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1.
A new simple and direct electroanalytical method was developed for the determination of azidothymidine in commercial pharmaceutical preparations. It is based on differential pulse voltammetry at silver solid amalgam electrode with polished surface (p‐AgSAE) or surface modified by mercury meniscus (m‐AgSAE). The electroreduction of azidothymidine in basic media at these electrodes gives rise to one irreversible cathodic peak. Its potential in 0.05 mol L?1 borate buffer, pH 9.3 at ca. ?1050 mV is comparable to that using hanging mercury drop electrode (HMDE). Achieved limits of quantitation are in the 10?7 mol L?1 concentration range for both amalgam electrodes. According to the procedure based on the standard addition technique, the recoveries of known amounts of azidothymidine contained in pharmaceutical preparations available in capsules were 101.4±1.8% (m‐AgSAE), 100.3±3.5% (p‐AgSAE) and 102.0±1.0% (HMDE) (n=10). There was no significant difference between the values gained by proposed voltammetric methods and the HPLC‐UV recommended by the United States Pharmacopoeia regarding the mean values and standard deviations.  相似文献   

2.
The voltammetric behavior of two genotoxic nitro compounds (4‐nitrophenol and 5‐nitrobenzimidazole) has been investigated using direct current voltammetry (DCV) and differential pulse voltammetry (DPV) at a polished silver solid amalgam electrode (p‐AgSAE), a mercury meniscus modified silver solid amalgam electrode (m‐AgSAE), and a mercury film modified silver solid amalgam electrode (MF‐AgSAE). The optimum conditions have been evaluated for their determination in Britton‐Robinson buffer solutions. The limit of quantification (LQ) for 5‐nitrobenzimidazole at p‐AgSAE was 0.77 µmol L?1 (DCV) and 0.47 µmol L?1 (DPV), at m‐AgSAE it was 0.32 µmol L?1 (DCV) and 0.16 µmol L?1 (DPV), and at MF‐AgSAE it was 0.97 µmol L?1 (DCV) and 0.70 µmol L?1 (DPV). For 4‐nitrophenol at p‐AgSAE, LQ was 0.37 µmol L?1 (DCV) and 0.32 µmol L?1 (DPV), at m‐AgSAE it was 0.14 µmol L?1 (DCV) and 0.1 µmol L?1 (DPV), and at MF‐AgSAE, it was 0.87 µmol L?1 (DCV) and 0.37 µmol L?1 (DPV). Thorough comparative studies have shown that m‐AgSAE is the best sensor for voltammetric determination of the two model genotoxic compounds because it gives the lowest LQ, is easier to prepare, and its surface can be easily renewed both chemically (by new amalgamation) and/or electrochemically (by imposition of cleaning pulses). The practical applicability of the newly developed methods was verified on model samples of drinking water.  相似文献   

3.
《Electroanalysis》2003,15(22):1778-1781
The voltammetric behavior of N,N‐dimethyl‐4‐amino‐2′‐carboxyazobenzene was investigated by differential pulse voltammetry (DPV) at a mercury meniscus‐modified silver solid amalgam electrode (m‐AgSAE). Conditions have been found for its determination by DPV at m‐AgSAE in the concentration range of 0.4 to 15 μmol L?1.  相似文献   

4.
《Electroanalysis》2006,18(2):127-130
The voltammetric behavior of 2‐methyl‐4,6‐dinitrophenol was investigated by differential pulse voltammetry (DPV) at a nontoxic mercury meniscus‐modified silver solid amalgam electrode (m‐AgSAE). Conditions have been found for its determination by DPV at m‐AgSAE in the concentration range of 0.2 to 1 μmol L?1.  相似文献   

5.
《Electroanalysis》2006,18(2):186-194
The complex of osmium tetroxide with 2,2′‐bipyridine has been utilized as a probe of DNA structure and an electroactive marker of DNA in DNA hybridization sensors. It produces several voltammetric signals, the most negative of them has been observed only at mercury electrodes. This signal is of catalytic nature affording a high sensitivity of DNA determination. The catalytic current due to evolution of hydrogen in voltammetry of DNA modified by complex of osmium tetroxide with 2,2′‐bipyridine (DNA‐Os,bipy) was studied. Solid amalgam electrodes (modified with mercury menisci) of silver (m‐AgSAE), copper (m‐CuSAE), gold, and of combined bismuth and silver, were used as possible substitutes for mercury electrodes. Besides the hanging mercury drop electrode (HMDE), the catalytic current was observed only on m‐AgSAE and m‐CuSAE. Electrodes of gold and bismuth amalgams did not give the catalytic current. The detection limit of DNA‐Os,bipy on HMDE was 0.1 ng mL?1 (RSD=2.3 %, N=11), and on m‐AgSAE 0.2 ng mL?1 (RSD=3.1%, N=11). The m‐AgSAE was successfully applied as a detection electrode in double‐surface DNA hybridization experiments offering highly specific discrimination between complementary (target) and nonspecific DNAs, as well as determination of the length of a repetitive DNA sequence. The m‐AgSAE has proved a convenient alternative to the HMDE or carbon electrodes used for similar purposes in previous work.  相似文献   

6.
《Analytical letters》2012,45(15):2339-2363
Abstract

Electrodes based on amalgam materials were re-introduced in electroanalytical chemistry in the year 2000, partially as reaction to unsubstantiated public fears of liquid mercury. In this publication, the voltammetric behavior of 1-nitronaphthalene and 2-nitronaphthalene was investigated at a mercury meniscus-modified silver solid amalgam electrode. The reduction mechanism in mixed neutral buffer-methanol medium includes the four-electron reduction to hydroxylaminoderivative followed by a two-electron reduction to the amine in acidic medium, similarly to mercury electrodes. In alkaline media, both compounds show the splitting of the main four-electron reduction peak typical for mercury electrodes in two new ones, the first one corresponding to a one electron reduction of the nitroderivative to the nitro radical anion, which was confirmed by microcoulometry. Using optimized conditions (differential pulse voltammetry, Britton-Robinson buffer pH 7.0 – methanol (9:1) medium) the calibration dependences are linear in the range of 2·10?7 (4·10?7) to 1·10?4 mol L?1 for 1-nitronaphthalene (2-nitronaphthalene). After preconcentration of the analytes from drinking and river water samples using solid phase extraction the limit of determination was lowered to ~3·10?8 mol L?1.  相似文献   

7.
A new analytical methodology for the electrochemical detection of the herbicide maleic hydrazide (3,6‐dihydroxypyridazine) by flow injection analysis is presented. This method is supported by the novel application of a palladium‐dispersed carbon paste electrode as an amperometric sensor for this herbicide. Maleic hydrazide shows anodic electrochemical activity on carbon‐based electrodes (glassy carbon or carbon paste electrodes) in all the pH range. This electrochemical activity is enhanced using metal‐dispersed carbon paste electrodes, especially at Pd‐dispersed CPE which displays good oxidation signals at 690 mV (0.050 M phosphate buffer pH 7.0), 140 mV lower than at unmodified electrodes. Under the optimized conditions, the electroanalytical performance of Pd‐dispersed CPE in flow injection analysis was excellent, with good reproducibility (RSD 3.3%) and a wide linear range (1.9×10?7 to 1.0×10?4 mol L?1). A detection limit of 1.4×10?8 mol L?1 (0.14 ng maleic hydrazide) was obtained for a sample loop of 100 μL at a fixed potential of 700 mV in 0.050 M phosphate buffer solution at pH 7.0 and a flow rate of 2.0 mL min?1. The proposed method was applied for the maleic hydrazide detection in natural drinking water samples.  相似文献   

8.
We present a simplified approach for the trace screening of toxic heavy metals utilizing bismuth oxide screen printed electrodes. The use of bismuth oxide instead of toxic mercury films facilitates the reliable sensing of lead(II), cadmium(II) and zinc(II). A linear range over 5 to 150 μg L?1 with detection limits of 2.5 and 5 μg L?1 are readily observed for cadmium and lead in 0.1 M HCl, respectively. Conducting a simultaneous multi‐elemental voltammetric detection of zinc, cadmium and lead in a higher pH medium (0.1 M sodium acetate solution) exhibited a linear range between 10 and 150 μg L?1 with detection limits of 5, 10 and 30 μg L?1 for cadmium, lead and zinc respectively. The sensor is greatly simplified over those recently reported such as bismuth nanoparticle modified electrodes and bismuth film coated screen printed electrodes. The scope of applications of this sensor with the inherent advances in electroanalysis coupled with the negliable toxicity of bismuth is extensive allowing high throughput electroanalysis.  相似文献   

9.
For the construction of the sensor, three different carbon black (CB) materials (VULCAN XC72R, BLACK PEARLS 4750 and CB N220) were explored as modifying nanomaterial. Firstly, the electrochemical activity of the each SPE modified was compared by cyclic voltammetry and electrochemical impedance spectroscopy technique, using [Fe(CN)6]3?/4? as redox couple. After demonstrating that electrodes modified with different types of CB were characterized by improved electrochemical performances when compared with bare electrodes, and among them, electrodes modified with CB BP4750 is characterised by slightly better electrochemical properties, this type of electrode was used for the development of the analytical method. By applying SWV technique in 0.2 mol L?1 phosphate buffer (pH 3.0), the obtained analytical curves for ACP and LVF were found linearly from 4.0 to 80.0 μmol L?1 and from 0.90 to 70.0 μmol L?1 with limit of detection of 2.6 μmol L?1 and 0.42 μmol L?1 for ACP and LVF, respectively. Finally, the quantification of these drugs in river water was evaluated using the new here‐proposed sensor by recovery method in spiked samples, obtaining satisfactory recovery values. The results achieved demonstrated that the developed analytical tool is of great analytical interest being easy to use, cost‐effective, miniaturized, and thus suitable for low cost on site analysis.  相似文献   

10.
Flow injection analysis with amperometric detection (FIA‐AD) at screen‐printed carbon electrodes (SPCEs) in optimum medium of Britton‐Robinson buffer (0.04 mol ? L?1, pH 2.0) was used for the determination of three tumor biomarkers (homovanillic acid (HVA), vanillylmandelic acid (VMA), and 5‐hydroxyindole‐3‐acetic acid (5‐HIAA)). Dependences of the peak current on the concentration of biomarkers were linear in the whole tested concentration range from 0.05 to 100 μmol ? L?1, with limits of detection (LODs) of 0.065 μmol ? L?1 for HVA, 0.053 μmol ? L?1 for VMA, and 0.033 μmol ? L?1 for 5‐HIAA (calculated from peak heights), and 0.024 μmol ? L?1 for HVA, 0.020 μmol ? L?1 for VMA, and 0.012 μmol ? L?1 for 5‐HIAA (calculated from peak areas), respectively.  相似文献   

11.
This work reports the application of screen‐printed electrodes bulk‐modified with bismuth precursors to the voltammetric determination of 2‐nitrophenol (2‐NP), 4‐nitrophenol (4‐NP) and 2,4‐dinitrophenol (2,4‐DNP) in water samples. A bismuth film was formed at the electrode surface via in situ reduction of the precursor compound contained in the electrode matrix by cathodic polarization at ?1.20 V. The formation of bismuth layer at the precursor‐modified electrodes was assessed by cyclic voltammetric (CV) at different pH values and by optical techniques. The target nitrophenols were voltammetrically determined by recording their reduction peaks in the differential pulse (DP) mode. The composition and content of the precursor compounds in the printed ink and the effect of the pH of the supporting electrolyte on the DP reduction currents of the 3 target nitrophenols were studied. The limits of quantification (LOQs) in three water matrices (distilled water, tap water and surface water) were in the range 1.1–2.2 µmol L?1. Using a simple solid‐phase extraction (SPE) procedure with Lichrolut EN cartridges and elution with methanol, a preconcentration factor of 100 was achieved; the LOQs were 0.021, 0.027 and 0.025 µmol L?1 for 2‐NP, 4‐NP and 2,4‐DNP, respectively. The recoveries of samples spiked with the 3 target nitrophenols at two concentration levels (0.04 and 0.1 µmol L?1) were always >87 %.  相似文献   

12.
An electrochemical method for the determination of carbaryl, after prior oxidation to 1,4-naphthoquinone in natural water and soils is reported. The coulometric oxidation of carbaryl at a platinum electrode was studied using 0.024 mol/L Britton-Robinson buffer (pH 7.0). The reduction of the oxidation product 1,4-naphthoquinone at a dropping mercury electrode was used for the indirect determination of carbaryl after separation on C18 Sep-pak cartridges by differential pulse polarography (detection limits: 0.41 mg L?1 of water and 0.47 mg kg?1 of soil) and directly without separation by adsorptive stripping voltammetry (detection limits: 5 μg L?1 of water and 7 μg kg?1 of soil, for 75 s preconcentration time). Relative errors were lower than 3.7% and relative standard deviations smaller than 4.5%.  相似文献   

13.
In this article, for the first time, the analytical method for determination of a novel antagonist of A2A adenosine receptors (8‐(4‐methoxyphenyl)‐4‐oxo‐4,6,7,8‐tetrahydroimidazo[2,1‐c][1,2,4]triazine‐3‐carbohydrazide, namely IMT), which can be used as a drug for liver diseases, was presented. For this purpose a commercially available boron‐doped diamond electrode (BDDE) in combination with differential pulse voltammetry (DPV) was applied. It was found by cyclic voltammetry (CV) that IMT displays at BDDE, as a sensor, two well‐defined oxidation peaks at potentials of 0.81 and 1.18 V and one reduction peak at 1.1 V vs. Ag/AgCl in 0.1 mol L?1 acetate buffer (pH 4.5±0.1). The oxidation and reduction mechanism of IMT was proposed. The developed DPV method allowed the successful determination of IMT in the range of 0.05–50 μmol L?1 with detection limit equal to 0.0094 μmol L?1 and without any chemical modifications and electrochemical pretreatment of the electrode surface. The proposed procedure allows the determination of IMT in vitro directly from urine samples.  相似文献   

14.
Composites of gold nanoparticles (Au) electrochemically deposited and different metal phthalocyanines (Co, Ni, Cu, and Fe) were chemically prepared. The composites were used as modifiers for carbon paste electrodes and were used for the determination of morphine in presence of ascorbic acid and uric acid. Central metal atoms of phthalocyanine moiety affected the rate of electron transfer. Thus, the electroactivity of different modifiers were evaluated towards morphine oxidation. Au‐CoPcM‐CPE possessed the highest rate for charge transfer rate in all studied pH electrolytes. Limit of detection was 5.48×10?9 mol L?1 in the range of 4.0×10?7 to 9.0×10?4 mol L?1.  相似文献   

15.
The electrochemical reduction of 5,5′-dichlorohydurilic acid has been studied at the dropping mercury electrode (DME) and the pyrolytic graphite electrode (PGE). At the DME the single polarographic reduction wave observed at pH 6–11 involves a direct 4e—2H+ reduction of the carbon-halogen bond to give hydurilic acid and chloride. The state of hydration or ionization of the 5,5′-dichlorohydurilic acid has no effect on the electrochemical reaction. At the PGE, 5,5′-dichlorohydurilic acid shows two voltammetric peaks. Peak Ic, observed between pH 5 and 7, arises from an overall 4e—2H+ reduction of 5,5′-dichlorohydurilic acid via a mechanism that involves initial electron attack at a carbonyl group alpha to a carbon-halogen bond with simultaneous elimination of chloride ion. The peak IIc process involves an initial 2e—1H+ reduction of a partially hydrated form of 5,5′-dichlorohydurilic acid with only one unhydrated halocarbonyl moiety available for reaction. Attack is again via the carbonyl group with simultaneous elimination of chloride and formation of 5-chlorohydurilic acid. A chemical dehydration step then occurs with a rate constant of ca. 0.24 s?1 at pH 8.2, with formation of a further reducible halocarbonyl group. This is again reduced in an overall 2e—2H+ reaction to give hydurilic acid and chloride ion. The peak IIc process hence proceeds via an ECE mechanism. The different mechanisms observed for reduction of 5,5′-dichlorohydurilic acid at mercury and pyrolytic graphite electrodes are unusual. Analytical methods have been developed for the polarographic determination of 5,5′-dichlorohydurilic acid via its reduction wave at the DME, and for the voltammetric determination of hydurilic acid via its first oxidation peak at the PGE.  相似文献   

16.
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   

17.
As an alternative selection of electrocatalytic surface modifier, the electrochemically generated copper oxides is re‐ investigated by using cyclic voltammetry (CV), scanning electron microscopy (SEM) and X‐ray photoelectron spectroscopy (XPS). Interesting phenomena have been found, which indicate that the electrodeposition from the Cu2+ solution under cyclic voltammetric conditions can generate a transparent Cu(OH)2 crystalline on the surface of glassy carbon electrodes, and this crystalline can be further transferred to a novel cubic opaque CuO crystalline of about 300 nm in size by second step of cyclic voltammetry in pH 12 NaOH solution. The final electrode (denoted as nano‐CuO/GCE) can catalyze the oxidation (as well as the reduction) of H2O2 in basic solutions. It shows pH dependent three‐part catalytic mechanism in the range from pH 7 to pH 14. In 0.10 mol/L NaOH solution, the amperometric response at 0.15 V (vs. SCE) can give a current sensitivity as high as 139 mA/(mol·L?1) in the rage of 5.0×10?7?6.0×10?4 mol/L with a lower detection limit (s/n=3) of 2.5×10?8 mol/L, and a current sensitivity of 78.4 mA/(mol·L?1) in the rage of 6.0×10?4–2.0×10?3 mol/L. This electrode also has excellent reproducibility and stability. The mechanisms for the two steps of preparation and the catalytic reactions are proposed. The nano‐CuO crystalline modified electrode may have more applications in the field of electrochemical sensing.  相似文献   

18.
《Electroanalysis》2005,17(17):1511-1515
Differential pulse voltammetric determination of selenocystine (SeC) using selenium‐gold film modified glassy carbon electrode ((Se‐Au)/GC) is presented. In 0.10 mol?L?1 KNO3 (pH 3.20) solution, SeC yields a sensitive reduction peak at ?740 mV on (Se‐Au)/GC electrode. The peak current has a linear relationship with the concentration of SeC in the range of 5.0×10?8–7.0×10?4 mol?L?1, and a 3σ detection limit of SeC is 3.0×10?8 mol?L?1. The relative standard deviation of the reduction current at SeC concentration of 10?6 mol?L?1 is 3.88% (n=8) using the same electrode, and 4.19% when using three modified electrodes prepared at different times. The content of SeC in the selenium‐enriched yeast and selenium‐enriched tea is determined. The total selenium in ordinary or selenium‐enriched tea is determined by DAN fluorescence method. The results indicate that in selenium‐enriched yeast about 20% of total selenium is present as SeC and in selenium‐enriched tea SeC is the major form of selenoamino acids. The total selenium content in selenium‐enriched tea soup is 0.09 μgSe/g accounting by 7% compared with that in selenium‐enriched tea. Hence, only a little amount of selenium is utilized by drinking tea, and most selenium still stay in tealeaf. Uncertainty are 22.4% and 16.1% for determination of SeC in selenium‐enriched yeast and selenium‐enriched tea by differential pulse voltammetry (DPV) on (Se‐Au)/GC electrode, respectively.  相似文献   

19.
The exploitation of metal‐free organic polymers as electrodes for water splitting reactions is limited by their presumably low activity and poor stability, especially for the oxygen evolution reaction (OER) under more critical conditions. Now, the thickness of a cheap and robust polymer, poly(p‐phenylene pyromellitimide) (PPPI) was rationally engineered by an in situ polymerization method to make the metal‐free polymer available for the first time as flexible, tailorable, efficient, and ultra‐stable electrodes for water oxidation over a wide pH range. The PPPI electrode with an optimized thickness of about 200 nm provided a current density of 32.8 mA cm?2 at an overpotential of 510 mV in 0.1 mol L?1 KOH, which is even higher than that (31.5 mA cm?2) of commercial IrO2 OER catalyst. The PPPI electrodes are scalable and stable, maintaining 92 % of its activity after a 48‐h chronoamperometric stability test.  相似文献   

20.
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   

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