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1.
《Electroanalysis》2002,14(24):1728-1732
An electrochemical study related to the electrooxidation of 4‐amino‐3‐thio‐5‐methyl‐1,2,4‐triazole (I), 4‐amino‐3‐thio‐5‐phenyl‐1,2,4‐triazole (II) and 3‐thio‐5‐phenyl‐1,2,4‐triazole (III), in 10% v/v methanol‐acetate buffer pH 4.6 has been performed. A variety of electrochemical techniques such as differential pulse voltammetry, cyclic voltammetry, double‐potential step chronoamperometry, rotating‐disk electrode voltammetry and coulometry, were employed to clarify that the mechanism of the electrode process follows the oxidation of thiol compounds. All the compounds exhibit similar redox behavior under the given conditions. They display one irreversible oxidation peak, which is diffusion controlled. From the plot of current function in cyclic voltammetry and the ratio of ic/ia less than one in double‐potential step chronoamperometry, it was established that these compounds undergo an one electron oxidation followed by a dimerization process involving the formation of disulfide derivative (EC mechanism). The pKa values were obtained by the dependence of limiting current and potential with in the wide pH interval. The transfer coefficients, the diffusion coefficients and rate constant of coupled chemical reaction were also reported. The substituent effects were also investigated.  相似文献   

2.
《Electroanalysis》2004,16(3):231-237
The electrochemical oxidation of antipsychotic drug amisulpride (AMS) has been studied in pH range 1.8–11.0 at a stationary glassy carbon electrode by cyclic, differential pulse and square‐wave voltammetry. Two oxidation processes were produced in different supporting electrolyte media. Both of the oxidation processes were irreversible and exhibited diffusion controlled. For analytical purposes, very resolved voltammetric peaks were obtained using differential pulse and square‐wave modes. The linear response was obtained in the range of 4×10?6 to 6×10?4 M for the first and second oxidation steps in Britton‐Robinson buffer at pH 7.0 and pH 3.0 (20% methanol v/v), respectively, using both techniques. These methods were used for the determination of AMS in tablets. The first oxidation process was chosen as indicative of the analysis of AMS in biological media. The methods were successfully applied to spiked human serum, urine and simulated gastric fluid samples.  相似文献   

3.
《Electroanalysis》2018,30(1):38-47
The aim of this study is the development of a miniaturized voltammetric method for the determination of an antimycobacterial agent 1‐hydroxy‐N‐(4‐nitrophenyl)naphthalene‐2‐carboxamide (HNN) in a single drop (20 μL) of a solution by cathodic and anodic voltammetry at a glassy carbon electrode. Cyclic voltammetry was used to investigate its redox properties followed by the optimization of differential pulse voltammetric determination in a regular 10 mL volume. The optimal medium for the analytical application of both cathodic and anodic voltammetry was found to be Britton‐Robinson buffer pH 7.0 and dimethyl sulfoxide (9 : 1, v/v). HNN gave one cathodic peak at around −0.6 V and one anodic peak at around +0.2 V vs. Ag|AgCl (3 mol L−1 KCl) reference electrode. Determination of HNN in a 10 mL volume gave the limit of quantification around 10 nmol L−1 by both adsorptive stripping anodic and cathodic voltammetry. Afterwards, miniaturized voltammetric methods in a single drop of solution (20 μL) were investigated. This approach requested some modifications of the cell design and voltammetric procedures. A novel method of removing dissolved oxygen in a single drop had to be developed and tested. Developed miniaturized voltammetric methods gave parameters comparable to the determination of HNN in 10 mL. The applicability of the miniaturized method was verified by the determination of HNN in a drop of a bacterial growth medium.  相似文献   

4.
A rapid method for the electroanalysis of ethanol is presented that incorporates flow extraction at room temperature, with voltammetric detection and potassium ferrocyanide [K4Fe(CN)6] as internal standard. In 0.1 M NaOH electrolyte, ethanol was oxidised at a platinum comb-shaped working electrode at −300 mV (vs. a Ag/AgCl reference electrode) and K4Fe(CN)6 was oxidized at +180 mV. The ratio of the anodic peak currents was linear with ethanol concentration in the range of 0.1 to 8.0% (v./v.), and the detection limit (calculated as 3 σ background) was 0.012 % (v./v.) for Osteryoung square wave voltammetry (OSWV) and 0.023 %(v./v.) for cyclic voltammetry (CV). The average extraction efficiency of ethanol from aqueous solutions, at 20 ± 1°C, was 8.5%. The repeatability was in the range of 2.5 to 3.3% RSD (n = 8), and accuracy was in the range of 95.2 to 104.7% for the determination of wine samples. Application to wines compared well with GC and HPLC methods and the nominal ethanol concentration determined by gravimetry. Analytical parameters in CV and OSWV are optimized, and the dependence of the extraction efficiency with temperature and nitrogen gas flow is presented.  相似文献   

5.
Reduced graphenes (belonging to the class of chemically modified graphenes, CMG) are one of the most investigated and utilized materials in current research. Oxygen functionalities on the CMG surfaces have dramatic influences on material properties. Interestingly, these functionalities are rarely comprehensively characterized. Herein, the four most commonly used CMGs, mainly electrochemically reduced graphene oxide (ER‐GO), thermally reduced graphene oxide (TR‐GO), and the corresponding starting materials, that is, graphene oxide and graphite oxide, were comprehensively characterized by a wide variety of methods, such as high‐resolution X‐ray photoelectron spectroscopy, electrochemical impedance spectroscopy, UV/Vis spectroscopy, transmission electron microscopy (TEM), and voltammetry, to establish connections between the structures of these materials that carry different oxygen functionalities and their electrochemical behaviors. This was followed by the quantification of the negatively charged oxygen‐containing groups (OCGs) by UV/Vis spectroscopy and of the electrochemically reducible OCGs by voltammetry. Lastly, a biofunctionalization with gold nanoparticle (AuNP)‐modified DNA sequences was performed by the formation of covalent bonds with the carboxylic groups (? COOH) on the CMG surfaces. There was an evident predominance of functionalizable ? COOH groups on the ER‐GO surface, as confirmed by a higher amount of Au detected both with differential‐pulse voltammetry and impedance spectroscopy, coupled with visualization by TEM. We exploited the DNA–Au bioconjugates as highly specific stains to localize and visualize the positions of carboxylic groups. Our findings are very important to clearly identify the presence, nature, and distribution of oxygen functionalities on different chemically modified graphenes.  相似文献   

6.
A multiresidue method was developed for the determination of fluoroquinolones in eggs. Extraction of eggs with ammoniacal acetonitrile was followed by liquid-liquid defatting, solvent evaporation, and redissolution in a small volume of buffer. The fluoroquinolones were further purified by on-line microdialysis, concentrated on a trace enrichment column, and separated by reversed-phase liquid chromatography with fluorescence detection. Norfloxacin (NOR), ciprofloxacin (CIP), and sarafloxacin (SAR) were extracted from fortified eggs over a range of 2-200 microg/kg, with recoveries of 65.7-78.9%, 65.6-77.1%, and 67.6-110%, respectively. Enrofloxacin (ENRO) was extracted over a range of 1-100 microg/kg, with recoveries of 71.5-86.7%, whereas desethylene ciprofloxacin (DCIP) and danofloxacin (DANO) were extracted over a range of 0.2-20 microg/kg, with recoveries of 68.7-90.7% and 76.0-93.8%, respectively. The limits of quantitation for the 6 fluoroquinolones were as follows: DCIP and DANO, 0.3 microg/kg; ENRO, 1 microg/kg; NOR and CIP, 2 microg/kg; and SAR, 3 microg/kg. Both SAR and ENRO incurred eggs were also successfully analyzed using this method.  相似文献   

7.
《Electroanalysis》2017,29(4):1095-1102
Using cyclic voltammetry (CV) and impedance (IMP), we report a simple approach to detect new fluorosurfactant ingredient formulated in aqueous film‐forming foam (AFFF), specifically the thioether‐based one. First, we employ ion chromatography (IC) to identify all possible elements with the help of chemical oxidation and infrared spectrum (IR) to identify all possible functional groups. We thus propose a possible thioether‐based molecular structure of fluorosurfactant formulated in AFFF. By studying the self‐assembled monolayer (SAM) formed on gold (Au) surface via thio‐Au bond, we establish a relationship between the SAM density and the amount of the thioether‐based fluorosurfactant for the AFFF detection. Solid phase extraction (SPE) and nanoporous Au electrode are employed to enhance the sensitivity. Consequently, a detection limit of 10 ppb (v/v) has been achieved for AFFF‐spiked tap water sample.  相似文献   

8.
《Analytical letters》2012,45(6):1085-1097
Abstract

A methodology for the determination of the pesticide chlorfenvinphos by microwave‐assisted solvent extraction and square‐wave cathodic stripping voltammetry at a mercury film ultramicroelectrode in soil samples is proposed. Optimization of microwave solvent extraction performed with two soils, selected for having significantly different properties, indicated that the optimum solvent for extracting chlorfenvinphos is hexane‐acetone (1∶1, v/v). The voltammetric procedure is based on controlled adsorptive accumulation of the insecticide at the potential of?0.60 V (vs. Ag/AgCl) in the presence of Britton‐Robinson buffer (pH 6.2). The detection limit obtained for a 10 s collection time was 3.0×10?8 mol l?1. The validity of the developed methodology was assessed by recovery experiments at the 0.100 µg g?1 level. The average recoveries and standard deviations for the global procedure reached by MASE‐square‐wave voltammetry were 90.2±2.8% and 92.1±3.4% for type I (soil rich in organic matter) and type II (sandy soil) samples, respectively. These results are in accordance to the expected values which show that the method has a good accuracy.  相似文献   

9.
Three novel low‐bandgap copolymers containing alkylated 4,7‐dithien‐2‐yl‐2,1,3‐benzothiadiazole (HBT) and different electron‐rich functional groups (dialkylfluorene (PFV‐HBT), dialkyloxyphenylene (PPV‐HBT) and dialkylthiophene (PTV‐HBT)) were prepared by Horner polycondensation reactions and characterized by 1H NMR, gel permeation chromatography, and elemental analysis. The alkyl side chain brings these polymeric materials good solubility in common organic solvents, which is critical for the manufacture of solar cells in a cost‐effective manner. The copolymers exhibit low optical bandgap from 1.48 to 1.83 eV. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels of the copolymers were measured by cyclic voltammetry. Theoretical calculations revealed that the variation laws of HOMO and the LUMO energy levels are well consistent with cyclic voltammetry measurement. The bulk heterojunction photovoltaic devices with the structure of ITO/PEDOT‐PSS/polymer:PCBM/LiF/Al were fabricated by using the three copolymers as the donor and (6,6)‐phenyl‐C61‐butyric acid methyl ester (PCBM) as the acceptor in the active layer. The device based on PTV‐HBT:PCBM (1:4 w/w) achieved a power conversion efficiency of 1.05% under the illumination of AM 1.5, 100 mW/cm2. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.  相似文献   

10.
A layered nanohybrid comprising of multi walled carbon nanotubes(MWCNT)‐gold nanoparticles (AuNPs) has been designed as a matrix for the development of Au dendritic nanostructures (AuDN) with enhanced catalytic activity. The developed sensor matrix was thoroughly characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), and energy dispersive X‐ray spectroscopy (EDX). The developed sensor probe MWCNT‐AuNPs/AuDN over glassy carbon electrode (GCE) was used for the label free detection of acetaminophen (AP), a commonly used drug associated with hepatotoxicity when overdosed, as a model molecule. The final sensor probe was characterized by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), linear sweep voltammetry (LSV), and differential pulse voltammetry (DPV). The sensor shows excellent analytical performances with a linear dynamic range (LDR) of 100 to 7500 nM, and a low limit of detection (LOD) of 2.12 (±0.03) nM, which is better than recently reported AP sensors. The practical application / clinical possibilities of the final sensor were evaluated by real sample analysis in human urine by spike and recovery method, where the AP recoveries were found in between 92 % to 96 %. The sensor probe shows negligible response towards co‐existing interfering molecules like glucose, urea, uric acid and various amino acids, which are commonly found in real samples (p<0.001, n=3). The shelf life of the sensor probe was evaluated and found to be stable for 8 weeks. The fabricated sensor probe using MWCNT‐AuNPs/AuDN is easy to fabricate, simple, robust, and able to detect AP in urine with high recoveries shows its possibilities to be used in clinical settings.  相似文献   

11.
《Analytical letters》2012,45(7):1381-1391
Abstract

A rapid, sensitive, and specific liquid chromatography‐electrospray ionization mass spectrometric (LC‐ESI‐MS) method has been developed for quantification of gliclazide in human plasma. The analyte and tolbutamide (internal standard, I.S.) were extracted from plasma samples with n‐hexane–dichloromethane (1:1, v/v) and analyzed on a C18 column. The chromatographic separation was achieved within 4.0 min by using methanol–0.5% formic acid (80:20, v/v) as mobile phase and the flow rate was 1.0 mL/min. Ion signals m/z 324.0 and 271.0 for gliclazide and internal standard were measured in the positive mode, respectively. The method was linear within the range of 2.5–2000 ng/mL. The lower limit of quantification (LLOQ) was 2.5 ng/mL. The intra‐ and inter‐day precisions were lower than 2.8% in terms of relative standard deviation (RSD). The inter‐day relative error (RE) as determined from quality control samples (QCs) ranged from ?1.93% to 1.85%. This validated method was successfully applied for the evaluation of pharmacokinetic profiles of gliclazide modified‐release tablets in 20 healthy volunteers.  相似文献   

12.
A rapid multianalyte‐multiclass method with little sample manipulation has been developed for the simultaneous determination of eleven mycotoxins in different food commodities by using ultra‐high‐pressure liquid chromatography coupled to triple quadrupole mass spectrometry (UHPLC/MS/MS). Toxins were extracted from the samples with acetonitrile/water (80:20, v/v) 0.1% HCOOH and, after a two‐fold dilution with water, directly injected into the system. Thanks to the fast high‐resolution separation of UHPLC, the eleven mycotoxins were separated by gradient elution in only 4 min. The method has been validated in three food matrices (maize kernels, dry pasta (wheat), and eight‐multicereal babyfood (wheat, maize, rice, oat, barley, rye, sorghum, millet)) at four different concentration levels. Satisfactory recoveries were obtained (70–110%) and precision (expressed as relative standard deviation) was typically below 15% with very few exceptions. Quantification of samples was carried out with matrix‐matched standards calibration. The lowest concentration successfully validated in sample was as low as 0.5 µg/kg for aflatoxins and ochratoxin A in babyfood, and 20 µg/kg for the rest of the selected mycotoxins in all matrices tested. Deoxynivalenol could be only validated at 200 µg/kg, due the poor sensitivity for this mycotoxin analysis. With only two exceptions (HT‐2 and deoxynivalenol), the limits of detection (LODs), estimated for a signal‐to‐noise ratio of 3 from the chromatograms of samples spiked at the lowest level validated, varied between 0.1 and 1 µg/kg in the three food matrices tested. The method was applied to the analysis of different kinds of samples. Positive findings were confirmed by acquiring two transitions (Q quantification, q confirmation) and evaluating the Q/q ratio. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

13.
Capsaicin and dihydrocapsaicin are two main bioactive components of Capsicum frutescens and are widely used as food additives and drugs in China and India. Due to their similarity in structures, isolation of capsaicin and dihydrocapsaicin with traditional methods such as silica gel column chromatography, normal‐phase thin‐layer chromatography (TLC) becomes difficult. This study involves separating capsaicin and dihydrocapsaicin with sufficient purity and recovery using high‐speed counter‐current chromatography (HSCCC) with a solvent system composed of n‐hexane–ethyl acetate–methanol–water–acetic acid (20:20:20:20:2, v/v/v/v/v). Separation parameters such as sample volume, and sample concentration were first optimized on analytical HSCCC, and then scaled up to preparative HSCCC. 0.65 g capsaicin and 0.28 g dihydrocapsaicin were obtained from 1.2 g crude extract and their purities were 98.5 and 97.8%, respectively. The recoveries of the two compounds were 86.3 and 85.4%, respectively. The purity of the isolated compounds was analyzed by high‐performance liquid chromatography (HPLC) and their structures were identified by 1H nuclear magnetic resonance (NMR) and 13C NMR analysis.  相似文献   

14.
A new method, pressurized CEC with end‐column amperometric detection using carbon paste electrode, has been developed for the separation and determination of five phenolic xenoestrogens in chicken eggs and milk powder samples. Efficient separation of five analytes was performed by pressurized CEC using a mobile phase consisting of 60% v/v ACN and 40% v/v Tris buffer (5 mmol/L, pH 8.0), +6 kV of applied voltage and 7.0 MPa of supplementary pressure. Detection limits of 50, 5, 2, 10 and 20 ng/mL for pentachlorophenol, bisphenol‐A, 2,4‐dichlorophenol, 4‐tert‐octylphenol and 4‐nonylphenol, respectively, were achieved using carbon paste electrode as working electrode and +0.8 V as detection potential. Matrix solid phase dispersion extraction method had been employed during sample preparation procedure, and mean recoveries ranged from 79.2 to 102.6% at different concentrations of phenolic xenoestrogens for spiked egg and milk powder samples were obtained.  相似文献   

15.
《Electroanalysis》2018,30(1):20-23
This work presents a simple electrochemical method for Hg determination in fish oil capsules using anodic stripping voltammetry (ASV) on a screen‐printed gold electrode (SPGE). Samples were treated in an ultrasonic bath for 15 min in the presence of a 1 : 1 (v/v) concentrated HCl/H2O2 mixture at room temperature. The limit of detection (LOD) was estimated as 0.25 μg L−1 (corresponding to 7.6 μg kg−1 of oil) with a linear range between 5 and 400 μg L−1 (90 s of deposition time). The analyzed fish oil samples presented Hg concentration below the LOD value. Recovery values for samples spiked with oil standard containing Hg ranged from 95 to 105 %. The method is precise (inter‐day and intra‐day RSD<4 % for n=3) as well as the SPGE sensors (RSD=4.3 %, n=3), which were used continuously (around 100 analyses without replacement) under such oxidation media. The proposed method is feasible to be applied for on‐site determinations due to the portability of sensing and sample treatment approaches.  相似文献   

16.
A novel approach for the determination of parts‐per‐billion level of 5‐hydroxymethyl‐2‐furaldehyde, furfuryl alcohol, furfural, 2‐furyl methyl ketone, and 5‐methylfurfural in transformer or rectifier oils has been successfully innovated and implemented. Various extraction methods including solid‐phase extraction, liquid–liquid extraction using methanol, acetonitrile, and water were studied. Water was by far the most efficient solvent for use as an extraction medium. Separation of the analytes was conducted using a 4.6 mm × 250 mm × 3.5 μm Agilent Zorbax column while detection and quantitation were conducted with a variable wavelength UV detector. Detection limits of all furans were at 1 ppb v/v with linear ranges range from 5 to 1000 ppb v/v with correlation coefficients of 0.997 or better. A relative standard deviation of at most 2.4% at 1000 ppb v/v and 7.3% at 5 ppb v/v and a recovery from 43% to 90% depending on the analyte monitored were obtained. The method was purposely designed to be environmental friendly with water as an extraction medium. Also, the method uses 80% water and 20% acetonitrile with a mere 0.2 mL/min of acetonitrile in an acetonitrile/water mixture as mobile phase. The analytical technique has been demonstrated to be highly reliable with low cost of ownership, suitable for deployment in quality control labs or in regions where available analytical resources and solvents are difficult to procure.  相似文献   

17.
Two β‐adrenergic blocking agents, 1‐[(1‐methylethyl)amino]‐3‐phenoxy‐2‐propanol ( 1 ) and 1‐[(1‐methylethyl)amino]‐3‐(3‐methylphenoxy)‐2‐propanol ( 2 ; Toliprolol), were enantioseparated by pH‐zone‐refining countercurrent chromatography. A two‐phase solvent system composed of chloroform containing 0.10 mol/L of di‐n‐hexyl l‐ tartrate/0.10 mol/L of boric acid aqueous solution (1:1, v/v) was selected, in which 20 mmol/L triethylamine was added in the organic phase as a retainer and 2 mmol/L HCl was added in the aqueous phase as an eluter. Fifty milligrams of each racemate was completely enantioseparated by pH‐zone‐refining countercurrent chromatography to yield each enantiomer with a purity of more than 98%, and the recovery of each separated enantiomer reached around 76–82%.  相似文献   

18.
The feasibility of fabricating copper-sensitive chemically modified electrodes (CMEs) for trace analysis in aqueous and in 40% (v/v) ethanol-water media was investigated. Carbon paste electrodes modified with crown ethers were constructed by mixing the crown ethers into a graphite powder-paraffin oil matrix. The electrodes so formed were able to bind Cu(II) ions chemically and gave better voltammetric responses than the unmodified ones. The crown ethers studied and compared were 15-crown-5, benzo-15-crown-5 and dibenzo-18-crown-6. With a 3% benzo-15-crown-5 CME, Cu(II) could be quantified at sub-ppm levels by differential pulse voltammetry with a detection limit of 0.05 ppm. By differential pulse anodic stripping voltammetry Cu(II) could be quantified over the range 1 to 100 ppb. Interference from metal ions like Ni(II), Co(II), Mn(II), Fe(II), etc. have also been studied. The method was successfully applied to artificial as well as commercial samples of alcoholic beverages. Received: 12 January 2000 / Revised: 14 March 2000 / Accepted: 16 March 2000  相似文献   

19.
A simple, sensitive, and rapid method for determination of L‐trantinterol in rat plasma was developed for the first time by using LC coupled to MS/MS based on chiral stationary phase. A baseline separation of the enantiomers of trantinterol was achieved on a Chirobiotic V column, using a mixture of acetonitrile–methanol–ammonia–acetic acid (80:20:0.01:0.02, v/v/v/v) as the mobile phase. The detection was performed on a triple‐quadrupole tandem mass spectrometer by multiple reaction monitoring mode via ESI. The calibration curve was linear in concentration range from 0.270 to 108 ng/mL in plasma with the lower limit of quantification of 0.270 ng/mL. The intra‐ and interday precision (relative standard deviation) values were within 10.9% and the accuracy (relative error) was from 2.6 to 9.2% at all quality control levels. The method has been successfully applied to a study of L‐trantinterol pharmacokinetics in rats.  相似文献   

20.
The feasibility of fabricating copper-sensitive chemically modified electrodes (CMEs) for trace analysis in aqueous and in 40% (v/v) ethanol-water media was investigated. Carbon paste electrodes modified with crown ethers were constructed by mixing the crown ethers into a graphite powder-paraffin oil matrix. The electrodes so formed were able to bind Cu(II) ions chemically and gave better voltammetric responses than the unmodified ones. The crown ethers studied and compared were 15-crown-5, benzo-15-crown-5 and dibenzo-18-crown-6. With a 3% benzo-15-crown-5 CME, Cu(II) could be quantified at sub-ppm levels by differential pulse voltammetry with a detection limit of 0.05 ppm. By differential pulse anodic stripping voltammetry Cu(II) could be quantified over the range I to 100 ppb. Interference from metal ions like Ni(II), Co(II), Mn(II), Fe(II), etc. have also been studied. The method was successfully applied to artificial as well as commercial samples of alcoholic beverages.  相似文献   

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