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1.
This study is aimed to develop an electroanalytical methodology using a boron-doped diamond electrode to determine simultaneously and selectively carbendazim (CBZ) and carbaryl (CAR). In previous studies using cyclic voltammetry oxidation, peaks were observed at 1.03 V (CBZ) and 1.44 V (CAR), with characteristics of an irreversible process controlled by diffusion of species, with a supporting electrolyte of BR buffer (0.1 mol L?1) and pH adjusted to 6.0. The differences between the potentials for both pesticides, about 400 mV, indicate the possibility of selective determination of CBZ and CAR. The square-wave voltammetric parameters were optimised. The best separation conditions were pH 6.0, square-wave frequency of 100 s?1, pulse amplitude of 50 mV and scan increment of 2.0 mV. These parameters were used to obtain the calibration curves of CBZ and CAR. An analytical curve was constructed in the range concentration of CBZ of 1.3 mg L?1 to 15.3 mg L?1 and CAR of 1.0 mg L?1 to 11.4 mg L?1, respectively. The limits of detection (LOD) and limits of quantification (LOQ) for CBZ were 0.40 mg L?1 and 1.30 mg L?1, respectively. For CAR, the LOD and LOQ were 0.30 mg L?1 and 1.00 mg L?1, respectively. Sensitivity values were 0.78 and 2.60 µA/mg L?1 for CBZ and CAR, respectively. The electroanalytical method was applied in Mikania glomerata infusions. The recovery values were 106.2% and 116.5% for CBZ and CAR, respectively. The results show that the developed method is suitable for application in medicinal plant samples.  相似文献   

2.
《Electroanalysis》2003,15(22):1751-1755
A sensitive, selective and economic stripping voltammetry is described for the determination of trace amounts of zirconium at a morin‐modified carbon paste electrode (morin‐MCPE). Zirconium(IV) can be preconcentrated on the surface of the morin‐MCPE due to forming the Zr(IV)–morin complex. The complex produces two second‐order derivative anodic peaks at 0.69 V (vs. SCE) and 0.75 V when linear‐scanning from 0.0 to 1.0 V. The optimum analytical conditions are: 2.2 mol L?1 HCl, 0.0 V accummulation potential, 90 s accummulation time, 250 mV s?1 scan rate. A linear relationships between the peak currents at 0.75 V and the Zr(IV) concentration are in the range of 2.0×10?8 to 3.0×10?6 mol L?1. The detection limit is 1.0×10?8 mol L?1 (S/N=3) for 120 s accumulation. The RSD for determination of 4.0×10?7 mol L?1 Zr(IV) is 4.8% (n=8). The proposed method has been applied to determine zirconium in ore samples, unnecessarily extracted.  相似文献   

3.
This paper describes a rapid and sensitive method for determination of the hair dye Basic Blue 41 in wastewater samples using screen‐printed carbon electrodes modified with graphene (SPCE/Gr). The method is based on the reversible reduction of azo groups of the dye at potential of ?0.23 V/?0.26 V, where both the anodic and cathodic currents increased 1,300 % when compared to screen‐printed carbon (SPCE) and glassy carbon electrodes (GCE). The optimization of a square wave voltammetric method was performed by means of 23 factorial design, Doehlert matrix and multi‐response assays, and the best parameters were: frequency (54.8 Hz), step potential (6 mV), pulse amplitude (43.7 mV) and pH 4.5. The analytical curve was constructed from 3.00×10?8 to 2.01×10?6 mol L?1, with detection and quantification limits of 5.00×10?9 and 1.70×10?8 mol L?1, respectively. The repeatability of the method evaluated for 10 consecutive measurements at concentrations of 1.70×10?7 mol L?1 and 1.70×10?6 mol L?1, showed relative standard deviation of 3.56 and 0.57 %, respectively. The sensor based in SPCE/Gr was successfully applied in wastewater samples collected from a drinking water treatment plant and validated by comparison with HPLC‐DAD method with good accuracy.  相似文献   

4.
Electrochemical behavior of dopamine (DA) was investigated at the gold nanoparticles self‐assembled glassy carbon electrode (GNP/LC/GCE), which was fabricated by self‐assembling gold nanoparticles on the surface of L ‐cysteine (LC) modified glassy carbon electrode (GCE) via successive cyclic voltammetry (CV). A pair of well‐defined redox peaks of DA on the GNP/LC/GCE was obtained at Epa=0.197 V and Epc=0.146 V, respectively. And the peak separation between DA and AA is about 0.2 V, which is enough for simultaneous determination of DA and AA. The peak currents of DA and AA were proportional with their concentrations in the range of 6.0×10?8–8.5×10?5 mol L?1 and 1.0×10?6–2.5×10?3 mol L?1, with the detection limit of 2.0×10?8 mol L?1 and 3.0×10?7 mol L?1 (S/N=3), respectively. The modified electrode exhibits an excellent reproducibility, sensibility and stability for simultaneous determination of DA and AA in human serum with satisfactory result.  相似文献   

5.
A simple and sensitive method for simultaneously measuring dopamine (DA), ascorbic acid (AA), and uric acid (UA) using a poly(1‐aminoanthracene) and carbon nanotubes nanocomposite electrode is presented. The experimental parameters for composite film synthesis as well as the variables related to simultaneous determination of DA, AA, and UA were optimized at the same time using fractional factorial and Doehlert designs. The use of carbon nanotubes and poly(1‐aminoanthracene) in association with a cathodic pretreatment led to three well‐defined oxidation peaks at potentials around ?0.039, 0.180 and 0.351 V (vs. Ag/AgCl) for AA, DA, and UA, respectively. Using differential pulse voltammetry, calibration curves for AA, DA, and UA were obtained over the range of 0.16–3.12×10?3 mol L?1, 3.54–136×10?6 mol L?1, and 0.76–2.92×10?3 mol L?1, with detection limits of 3.95×10?5 mol L?1, 2.90×10?7 mol L?1, and 4.22×10?5 mol L?1, respectively. The proposed method was successfully applied to determine DA, AA, and UA in biological samples with good results.  相似文献   

6.
A novel voltammetric method using the Ppyox/NFR/Au (poly pyrrole – nuclear fast red – gold) modified electrode was developed for simultaneous measurement of various combinations of ascorbic acid (AA) and methyldopa (MDA). Polypyrrole film was prepared by incorporation of nuclear fast red (NFR) as doping anion, during the electropolymerization of pyrrole onto a gold (Au) electrode in aqueous solution using cyclic voltammetric (CV) method, and then it was overoxidized at constant potential. Differential pulse voltammetry was utilized for the measurement of both analytes using modified electrode. Well‐separated voltammetric peaks were observed for ascorbic acid (AA) and methyldopa at the Ppyox/NFR/Au modified electrodes with peak separation of 0.210 V. It has been found that under optimum condition (pH 3.0), the oxidation of AA and MDA at the surface of the electrode occurs at a potential about 260 and 50 mV less positive than unmodified Au electrode respectively. The current catalytic oxidation peaks showed a linear dependent on the concentration of AA and MDA in the range of 9.0×10?6 to 1.0×10?3 and 1.0×10?7 to 2.0×10?5 mol L?1 respectively. The detection limit of 5.8×10?6 and 5.0×10?8 mol L?1 (S/N=3) were obtained for AA and MDA respectively. The modified electrode was used for determination of AA and MDA in some real samples such as human serum and tablet.  相似文献   

7.
An electrochemical biosensor was fabricated by covalent modification of 5-hydroxytryptophan (5-HTP) on the surface of glassy carbon electrode (GCE). The electrode, denoted as 5-HTP/GCE, was characterized by X-ray photoelectron spectroscopy, cyclic voltammetry and differential pulse voltammetry. For comparison, tryptophan modified GCE (TRP/GCE) and serotonin modified GCE (5-HT/GCE) were prepared by the same method. It was found that electrocatalytic ability of these electrodes was in the order of 5-HTP/GCE?>?TRP/GCE?>?5-HT/GCE for the oxidation of dopamine (DA) and 5-HT. The sensor was effective to simultaneously determine DA and 5-HT in a mixture. It can resolve the overlapping anodic peaks into two well-defined voltammetric peaks at 0.24 and 0.39 V (versus SCE). The linear response is in the range of 5.0?×?10?7–3.5?×?10?5 mol L?1 with a detection limit of 3.1?×?10?7 mol L?1 for DA, and in the range of 5.0?×?10?6–3.5?×?10?5 mol L?1 with a detection limit of 1.7?×?10?6 mol L?1 for 5-HT (s/n?=?3), respectively.  相似文献   

8.
The present work describes the individual, selective and simultaneous quantification of acetaminophen (ACP) and tramadol hydrochloride (TRA) using a modification‐free boron‐doped diamond (BDD) electrode. Cyclic voltammetric measurements revealed that the profile of the binary mixtures of ACP and TRA were manifested by two irreversible oxidation peaks at about +1.04 V (for ACP) and +1.61 V (for TRA) in Britton‐Robinson (BR) buffer pH 3.0. TRA oxidation peak was significantly improved in the presence of anionic surfactant, sodium dodecyl sulfate (SDS), while ACP signal did not change. By employing square‐wave stripping mode in BR buffer pH 3.0 containing 8×10?4 mol L?1 SDS after 30 s accumulation under open‐circuit voltage, the BDD electrode could be used for quantification of ACP and TRA simultaneously in the ranges 1.0–70 μg mL?1 (6.6×10?6–4.6×10?4 mol L?1) and 1.0–70 μg mL?1 (3.3×10?6–2.3×10?4 mol L?1), with detection limits of 0.11 μg mL?1 (7.3×10?7 mol L?1) and 0.13 μg mL?1 (4.3×10?7 mol L?1), respectively. The practical applicability of the proposed approach was tested for the individual and simultaneous quantification of ACP and/or TRA in the pharmaceutical dosage forms.  相似文献   

9.
Three types of ion‐selective electrodes: PVC membrane, modified carbon paste (CPE), and coated graphite electrodes (CGE) have been constructed for determining paroxetine hydrochloride (Prx). The electrodes are based on the ion pair of paroxetine with sodium tetraphenylborate (NaTPB) using dibutyl phthalate as plasticizing solvent. Fast, stable and potentiometric response was obtained over the concentration range of 1.1×10?5–1×10?2 mol L?1 with low detection limit of 6.9×10?6 mol L?1 and slope of a 56.7±0.3mV decade?1 for PVC membrane electrode, the concentration range of 2×10?5–1×10?2 mol L?1 with low detection limit of 1.2×10?5 mol L?1 and slope of a 57.7±0.6 mV decade?1 for CPE, and the concentration range of 2×10?5–1×10?2 mol L?1 with low detection limit of 8.9×10?6 mol L?1 and slope of a 56.1±0.1 mV decade?1 for CGE. The proposed electrodes display good selectivity for paroxetine with respect to a number of common inorganic and organic species. The electrodes were successfully applied to the potentiometric determination of paroxetine hydrochloride in its pure state, its pharmaceutical preparation, human urine and plasma.  相似文献   

10.
《Electroanalysis》2006,18(15):1457-1462
This work describes an electroanalytical method for determining gold(I) thiomalate, aurothiomalate, widely used for treatment of reumatoid arthiritis, using a screen‐printed carbon electrode (SPCE). Aurothiomalate (AuTM) was determined indirectly at the same electrode by accumulating it first at ?1.5 V vs. printed carbon. At this potential in the adsorbed state, the AuTM is reduced to Au(0), which is then oxidized at two steps at ?0.22 V and +0.54 V on SPCE. Using optimized conditions of 60 s deposition time, ?1.5 V (vs. printed carbon) accumulation potential, 100 mV s?1 scan rate, linear calibration graphs can be obtained by monitoring the peak at +0.54 V for AuTM in HCl 0.1 mol L?1 from 1.43×10?6 to 1.55×10?4 mol L?1. A limit of detection obtained was 6.50×10?7 mol L?1, and the relative standard deviation from five measurements of 3.0×10?5 mol L?1 AuTM is 4.5%. The method was successfully applied for AuTM determination in human urine sample.  相似文献   

11.
The electrochemical oxidation of promethazine hydrochloride was made on highly boron‐doped diamond electrodes. Cyclic voltammetry experiments showed that the oxidation mechanisms involved the formation of an adsorbed product that is more readily oxidized, producing a new peak with lower potential values whose intensity can be increased by applying the accumulation potential for given times. The parameters were optimized and the highest current intensities were obtained by applying +0.78 V for 30 seconds. The square‐wave adsorptive voltammetry results obtained in BR buffer showed two well‐defined peaks, dependent on the pH and on the voltammetric parameters. The best responses were obtained at pH 4.0, frequency of 50 s?1, step of 2 mV, and amplitude of 50 mV. Under these conditions, linear responses were obtained for concentrations from 5.96×10?7 to 4.76×10?6 mol L?1, and calculated detection limits of 2.66×10?8 mol L?1 (8.51 μg L?1) for peak 1 and of 4.61×10?8 mol L?1 (14.77 μg L?1) for peak 2. The precision and accuracy were evaluated by repeatability and reproducibility experiments, which yielded values of less than 5.00% for both voltammetric peaks. The applicability of this procedure was tested on commercial formulations of promethazine hydrochloride by observing the stability, specificity, recovery and precision of the procedure in complex samples. All results obtained were compared to recommended procedure by British Pharmacopeia. The voltammetric results indicate that the proposed procedure is stable and sensitive, with good reproducibility even when the accumulation steps involve short times. It is therefore very suitable for the development of the electroanalytical procedure, providing adequate sensitivity and a reliable method.  相似文献   

12.
In this work voltammetric techniques were explored for quantification of α‐Lipoic acid (ALA) using a pyrolytic graphite electrode modified with cobalt phthalocyanine. Cyclic voltammograms recorded in phosphate buffer solution containing 1×10?3 mol L?1 of ALA presented an oxidation peak located at +0.8 V vs. SCE. The modification of the electrode produced a 100 mV shift of the onset oxidation potential to less positive value and a substantial increase in the ALA oxidation current. Among the voltammetric techniques explored, differential pulse voltammetry showed the best performance for quantifications of the analyte in low concentrations. Limits of detection and quantification of ALA obtained corresponds to 3.4×10?9 mol L?1 and 1.2×10?8 mol L?1, respectively.  相似文献   

13.
Novel selective and sensitive poly (vinyl chloride) membrane sensors are developed for measuring alizarin red S (AR) based on the use of aliquate 336, MgIIphthalocyanine (MgPc), CuIIphthalocyanine (CuPc) and FeII phthalocyanine (FePc) plasticized poly (vinyl chloride) membrane. The sensors display Nernestian response with slopes of ‐50.6 ± 0.6 , ‐37.4 ± 0.5 , ‐37.7 ± 0.8 and ‐35.0 ± 0.7 mV decade?1 over the range of 5.2 × 10?6 to 1 × 10?2 mol L?1 for all of them and detection limits of 5.9 × 10?7, 1.9 × 10‐?6 2.3 × 10?6 and 1.9 × 10?6 mol L?1 for aliquate, MgPc, CuPc and FePc membrane based sensor, respectively. The sensors exhibit long life span, long term potential stability, high reproducibility, fast response and good discrimination ability towards alizarinate ion in comparison with many other anions. A tubular detector based on aliquate, MgPc, CuPc and FePc was further developed and coupled to a flow‐injection system for alizarin (AR) determination. Under optimized conditions, the linearity range is 1.0 × 10?5‐ 1.0 × 10?1 mol L?1, with a slope of ‐52.1 ± 0.8, 20.9 ± 0.7, 23.6 ± 0.4 and 25 ± 1.1 mV decade?1 and a reproducibility of ± 0.8 mV (n = 6) for aliquate, MgPc, CuPc and FePc membrane based sensors, respectively. The sensor based on aliquate is further utilized for a potentiodynamic quantification of aluminum in sludge samples and deodorants. The buffered solution of alizarin was allowed to react in a flow system with aluminum. The calibration curve of Al was found to be linear over a concentration range of 0.1 to 1.8 and 1.0 ‐ 40 μg mL?1 with a slope = 16.9 (r2 = 0.993) and 1.76 (r2 = 0.994) mV (μg/mL)?1 and a detection limit of 0.08 and 0.5 μg mL?1 for 10?4 and 10?3 mol L?1 AR? as a carrier, respectively. The method was successfully used for determining aluminum in sludge samples and deodorants. The data agree fairly well the nominal values and with results obtain by continuous flow hydride generation inductively coupled plasma (ICP) method.  相似文献   

14.
A new voltammetric procedure for the simultaneous determination of dopamine (DA) and paracetamol (PA) using boron doped diamond electrode modified with Nafion and lead films (PbF/Nafion/BDDE) was investigated. The use of this electrode resolved the overlapped voltammetric waves of DA and PA into well‐defined peaks with peak to peak separation of about 320 mV. Under the optimized experimental conditions in differential pulse voltammetric technique, DA and PA gave a linear response over the ranges 2.0×10?7–1.0×10?4 mol L?1*(R2=0.9996) and 5.0×10?7–1.0×10?3 mol L?1 (R2=0.9979), respectively. The detection limits were found to be 5.4×10?8 mol L?1 for DA and 1.4×10?7 mol L?1 for PA. They are lower, comparable or in some cases a little bit higher than those obtained using other electrochemical sensors. However, the proposed procedure of the sensor preparation is much simpler than procedures described in the literature with a lower detection limit. The proposed procedure was successfully applied to the determination of PA in some commercial pharmaceuticals as well as to the simultaneous determination of DA and PA in human urine, whole blood and serum samples directly without any separation steps.  相似文献   

15.
Two novel potentiometric azide membrane sensors based on the use of manganese(III)porphyrin [Mn(III)P] and cobalt(II)phthalocyanine [Co(II)Pc] ionophores dispersed in plasticized poly(vinyl chloride) PVC matrix membranes are described. Under batch mode of operation, [Mn(III)P] and [Co(II)Pc] based membrane sensors display near‐ and sub‐Nernstian responses of ?56.3 and ?48.5 mV decade?1 over the concentration ranges 1.0×10?2?2.2×10?5 and 1.0×10?2?5.1×10?5 mol L?1 azide and detection limits of 1.5×10?5 and 2.5×10?5 mol L?1, respectively. Incorporation of both membrane sensors in flow‐through tubular cell offers sensitive detectors for flow injection (FIA) determination of azide. The intrinsic characteristics of the [Mn(III)P] and [Co(II)Pc] based detectors in a low dispersion manifold show calibration slopes of ?51.2 and ?33.5 mV decade?1 for the concentration ranges of 1.0×10?5?1.0×10?2 and 1.0×10?4?1.0×10?2 mol L?1 azide and the detection limits are1.0×10?5 and 3.1×10?5 mol L?1, respectively. The detectors are used for determining azide at an input rate of 40–60 samples per hour. The responses of the sensors are stable within ±0.9 mV for at least 8 weeks and are pH independent in the range of 3.9?6.5. No interferences are caused by most common anions normally associated with azide ion.  相似文献   

16.
Amantadine potentiometric detectors were developed, evaluated and incorporated in a SIA‐LOV manifold in order to accomplish the control of pharmaceutical formulations and urine. The electrodes incorporate α‐cyclodextrin as ionophore, dibutyl phthalate or 2‐fluorophenyl 2‐nitrophenyl ether as plasticizers and potassium tetrakis[3,5‐bis‐(trifluoromethyl)phenyl]borate (KTFPB) as cationic additive. The slope increased from 61.2 to 63.8 mV decade?1 and the practical limit of detection from 2.6×10?6 mol L?1 to 2.5×10?5 mol L?1 when the plasticizer was changed from 2‐fluorophenyl 2‐nitrophenyl ether to dibutyl phthalate. When incorporated in the flow‐manifold the membranes composed by dibutyl phthalate or with 2‐fluorophenyl 2‐nitrophenyl ether presented slopes and a practical limit of detection of 69.8 mV decade?1 and 1.5×10?4 mol L?1 or 73.7 mV decade?1 and 5.4×10?5 mol L?1, respectively. The electrode presented stable responses for over a year, and were highly selective concerning the representative species of the two sample matrices assayed as interferents. Comparison of obtained results with those provided by reference methods and recovery assays, revealed adequate accuracy for control assays.  相似文献   

17.
The voltammetric behavior of paraquat was investigated at hydroxyapatite‐modified carbon paste electrode HAP‐CPE in K2SO4. A method was developed for the detection of the trace of this herbicide, based on their redox reaction. The reduction peaks of paraquat were observed around ?0.70 V and ?1.00 V (vs. SCE) in square‐wave voltammetry. Experimental conditions were optimized by varying the accumulation time, apatite loading and measuring solution pH. Calibration plots were linear under the optimized parameters over the herbicide's concentration range 8–200×10?7 mol L?1, with a detection and quantification limits about 1.5×10?8 mol L?1 and 6.4 10?8 mol L?1, respectively.  相似文献   

18.
Self‐organized Ti/TiO2 nanotubular array electrodes were prepared by electrochemical anodization and used to monitor the reduction of the hair dye basic brown 17 (BB17) at a potential of ?0.60 V vs. Ag/AgCl. Analytical curves were obtained from 1.0×10?6 to 8.0×10?5 mol L?1 with a detection limit of 1.3×10?7 mol L?1 by using the best experimental conditions, linear scan voltammetry at pH 6, scan rate=60 mV s?1, and accumulation time=5 min. The detection system performance was not interfered by other hair dyes and successfully used to determine the dye in tap water samples.  相似文献   

19.
A new electrode was developed by one-step potentiostatic electrodeposition (at ?2.0 V for 20 s) of Au/SiO2 nanoparticles on a glassy carbon electrode. The resulting electrode (nano-Au/SiO2/GCE) was characterized by scanning electronic microscopy, X-ray photoelectron spectroscopy and electrochemical techniques. The electrochemical behavior of dihydronicotinamide adenine dinucleotide (NADH) at the nano-Au/SiO2/GCE were thoroughly investigated. Compared to the unmodified electrode, the overpotential decreased by about 300 mV, and the current response significantly increased. These changes indicated that the modified electrode showed excellent catalytic activity in the oxidation of NADH. A linear relationship was obtained in the NADH concentration range from 1.0?×?10?6 to 1.0?×?10?4 mol?L?1. In addition, amperometric sensing of ethanol at the nano-Au/SiO2/GCE in combination with alcohol dehydrogenase and nicotinamide adenine dinucleotide was successfully demonstrated. A wide linear response was also found for ethanol in the range from 5.0?×?10?5 to 1.0?×?10?3 mol?L?1 and 1.0?×?10?3 to 1.0?×?10?2 mol?L?1, respectively. The method was successfully applied to determine ethanol in beer and biological samples.  相似文献   

20.
A (SiPy+Cl?/CuTsPc)5 layer‐by‐layer film was employed for the electroanalytical determination of promethazine hydrochloride in BR buffer pH 5.0 with peaks at 0.48 and 0.79 V. After optimisation of the square‐wave parameters (f=100 s?1, a=40 mV and ΔEs=2 mV), the peak at 0.79 V was used for quantification and a detection limit of 8.71×10?9 mol L?1 and a quantification limit of 9.31×10?8 were calculated. The applicability of this procedure was tested on commercial formulations of promethazine hydrochloride by observing the stability, specificity, recovery and precision of the procedure in complex samples, without any preliminary treatment.  相似文献   

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