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1.
A voltammetric study of the oxidation of Ceftazidime (CEFT) has been carried out at the glassy carbon electrode by cyclic, differential pulse (DPV) and square wave (SWV) voltammetry. The oxidation of CEFT was irreversible and exhibited diffusion controlled process depending on pH. The oxidation mechanism was proposed and discussed. According to the linear relationship between the peak current and concentration, DPV and SWV voltammetric methods for CEFT assay in pharmaceutical dosage forms and human urine were developed. For analytical purposes, a well resolved diffusion controlled voltammetric peak was obtained in 0.1 M H2SO4 at 1.00 and 1.02 V for differential pulse and square wave voltammetric techniques, respectively. The linear response was obtained within the range of 4 × 10?6?8 × 10?5 M with a detection limit of 6 × 10?7 M for differential pulse and 4 × 10?6–2 × 10?4 M with a detection limit of 1 × 10?6 M for square wave voltammetric technique. The determination of CEFT in 0.1 M H2SO4 was possible over the 2 × 10?6–1 × 10?4 M range in urine sample for both techniques. The standard addition method was used for the recovery studies.  相似文献   

2.
《Electroanalysis》2004,16(10):860-865
The electrocatalytic oxidation of sulfite has been studied on the cobalt pentacyanonitrosylferrate modified glassy carbon electrode (CoPCNF). The CoPCNF films on the glassy carbon electrodes show an excellent electrocatalytic activity toward the oxidation of sulfite in 0.5 M KNO3. The kinetics of the catalytic reaction was investigated by using cyclic voltammetry, rotating disk electrode (RDE) voltammetry and chronoamperometry. The average value of the rate constant, K, for the catalytic reaction and the diffusion coefficient, D, were evaluated by different approaches for sulfite and found to be 2.9×102 M?1s?1 and 4.6×10?6 cm2s?1, respectively. At a fixed potential under hydrodynamic conditions (stirred solutions), the oxidation current is proportional to the sulfite concentration and the calibration plot was linear over the concentration range 5×10?6–1×10?4 M. The detection limit of the method is 3×10?6 M., low enough for the trace sulfite determination.  相似文献   

3.
《Analytical letters》2012,45(12):1913-1931
Abstract

A voltammetric study of the oxidation of fexofenadine HCl (FEXO) has been carried out at the glassy carbon electrode. The electrochemical oxidation of FEXO was investigated by cyclic, linear sweep, differential pulse (DPV), and square wave (SWV) voltammetry using glassy carbon electrode. The oxidation of FEXO was irreversible and exhibited diffusion‐controlled process depending on pH. The dependence of intensities of currents and potentials on pH, concentration, scan rate, nature of the buffer was investigated. Different parameters were tested to optimize the conditions for the determination of FEXO. For analytical purposes, a very well resolved diffusion‐controlled voltammetric peak was obtained in Britton‐Robinson buffer at pH 7.0 with 20% constant amount of methanol for DPV and SWV techniques. The linear response was obtained in supporting electrolyte in the ranges of 1.0×10?6–2.0×10?4 M with a detection limit of 6.6×10?9 M and 5.76×10?8 M and in serum samples in the ranges of 2.0×10?6–1.0×10?4 M with a detection limit of 8.08×10?8 M and 4.97×10?8 M for differential pulse and square wave voltammetric techniques, respectively. Only square wave voltammetric technique can be applied to the urine samples, and the linearity was obtained in the ranges of 2.0×10?6–1.0×10?4 M with a detection limit of 2.00×10?7 M. Based on this study, simple, rapid, selective and sensitive two voltammetric methods were developed for the determination of FEXO in dosage forms and biological fluids. For the precision and accuracy of the developed methods, recovery studies were used. The standard addition method was used for the recovery studies. No electroactive interferences were found in biological fluids from the endogenous substances and additives present in tablets.  相似文献   

4.
The fluorescence quenching of polystyrene by oxygen at room temperature was investigated. The diffusion coefficient of oxygen in polystyrene films was taken as 3.1 × 10?7 cm2/sec; the energy migration coefficient of polystyrene in the excited singlet state was estimated as 6 × 10?6 cm2/sec.  相似文献   

5.
Poly(p-phenylene biphenyltetracarboximide) films with various thicknesses were prepared from the poly(amic acid) precursor by thermal imidization at 230–400°C for 1–10 h under a nitrogen atmosphere. The water sorption in the films was measured at 25°C over 22–100% relative humidity using a Cahn microbalance as a function of film thickness and thermal imidization history. The water diffusion in all the films followed nearly Fickian process despite the morphological heterogeneity due to the ordered and less ordered phases. The diffusion coefficient and water uptake varied in 0.85 × 10?10 ? 7.50 × 10?10 cm2/s and 0.12–2.4 wt %, respectively, depending upon humidity, film thickness, and imidization history. Both diffusion coefficient and water uptake increased with increasing humidity, but decreased as imidization temperature and time increased. With increasing film thickness, the diffusion coefficient increased whereas the water uptake decreased. The water sorption behavior was interpreted with the consideration of morphological variations, such as polymer chain order, in-plane orientation, and intermolecular packing order due to the film thickness and imidization history. © 1995 John Wiley & Sons, Inc.  相似文献   

6.
Polydimethylsiloxane (PDMS) networks having strands of molecular weight in the range 11,000–36,000 have been prepared by endlinking linear PDMS molecules of these molecular weights with a tetrafunctional linking agent. Absorption of a series of homologous linear PDMS molecules by the resulting PDMS networks has been investigated. The diffusion coefficients at 70°C were found to be rather large, 1 × 10?12–6 × 10?12 m2/s, and approximately inversely proportional to the molecular weight of the diffusing liquid, over the range 5000–38,000. The amount of liquid absorbed at equilibrium was relatively small, 10–80%, in good agreement in all cases with an especially simple version of the Flory–Huggins theory when the heat of mixing is made vanishingly small and only entropic terms are retained.  相似文献   

7.
刘佩芳  文利柏 《中国化学》1998,16(3):234-242
The mass transport and charge transfer kinetics of ozone reduction at Nafion coated Au electrodes were studied in 0.5 mol/L H2SO4 and highly resistive solutions such as distilled water and tap water. The diffusion coefficient and partition coefficient of ozone in Nafion coating are 1.78×10-6 cm2·s-1 and 2.75 at 25℃ (based on dry state thickness), respectively. The heterogeneous rate constants and Tafel slopes for ozone reduction at bare Au are 4.1×10-6 cm·s-1, 1.0×10-6 cm·s-1 and 181 mV, 207 mV in 0.5 mol/L H2SO4 and distilled water respectively and the corresponding values for Nafion coated Au are 5.5×10-6 cm·s-1, 1.1×10-6 cm·s-1 and 182 mV, 168 mV respectively. The Au microelectrode with 3 μm Nafion coating shows good linearity over the range 0-10 mmol/L ozone in distilled water with sensitivity 61 μA·ppm-1 ·cm-2, detection limit 10 ppb and 95% response time below 5 s at 25℃. The temperature coefficient in range of 11-30℃ is 1.3%.  相似文献   

8.
Using laser interferometry, we have determined in situ the thickness increase with time of thin supported polyimide films (4–8 μm in initial thickness) immersed in n-methyl-2-pyrrolidone (NMP) as a function of NMP temperature (22–120°C). Similar experiments were also performed in dimethyl sulfoxide (DMSO) at 22°C with polyimide films of 4.1 μm in thickness. For NMP, the equilibrium fractional thickness increase (about 20%) is independent of initial polyimide thickness and temperature. The time scale for reaching equilibrium sharply decreases with temperature from 2–3 days at 22°C to 30–60 min at 120°C. Compared with NMP, the rate of DMSO sorption is considerably faster, reaching equilibrium swelling of about 28% in about 5 h at 22°C. To describe the transport process, we applied a phenomenological model proposed by Astarita and Sarti1 but reformulated in polymer fixed frame to enable straightforward comparison with the thickness data. Our analysis indicated that the transport of NMP is best described as anomalous, that is, intermediate between diffusion controlled and case II transport. The effective diffusion coefficient Deff and the front velocity U0 at 22°C were found to be 3–6 × 10?12 cm2/s and 8 × 10?9 cm/s, respectively. Our front velocity is in good accord with the value of 6 × 10?9 cm/s obtained for a similar polyimide based on gravimetric measurements.2 Both Deff and U0 show an activation energy of ~56 kJ/mol. For DMSO, however, the transport is clearly case II. The front velocity at 22°C was found to be about 6 × 10?8 cm/s, which is about four times that obtained by Rutherford back-scattering spectrometry.3  相似文献   

9.
《Analytical letters》2012,45(12):2171-2185
Abstract

The electrooxidative behavior of citalopram (CTL) in aqueous media was studied by cyclic voltammetry (CV) and square-wave voltammetry (SWV) at a glassy-carbon electrode. The electrochemical behaviour of CTL involves two electrons and two protons in the irreversible and diffusion controlled oxidation of the tertiary amine group. The maximum analytical signal was obtained in a phosphate buffer (pH = 8.2). For analytical purposes, an SWV method and a flow-injection analysis (FIA) system with amperometric detection were developed. The optimised SWV method showed a linear range between 1.10 × 10?5–1.20 × 10?4 mol L?1, with a limit of detection (LOD) of 9.5 × 10?6 mol L?1. Using the FIA method, a linear range between 2.00 × 10?6–9.00 × 10?5 mol L?1 and an LOD of 1.9 × 10?6 mol L?1 were obtained. The validation of both methods revealed good performance characteristics confirming applicability for the quantification of CTL in several pharmaceutical products.  相似文献   

10.
Abstract

The synthesis and characterization of peripherally 2′,3′,5′,6′-tetrafluoro-4′-pentoxy-benzyloxy-substituted metal-free and metallo (Zn(II) and Co(II)) phthalocyanines are described in this study. Aggregation properties of these phthalocyanines were studied in the concentration range of 1 × 10?5?1 × 10?6 M in tetrahydrofuran. Thin films of phthalocyanines were prepared by spin-coating technique. The spectrophotometric measurements of transmittance spectra were carried out in the wavelength range of 200–1000 nm. Optical band gaps of phthalocyanine thin films were also calculated. Surface morphologies and thickness of the films were examined by Scanning Electron Microscopy. Results show that film thickness can be changed significantly depending on the type of metal in the phthalocyanine.  相似文献   

11.
For polyimide thin films, the dielectric properties were investigated with the capacitance and optical methods. The dielectric constants of the 4,4′‐oxydianiline (ODA)‐based polyimide thin films varied from 2.49 to 3.10 and were in the following decreasing order: 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA)–ODA > 1,2,4,5‐benzenetetracarboxylic dianhydride (PMDA)–ODA > 4,4′‐hexafluoroisopropylidene diphthalic dianhydride (6FDA)–ODA. According to the absorption of water, the diffusion coefficients in the films varied from 4.8 × 10?10 to 7.2 × 10?10 cm2/s and were in the following increasing order: BPDA–ODA < PMDA–ODA < 6FDA–ODA. The dielectric constants and diffusion coefficients of the polyimides were affected by the morphological structures, including the molecular packing order. However, because of the water uptake, the changes in the dielectric constants in the polyimide thin films varied from 0.49 to 1.01 and were in the following increasing order: BPDA–ODA < 6FDA–ODA < PMDA–ODA. Surprisingly, 6FDA–ODA with bulky hexafluoroisopropylidene groups showed less of a change in its dielectric constant than PMDA–ODA. The total water uptake for the polyimide thin films varied from 1.43 to 3.19 wt % and was in the following increasing order: BPDA–ODA < 6FDA–ODA < PMDA–ODA. This means that the changes in the dielectric constants in the polyimide thin films were significantly related to the morphological structure and hydrophobicity of hexafluoroisopropylidene groups. Therefore, the morphological structure and chemical affinity in the polyimide thin films were important factors in controlling the dielectric properties. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2190–2198, 2002  相似文献   

12.
The complexation of thiabendazole (TBZ) with the cucurbit[6]uril (Q[6]), cucurbit[7]uril (Q[7]) and symmetric tetramethyl-cucurbit[6]uril (TMeQ[6]) in aqueous solution has been investigated using UV–vis and fluorespectrometry. The experimental results show 1:1 host–guest inclusion complexes at pH 6.5 for all three macrocyclic hosts, and the corresponding formation constants by UV and fluorescence methods are (5.37?±?1.05)?×?104?L?mol?1 and (1.47?±?0.41)?×?104?L?mol?1 for the Q[6]-TBZ system (7.76?±?0.51)?×?104?L?mol?1 and (9.36?±?0.22)?×?104?L?mol?1 for the Q[7]-TBZ system (1.28?±?0.78)?×?104?L?mol?1 and (2.69?±?0.55)?×?104?L?mol?1 for the TMeQ[6]-TBZ system, respectively. Based on the enhancement of the fluorescence intensity of TBZ with the addition of Q[n]s in neutral media, a fluorespectrometry method for the determination of TBZ in aqueous solution in the presence of Q[n] was established. In the range of 6.0?×?10?8?mol?L?1–8.0?×?10?6?mol?L?1 a linear relationship was obtained between fluorescence intensity and TBZ concentration. The detection limit was found to be between 5.51 and 8.85?×?10?9?mol?L?1. The interference of coexisting ions was found to be slight. The proposed method has been successfully applied to the determination of TBZ in different aqueous solutions with satisfactory recoveries of 92–103%. The method seems to be suitable for environmental water analysis.  相似文献   

13.
The microstructural and electrochemical properties of rf-sputtered LiMn2O4 films were investigated as a function of post-deposition process. The degree of crystallization in the films gradually increased with the increase of annealing temperature (T a). The films annealed at T a?=?973 K exhibited characteristic peaks with predominant (111) orientation representing the cubic spinel structure of Fd3m symmetry. The estimated Mn–Mn and Mn–O distances obtained from the X-ray diffraction data were observed to be increased slightly with T a. Characteristic changes in surface morphological features were observed as a function of T a as evidenced from scanning electron microscopy. The estimated root mean square (RMS) roughness of the films increased from 97 to 161 nm with augmentation of T a. The electrochemical studies, viz. cyclic voltammetry (CV), specific discharge capacity and Li ion diffusion coefficient were carried out for annealed LiMn2O4 films in saturated aqueous electrolyte (Li2SO4) in the potential window of 0–1.2 V and correlated with surface morphology and grain size. The LiMn2O4 films annealed at T a?=?973 K exhibited better electrochemical performance and demonstrated a discharge capacity of about 53.5 μA h cm?2 μm?1 with diffusion coefficient of 1.2?×?10?13 cm2 s?1.  相似文献   

14.
Carbon-coated Na3V2(PO4)3 (NVP) was prepared by a standard sol–gel procedure. The apparent diffusion coefficients of sodium ions in the rhombohedral NVP have been determined by different techniques such as galvanostatic intermittent titration technique (GITT) and cyclic voltammetry (CV). It was found that the apparent diffusion coefficients range from 6?×?10?13 cm2 s?1 to 2?×?10?15 cm2 s-1. These sodium ion apparent diffusion coefficients follow a similar trend as observed for lithium ions in the closely related monoclinic modification of Li3V2(PO4)3, demonstrating a minimum at the potential where the ion extraction/insertion occurs.  相似文献   

15.
The electrooxidation of dextromethorphan on a composite constructed with carbon nanotube–ionic liquid–carbon microparticles was investigated by cyclic voltammetry in a 100 mM phosphate buffer solution, pH 7.40. In the voltammograms, an irreversible diffusion-controlled anodic peak appeared. The diffusion coefficient of dextromethorphan, the electron-transfer coefficient, and the standard rate constant of the electrooxidation process were found to be 3.45?×?10?6 cm2 s?1, 0.65, and 1.67?×?10?3 cm s?1, respectively. A sensitive and timesaving determination procedure was developed for the analysis of dextromethorphan, and the corresponding analytical parameters were reported. Using this method, dextromethorphan was determined with an LOD and LOQ of 8.81 and 29.36 μM in a linear range of 2.5?×?10?4 to 3.3?×?10?3 M, respectively. The proposed amperometric method was successfully applied to the analysis of commercial pharmaceutical products (syrup and oral drop), and the results were in good agreement with the declared values.  相似文献   

16.
An amperometric pesticides inhibition biosensor has been developed and used for determination of pesticides in vegetable samples. To eliminate the interference of ascorbic acid, multilayer films of polyelectrolyte (chitosan/polystyrensulfonate) were coated on the glass carbon electrode. Then, acetylcholinesterase was immobilized on the electrode based on surface-treated nanoporous ZrO2/chitosan composite film as immobilization matrix. As a modified substrate, acetylthiocholine was hydrolysed by acetylcholinesterase and produced thiocholine which can be oxidized at +700?mV vs. SCE. Pesticides inhibit the activity of enzyme with an effect of decreasing of oxidation current. The experimental conditions were optimized. The electrode has a linear response to acetylthiocholine within 9.90?×?10?6 to 2.03?×?10?3?M. The electrode provided a linear response over a concentration range of 6.6?×?10?6 to 4.4?×?10?4?M for phoxim with a detection limit of 1.3?×?10?6?M, over a range of 1.0?×?10?8 to 5.9?×?10?7?M for malathion, and over a range of 8.6?×?10?6 to 5.2?×?10?4?M for dimethoate. This biosensor has been used to determine pesticides in a real vegetable sample.  相似文献   

17.
To improve the oil absorbency of caster oil‐based polyurethane foam, nano‐organic‐montmorillonite (OMMT) was used for the additives. The aim of this study is to evaluate the oil diffusion mechanism and dispersion uniformity of OMMT modified caster oil‐based polyurethane (MPU) using experiments and molecular dynamic simulation. Molecule movement and molecule trajectory of oil was investigated by molecular dynamic simulation and numerical simulation. According to the quantitative analyzing results, the diffusion model was put forward. The average diffusion coefficient of crude oil in 0, 1, 2 wt%, 4, and 6 wt% MPU is 2.4 × 10?4 cm2/s, 2.6 × 10?4 cm2/s, 3.0 × 10?4 cm2/s, 3.2 × 10?4 cm2/s, and 3.3 × 10?4 cm2/s, respectively. It indicated that crude oil appeared gradient in the MPU. The optimal diffusion direction of crude oil is (0, 0, 1) crystal face, and the small particles of crude oil are easy to be adsorbed. The two‐dimensional diffusion trajectory of crude oil is nonlinear. The diffusion model includes the diffusion of crude oil at the interface of oil and polyurethane, surface diffusion and pore diffusion, and pore adsorption. Furthermore, the diffusion model showed that the van der Waals force was the main reason for crude oil diffusion or adsorption. OMMT could improve the ability of oil/water separation of polyurethane.  相似文献   

18.
The radiation-induced grafting of styrene vapor to low-density polyethylene film of 0.063 mm thickness was studied at 23°C at a dose rate of 1.98 × 104 rad/hr. The concentration C of monomer in the film was measured as a function of pre-irradiation exposure time to monomer vapor. The concentration-dependent diffusion coefficient of styrene in polyethylene was calculated to be 4.9 × 10?9 exp {2.0C/C0} cm2/sec, where C0 is the saturation concentration of styrene in the film, and a linear boundary diffusion coefficient for styrene vapor into polyethylene film was found to be 2.0 × 10?7 cm/sec. The rate of grafting was determined as a function of the concentration of styrene absorbed in the film. The maximum graft yield was obtained with an initial styrene concentration in the film of 4 wt-%. Under conditions of low initial monomer concentration, the grafting rate increases with irradiation time. The results are compared with previously published data on grafting of polyethylene from methanol–styrene solutions. They are explained in terms of the viscosity of the amorphous region as a function of styrene content and the resistance to the diffusion of monomer at the film–vapor interface.  相似文献   

19.
Novel films consisting of multi-walled carbon nanotubes (MWCNTs) were fabricated by means of chemical vapor deposition with decomposition of either acetonitrile (ACN) or benzene (BZ) using ferrocene as catalyst. The electrochemical responses of MWCNT-based films towards the ferrocyanide/ferricyanide, [Fe(CN)6]3?/4? redox couple were probed by means of cyclic voltammetry and electrochemical impedance spectroscopy at 25.0?±?0.5?°C. Both MWCNT-based films exhibit Nernstian response towards [Fe(CN)6]3?/4? with some slight kinetic differences. Namely, heterogeneous electron transfer rate constants lying in ranges of 2.69?×?10?2?C1.7?×?10?3 and 9.0?×?10?3?C2.6?×?10?3?cm·s?1 were obtained at v?=?0.05?V·s?1 for MWCNTACN and MWCNTBZ, respectively. The detection limit of MWCNTACN, estimated to be about 4.70?×?10?7?mol·L?1 at v?=?0.05?V·s?1, tends to become slightly poorer with the increase of the scan rate, namely at v?=?0.10?V·s?1 the detection limit of 1.70?×?10?6?mol·L?1 was determined. Slightly poorer response ability was exhibited by MWCNTBZ; specifically the detection limits of 1.57?×?10?6 and 4.35?×?10?6?mol·L?1 were determined at v?=?0.05 and v?=?0.10?V·s?1, respectively. The sensitivities of MWCNTACN and MWCNTBZ towards [Fe(CN)6]3?/4? were determined as 1.60?×?10?7 and 1.51?×?10?7?A·L·mol?1·cm?2, respectively. The excellent electrochemical performance of MWCNTACN is attributed to the presence of incorporated nitrogen in the nanotube??s structure.  相似文献   

20.
《Analytical letters》2012,45(12):1869-1885
Abstract

A glassy carbon electrode surface was modified with an electropolymerized film made of pyrrole and β‐cyclodextrin 1∶1, in a 0.1 M LiClO4 solution using cyclic voltammetry. The resulting modified electrode (Ppy/β‐CD) exhibits interesting electrocatalytic activity toward the electrochemical oxidation of neurotransmitters such as dopamine (DA) and norepinephrine (NE). Well‐resolved and reversible cyclic voltammograms (CVs) were obtained for these organic compounds in a 0.1 M H2SO4 solution. The effect of the pH on the voltammetric response of DA and NE was also investigated inside the range of pH 2.8–8.4. The oxidation current of norepinephrine increase linearly with the concentration inside the range of 4×10?7 M–2×10?6 M. The oxidation current of dopamine also followed the same trend range of 2×10?6 M–10?5 M. The detection limit was 6×10?6 M for (DA) and 8×10?7 M for (NE). As an example, the relative standard deviation for 1×10?5 M of DA was 2.056%. The diffusion coefficients D for the molecules studied were determined by means of the measurement of the effect of the scan rate on the CVs of the neurotransmitters. All the results showed that the electron transfer was predominantly diffusion controlled at the conducting polymer/solution interface.

Interference phenomenon due to ascorbic acid (AA) toward the neurotransmitters was also investigated. The novel modified electrodes presented capability to resolve perfectly the AA and neurotransmitters oxidation peaks. This performance could be achieved even at a concentration 20 times higher than the neurotransmitters.

Finally, the newly fabricated Ppy/β‐CD film exhibits interesting analytical performances compared with other systems in the literature, such as higher sensitivity, rapid response, good mechanical stability and reproducibility.  相似文献   

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