/water solution (50/50 or 75/25 (v/v)) than water or ethanol. For all studied dental resins the diffusion coefficient was higher in water than in ethanol/water solution or ethanol.  相似文献   

8.
A highly sensitive voltammetric detection of silicic acid (SA), the main chemical species of dissolved silica in sea water, is described. The protocol relies on a fast square-wave voltammetric measurement of the decreased molybdenum stripping signal due to the formation of silicomolybdate complex. The cathodic stripping experiments were performed at the bismuth film electrode using HCl–KCl (pH 1.6) buffer solution. Different ligands, pH, ligand concentration, deposition potential and accumulation time were evaluated. Under the optimal conditions, a linear response is observed over the 50–400 μg L−1 SA concentration range with a detection limit of 2 μg L−1. A highly stable response, with a relative standard deviation (RSD) of 4.8%, is observed for 10 repetitive measurements. Such an electrochemical approach offers great promise for a simple, rapid, sensitive, and on-site or in situ real-time detection of SA.  相似文献   

9.
Manganese oxides nanoparticles were chemically deposited on a high area (ca. 300 m2 g−1) carbon black substrate to act as electrocatalysts for oxygen reduction. The morphology and chemistry of the carbon-supported MnOx nanoparticles was characterised by Transmission Electron Microscopy), X-ray Diffraction, and chemical analysis. The oxygen reduction reaction (ORR) catalytic activity was studied in the 7–10 pH range using a rotating disk electrode (RDE). High activity towards oxygen reduction and very good stability in neutral and slightly basic solution were obtained. At low current densities, at 25 °C, MnOx/C displayed a reaction order with respect to OH ions of −0.5 and Tafel slopes of −0.153 and −0.167 V dec−1 at pH 7 and 10 respectively; showing that the ORR mechanism on MnOx/C is unchanged in the 7–10 pH range. From the data, we propose that the first electrochemical step of the 4-electron ORR mechanism, in the 7–10 pH range, is the quasi equilibrium proton insertion process in MnO2 yielding MnOOH (insoluble in neutral or slightly basic solution). The ORR activity of the MnOx/C materials increased with increasing temperatures from 5 to 40 °C. The 2-electron pathway of oxygen reduction, yielding hydrogen peroxides as intermediates, may however be favoured over the 4-electron O2 reduction at higher temperatures.  相似文献   

10.
The nano composited film of indigotetrasulfonate (ITS) electrodeposited onto poly-l-lysine (PLL)–glutaraldehyde (GA) (ITS/PLL–GA) was modified on glassy carbon electrode (GCE) by multiple scan cyclic voltammetry. Composited of the proposed film was characterized by atomic force microscopy (AFM), scanning electron microscopy (SEM), electrochemical quartz crystal microbalance (EQCM), electrochemical impedance spectroscopy (EIS), and UV–vis spectrum for the absorption at λmax at 566 nm. For the electrocatalytic reduction of dissolved oxygen, ITS/PLL–GA film modified electrodes was determined in 0.1 M acetate buffer solution (pH 5.6) by cyclic voltammetry and rotating disk electrode voltammetry. This dissolved oxygen electrochemical sensor exhibited a linear response range (from 0 to 178.4 μM, R2 = 0.9949), lowest detection limit (2.2 μM), lowest overpotential at −0.09 V, high sensitivity (906 μA mM−1) and relative standard deviation (RSD) for determining dissolved oxygen (n = 3) was 4.2%. In addition, the ITS/PLL–GA/GCE was advantageous in terms of its simple preparation, specificity, stability and the ability of regeneration.  相似文献   

11.
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   

12.
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   

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.
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   

15.
We report in this work, for the first time, the results obtained from both Pitzer, Pitzer–Simonson–Clegg (PSC) and an extended PSC ion-interaction approaches for modeling the non-ideal behavior of HCl electrolyte in the mixed ethanol + water solvent systems. In this context, a review of literature shows that the use of an exact and complete form of PSC ion-interaction approach for modeling electrolyte in mixed solvent systems was only limited to the works of two research groups. In this work, the modeling purposes were achieved based on the experimental potentiometric data of a galvanic cell containing a pH glass membrane and Ag/AgCl electrodes. The measurements were achieved over the HCl electrolyte molality ranging from 0.02 up to about 5 mol kg−1 in mixed ethanol (x%) + water (100 − x%) solvent with different solvent mass fractions percent (x% = 10%, 20%, 30%, 40% and 50%), at 298.15 ± 0.05 K.  相似文献   

16.
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   

17.
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   

18.
The inhibitive action of urea on the corrosion behavior of copper was investigated in borate buffer pH (8.4) by means of cyclic voltammetry and electrochemical impedance spectroscopy (EIS). A consistent trend of increase in inhibition efficiency was observed as a function of concentration of urea. The adsorption of urea on copper surface was found to obey the Langmuir adsorption isotherm with ΔG = −35.2 kJ/mole and adsorption constant K = 2.7 × 104 dm3/mole. Impedance spectroscopic measurements confirmed that charge transfer resistance increases in presence of urea upon increasing its concentration.  相似文献   

19.
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   

20.
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   

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