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1.
Ly SY 《Talanta》2008,74(5):1635-1641
The voltammetric assay of Cu(II) was investigated using a carbon nanotube electrode (CNE) and fluorine immobilized onto a carbon nanotube electrode (FCNE) in cyclic voltammetry (CV), square-wave (SW) stripping voltammetry, and chronoamperometry. Optimum SW conditions were attained at working ranges of 0.01–0.11 ng L−1 Cu(II) (11 points), and a relative standard deviation of 1.68% (RSD, n = 15) was observed at 10.0 μg L−1 Cu(II). Within a 200 s accumulation time, detection limit of 0.006 μg L−1 was attained. The life span of each electrode was more than 1 month. The sensor was applied to tap water, blood, and rat tail vascular (in vivo). It was found that the sensor could be used with an interface system in the assay of live cells and non-treated blood.  相似文献   

2.
A highly selective, fast and stable biosensor for determination of glucose in soluble coffee has been developed. The biosensor electrode consist of a thin film of ferric hexacyanoferrate (Prussian Blue or PB) electrodeposited on the glassy carbon electrode (GCE) (to provide a catalytic surface for the detection of hydrogen peroxide) glucose oxidase immobilized on top of the electrode and a Nafion® polymer layer. The stability of the PB film and the biosensor was evaluated by injecting standard-solution (50 μM H2O2 and 0.5 mM glucose) during 4 h in a flow-injection system with the electrodes polarized at −50 mV versus Ag/AgCl. The system is able to handle about 60 samples per hour and is very stable and suitable for industrial control. Determination of glucose in the range 2.5 and 15% (w/v) in phosphate buffer with precision (r.s.d. < 1.5%) has been achieved and is in agreement with the conventional procedures. Linear calibration in the range of 0.15 and 2.50 mM with detection limits of ca. 0.03 mM has been obtained. The morphology of the enzyme glucose oxidase on the modified electrode has been analyzed by scanning electron microscopy (SEM) measurements.  相似文献   

3.
Flow injection (FI) and sequential injection (SI) systems with anodic stripping voltammetric detection have been exploited for simultaneous determination of some metals. A pre-plated mercury film on a glassy carbon disc electrode was used as a working electrode in both systems. The same film can be repeatedly applied for at least 50 analysis cycles, thus reducing the mercury consumption and waste. A single line FI voltammetric system using an acetate buffer as a carrier and an electrolyte solution was employed. An injected standard/sample zone was mixed with the buffer in a mixing coil before entering a flow cell. Metal ions were deposited on the working electrode by applying a potential of −1.1 V vs Ag/AgCl reference electrode. The stripping was performed by anodically scanning potential of working electrode to +0.25 V, resulting a voltammogram. Effects of acetate buffer concentration, flow rate and sample volume were investigated. Under the selected condition, detection limits of 1 μg l−1 for Cd(II), 18 μg l−1 for Cu(II), 2 μg l−1 for Pb(II) and 17 μg l−1 for Zn(II) with precisions of 2–5% (n=11) were obtained. The SI voltammetric system was similar to the FI system and using an acetate buffer as a carrier solution. The SI system was operated by a PC via in-house written software and employing an autotitrator as a syringe pump. Standard/sample was aspirated and the zone was then sent to a flow cell for measurement. Detection limits for Cd(II), Cu(II), Pb(II) and Zn(II) were 6, 3, 10 and 470 μg l−1, respectively. Applications to water samples were demonstrated. A homemade UV-digester was used for removing organic matters in the wastewater samples prior to analysis by the proposed voltammetric systems.  相似文献   

4.
Silva AR  Nogueira JM 《Talanta》2008,74(5):1498-1504
Stir bar sorptive extraction and liquid desorption followed by high performance liquid chromatography with diode array detection (SBSE-LD-LC-DAD) is proposed for the determination of triclosan in personal care products, biological and environmental matrices, which is included in the priority lists, set by several international regulatory organizations. Instrumental conditions and experimental parameters that affecting SBSE-LD efficiency are fully discussed. Throughout systematic assays on 25 mL water samples spiked at the 10.0 μg L−1 level, it had been established that stir bars coated with 126 μL of polydimethylsiloxane, an equilibrium time of 1 h (1000 rpm) and acetonitrile under sonification (60 min) as back-extraction solvent, allowed the best analytical performance to determine triclosan in water matrices. From the data obtained, good recovery and remarkable repeatability were attained, providing experimental average yields (78.5 ± 2.2%), although slightly lower than the theoretical equilibrium (99.7%) described by the octanol–water partition coefficients (KPDMS/W < KO/W). The analytical performance proved suitable precision (<3.6%), convenient detection limits (0.1 μg L−1) and excellent linear dynamic range (r2 > 0.9992) from 0.4 to 108.0 μg L−1. The application of the present method to determine triclosan in real matrices such as commercial toothpaste, saliva and urban wastewater samples, allowed appropriate selectivity, high sensitivity and accuracy using the standard addition methodology. The proposed method showed to be feasible and sensitive with a low-sample volume requirement to monitor triclosan in personal care products, biological and environmental matrices at the trace level, in compliance with international regulatory directives.  相似文献   

5.
Siswana M  Ozoemena KI  Nyokong T 《Talanta》2006,69(5):1136-1142
This paper describes the construction of a carbon paste electrode (CPE) impregnated with nanoparticles of iron(II) phthalocyanine (nanoFePc). The new electrode (nanoFePc-CPE) revealed interesting electrocatalytic behaviour towards amitrole; pure catalytic diffusion-controlled process, with high Tafel slope (235 mV/decade) suggesting strong binding of amitrole with nanoFePc catalyst. The effects of catalyst loading, varying pH and electrolytes were studied. The mechanism for the interaction of amitrole with the nanoFePc is proposed to involve the Fe(III)Pc/Fe(II)Pc redox process. Using chronoamperometry (E = +0.42 V versus Ag/AgCl) technique, the sensor was reliably employed for amitrole assay at pH 12.0 phosphate buffer (with sodium sulphate as the supporting electrolyte) for up to 12 nM amitrole with excellent sensitivity (ca. 3.44 μA/nM) and low detection limit (3.62 ± 0.11 nM, i.e. 0.305 μg L−1 using the YB + 3σB criterion and 0.85 ± 0.03 nM, i.e. 70 ng/L with the YB + 2σB criterion) as well as satisfactory amperometric selectivity coefficient (Kamp ≈ 7.4 × 10−4 for ammonium thiocyanate, a component of many amitrole herbicides, and 3.2 × 10−3 for asulam pesticide). The surface of the electrode can easily be regenerated by simple polishing on an alumina paper, obtaining a fresh surface ready for use in a new assay. The proposed electrode was successfully applied in the quantification of amitrole in its commercial formulation as well as in tap water samples.  相似文献   

6.
An electrochemiluminescence (ECL) sensor with good long-term stability and fast response time has been developed. The sensor was based on the immobilization of tris(2,2′-bipyridyl)ruthenium(II) (Ru(bpy)32+) into the Eastman-AQ55D–silica composite thin films on a glassy carbon electrode. The ECL and electrochemistry of Ru(bpy)32+ immobilized in the composite thin films have been investigated, and the modified electrode was used for the ECL detection of oxalate, tripropylamine (TPA) and chlorpromazine (CPZ) in a flow injection analysis system and showed high sensitivity. Because of the strong electrostatic interaction and low hydrophobicity of Eastman-AQ55D, the sensor showed no loss of response over 2 months of dry storage. In use, the electrode showed only a 5% decrease in response over 100 potential cycles. The detection limit was 1 μmol l−1 for oxalate and 0.1 μmol l−1 for both TPA and CPZ (S/N=3), respectively. The linear range extended from 50 μmol l−1 to 5 mmol l−1 for oxalate, from 20 μmol l−1 to 1 mmol l−1 for TPA, and from 1 μmol l−1 to 200 μmol l−1 for CPZ.  相似文献   

7.
Capillary electrophoresis (CE) was employed for the determination of cytochrome c using a wall-jet amperometric detector consisting a copper(I) oxide-modified sol–gel carbon composite electrode (CCE), which exhibits a sensitive electrocatalytic response for the oxidation of cytochrome c. The optimum conditions of separation and detection are 0.08 M NaOH for the separation solution, 12 kV for separation voltage and +0.60 V versus saturated calomel electrode (SCE) for the detection potential. Calibration was linear over the concentration range 1–600 μM with the limit of detection of 3.4 μM, based on a signal-to-noise ratio (S/N) of 3.  相似文献   

8.
Zen JM  Hsu CT 《Talanta》1998,46(6):1363-1369
A square-wave voltammetric method together with Nafion®-coated carbon paste electrodes were used for the selective determination of uric acid in the presence of a high concentration of ascorbic acid. Since the oxidation potential of uric acid is about 200 mV more positive than that of ascorbic acid at the Nafion®-coated carbon paste electrode, the selectivity can be greatly improved simply by applying an electrolysis potential of +0.4 V vs. Ag/AgCl where only ascorbic acid is oxidised. The acceptable tolerance of ascorbic acid concentration for the determination of uric acid is as high as 1.5 mM. With 30 s of electrolysis time, a linear calibration curve is obtained over the 0–50 μM range in 0.05 M citrate buffer solution, pH 4.0, with slope (μA/μM) and correlation coefficient of 0.34 and 0.9984, respectively. The detection limit (3σ) is 0.25 μM. The practical analytical utility is illustrated by selective measurements of uric acid in human urine without any preliminary treatment.  相似文献   

9.
A highly selective dopamine quantification at a new polymer-modified electrode in the presence of large excess of ascorbic acid and 3,4-dihydroxyphenyl acetic acid (dopac) is described. The electrochemical detection was performed at a glassy carbon electrode modified with a melanin-type polymer obtained by polymerization of 3.0×10−3 M -dopa in 0.050 M phosphate buffer solution pH 7.40 by applying 1.00 V for 60 min. The polymeric film exhibits attractive permselectivity excluding anionic species such as potassium ferricyanide, ascorbic acid, dopac and uric acid. Cationic species such as epinephrine, norepinephrine and dopamine and neutral ones such as catechol and hydrogen peroxide can be oxidized at the polymer-modified electrode. The use of ascorbic acid in the measurement solution allows the amplification of dopamine oxidation signal due to the reduction of the electrochemically generated dopaminequinone. By using 1.0×10−3 M ascorbic acid, the detection limit for dopamine is 5.0 nM. The interference for the maximum physiological concentrations of ascorbic acid and dopac in nervous centers, i.e. 500 μM ascorbic acid and 50 μM dopac is 8.1 and 1.4%, respectively.  相似文献   

10.
Shih Y  Zen JM  Kumar AS  Chen PY 《Talanta》2004,62(5):912-917
Zinc pyrithione (ZPT) is an antibacterial and antifungal reagent that is often utilized for the antidandruff activity in hair-care shampoos with a composition level up to 1% in the formulation. It has some adverse effects to human and animal if consumed orally. A disposable type of cobalt phthalocyanide modified screen-printed carbon electrode (CoPc/SPE) in couple with flow injection analysis (FIA) was developed for easy and selective analysis of ZPT in commercial hair-care products. Under the optimized FIA conditions, the CoPc/SPE yielded a linear calibration plot in the window of 6–576 μM with sensitivity and detection limit of 1.65 nA μM−1 and 0.9 μM (i.e. 1.42 pg in 5 μl sample loop), respectively, in 0.1 M KOH solution at an applied potential of 0.3 V versus Ag/AgCl. Since the approach is simple, easy, selective, and inexpensive, it offers a potential application of daily ZPT analysis in hair-care products.  相似文献   

11.
Flow injection (FI) analysis of copper as the copper diethylthiocarbamate complex (Cu(Et2dtc)2) has been performed in a high resistance toluene carrier stream. The method is based on the oxidation of the copper complex at a platinum microelectrode fabricated to fit a Metrohm wall-jet flow cell. Electrodes of sizes 5 to 25 μm radii were tested in toluene-based carriers containing either 0.03 M tetrahexylammonium perchlorate (Hex4NClO4) or 35% acetonitrile. Detection limits (3 : 1 signal to noise ratio) in the range 1 × 10−7 M (5 μm radius electrode) to 5 × 10−8 M (25 μm radius electrode) were achieved, which are comparable to detection limits reported in lower resistance media under similar conditions. The system was applied to the analysis of copper in water samples after extraction of the metal as its diethyldithiocarbamate into toluene and good agreement was found with data obtained by other voltammetric methods.  相似文献   

12.
The bismuth film electrode (BiFE), in combination with anodic stripping voltammetry, offers convenient measurement of low concentrations of tin. The procedure involves simultaneous in situ formation of the bismuth film electrode on a glassy carbon substrate electrode, together with electrochemical deposition of tin, in a non-deaerated model solution containing bismuth ions, catechol as complexing agent and the metal analyte, followed by an anodic stripping scan. The BiFE is characterized by an attractive electroanalytical performance, with two distinct voltammetric stripping signals corresponding to tin, accompanied with low background contributions. Several experimental parameters were optimized, such as concentration of bismuth ions and catechol, deposition potential, deposition time and pH of the model solution. In addition, a critical comparison is given with bare glassy carbon and mercury film electrodes, revealing the superior characteristics of BiFE for measurement of tin. BiFE exhibited highly linear behavior in the examined concentration range from 1 to 100 μg L−1 of tin (R2 = 0.997), an LoD of 0.26 μg L−1 tin, and good reproducibility with a calculated R.S.D. of 7.3% for 10 μg L−1 tin (n = 10). As an example, the practical applicability of BiFE was tested with the measurement of tin in a real sample of seawater.  相似文献   

13.
Automated sequential injection (SIA) method for chemiluminescence (CL) determination of nonsteroidal anti-inflammatory drug indomethacin (I) was devised. The CL radiation was emitted in the reaction of I (dissolved in aqueous 50% v/v ethanol) with intermediate reagent tris(2,2′-bipyridyl)ruthenium(III) (Ru(bipy)33+) in the presence of acetate. The Ru(bipy)33+ was generated on-line in the SIA system by the oxidation of 0.5 mM tris(2,2′-bipyridyl)ruthenium(II) (Ru(bipy)32+) with Ce(IV) ammonium sulphate in diluted sulphuric acid. The optimum sequence, concentrations, and aspirated volumes of reactant zones were: 15 mM Ce(IV) in 50 mM sulphuric acid 41 μL, 0.5 mM Ru(bipy)32+ 30 μL, 0.4 M Na acetate 16 μL and I sample 15 μL; the flow rates were 60 μL s−1 for the aspiration into the holding coil and 100 μL s−1 for detection. Calibration curve relating the intensity of CL (peak height of the transient CL signal) to concentration of I was curvilinear (second order polynomial) for 0.1–50 μM I (r = 0.9997; n = 9) with rectilinear section in the range 0.1–10 μM I (r = 0.9995; n = 5). The limit of detection (3σ) was 0.05 μM I. Repeatability of peak heights (R.S.D., n = 10) ranged between 2.4% (0.5 μM I) and 2.0% (7 μM I). Sample throughput was 180 h−1. The method was applied to determination of 1 to 5% of I in semisolid dosage forms (gels and ointments). The results compared well with those of UV spectrophotometric method.  相似文献   

14.
This article reports on the use of cobalt(II) phthalocyanine (CoPc)-modified carbon paste amperometric detector for monitoring hydrazine compounds following their microchip separation. The marked catalytic electrochemical properties of CoPc-modified electrode display enhanced sensitivity compared with unmodified carbon pastes at a relatively low detection potential (+0.5 V versus Ag/AgCl). Factors influencing the on-chip separation and detection processes have been optimized. Three hydrazines (hydrazine, 1,1 dimethylhydrazine, and phenylhydrazine) have been separated within 130 s at a separation voltage of 1 kV using a 10 mM phosphate run buffer (pH 6.5). The detection limits obtained from using the CoPc-modified carbon paste electrodes for hydrazine and phenylhydrazine are 0.5 and 0.7 μM, respectively, with linearity over the 20–200 μM range examined. Such miniaturization and speed advantages of microchip CE are coupled to the highly sensitivity and convenient preparation of CoPc-modified carbon paste electrode. The resulting microsystem should be attractive for field monitoring of toxic hydrazine compounds in environmental applications.  相似文献   

15.
Previously it was shown that four different aliphatic polyamines can be quantitatively electrooxidized at boron-doped diamond thin film electrodes without derivatization or the use of pulsed voltammetric waveforms [Anal. Chem. 71 (1999) 1188; Anal. Chem. 69 (1997) 4041]. The flow injection analysis (FIA-EC) investigation (amperometric detection mode) of cadaverine (CAD), putrescine (PUT), spermine (SPM) and spermidine (SPMD), reported previously [Anal. Chem. 71 (1999) 1188], are updated herein with particular emphasis on the electrode response variability and stability. Most of the measurements were made with a film deposited from a 0.50% methane-to-hydrogen (C/H) volumetric ratio. In general, films deposited with C/H ratios near this value tend to possess the requisite physicochemical properties to support anodic oxygen transfer reactions. The electrode performance was evaluated in terms of the linear dynamic range, limit of quantitation, response variability and response stability. A linear dynamic range from 1.0 μM to 1.0 mM and a limit of quantitation of 1.0 μM or 20 pmol injected (S/N≥3) were found for CAD, PUT, and SPMD. For SPM, a linear dynamic range from 0.32 μM to 1.0 mM and a limit of quantitation of 0.32 μM or 6.4 pmol were observed. The response variability, as low as 2–4%, was observed which is vastly improved over previous results. The improvement was achieved by introducing a 3–6 min delay period between injections. The long-term response stability was good with no evidence for any progressive response attenuation or complete fouling by the reaction product, even though a solid deposit was observed to accumulate on the electrode surface with extended use. The deposit appears to partially reduce the active electrochemical area for polyamine oxidation and to decrease the overpotential for water discharge. Preliminary chromatographic results demonstrated the possibility of separating and detecting the polyamines by a simple reverse-phase scheme at constant applied potential.  相似文献   

16.
Manesh KM  Santhosh P  Gopalan A  Lee KP 《Talanta》2008,75(5):1307-1314
A new modified electrode is fabricated by dispersing gold nanoparticles onto the matrix of poly(3,4-ethylenedioxythiophene)–poly(styrene sulfonic acid), PEDOT–PSS. The electrocatalytic activity of the PEDOT–PSS-Aunano electrode towards the oxidation of β-nicotinamide adenine dinucleotide (NADH) is investigated. A substantial decrease in the overpotential (>0.7 V) has been observed for the oxidation of NADH at the PEDOT–PSS-Aunano electrode in comparison to the potential at PEDOT–PSS electrode. The Au nanoparticles dispersed in the PEDOT–PSS matrix prevents the fouling of electrode surface by the oxidation products of NADH and augments the oxidation of NADH at a less positive potential (+0.04 V vs. SCE). The electrode shows high sensitivity to the electrocatalytic oxidation of NADH. Further, the presence of ascorbic acid and uric acid does not interfere during the detection of NADH. Important practical advantages such as stability of the electrode (retains 95% of its original activity after 20 days), reproducibility of the measurements (R.S.D.: 2.8%; n = 5), selectivity and wide linear dynamic range (1–80 μM; R2 = 0.996) are achieved at PEDOT–PSS-Aunano electrode. The ability of PEDOT–PSS-Aunano electrode to promote the electron transfer between NADH and the electrode makes us to fabricate a biocompatible dehydrogenase-based biosensor for the measurement of ethanol. The biosensor showed high sensitivity to ethanol with rapid detection, good reproducibility and excellent stability.  相似文献   

17.
The electrochemical determination of iodide was studied at boron-doped diamond thin film electrodes (BDD) using cyclic voltammetry (CV) and flow-injection (FI) analysis, with amperometric detection. Cyclic voltammetry of iodide was conducted in a phosphate buffer pH 5. Experiments were performed using glassy carbon (GC) electrode as a comparison. Well-defined oxidation waves of the quasi-reversible cyclic voltammograms were observed at both electrodes. Voltammetric signal-to-background ratios (S/B) were comparable. However, the GC electrode gives much greater in the background current as usual. The potential sweep rate dependence exhibited that the peak current of iodide oxidation at 1 mM varied linearly (r2 = 0.998) with the square root of the scan rate, from 0.01 to 0.30 V s−1. This result indicates that the reaction is a diffusion-controlled process with negligible adsorption on BDD surface, at this iodide concentration. Results of the flow-injection analysis show a highly reproducible amperometric response. The linear working range was observed up to 200 μM (r2 = 0.999). The detection limit, as low as 0.01 μM (3σ of blank), was obtained. This method was successfully applied for quantification of iodide contents in nuclear emergency tablets.  相似文献   

18.
A stable electro active thin film of cobalt hexacyanoferrate (CoHCF) was deposited on the surface of an amine adsorbed graphite wax composite electrode using a simple method. Cyclic voltammetric experiments showed two pairs of well defined peaks for this CoHCF modified electrode which exhibited excellent electrocatalytic property for the oxidation of paracetomol at a reduced overpotential of 100 mV and over a concentration range of 3.33 × 10−6 to 1.0 × 10−3 M with a slope of 0.208 μA/μM with good sensitivity. The influence of the supporting electrolyte on peak current and peak potential were also obtained in addition with effects of common interference (e.g., ascorbic acid) on the response of the modified electrode. Various parameters that influence the electrochemical behavior of the modified electrode were optimized by varying scan rates and pH. Electrochemical impedance spectroscopy studies suggested that the electrode reaction of the CoHCF film is mainly controlled by transport of counter ion. The immobilized CoHCF maintained its redox activity showing a surface controlled electrode reaction with the electron transfer rate constant (Ks) of 0.94 s−1 and charge transfer coefficient of 0.42. Hydrodynamic and chronoamperometric studies were done to explore the utility of the modified electrode in dynamic systems. The results of the differential pulse voltammetry (DPV) using the modified electrode was applied for the determination of paracetomol in commercially available tablets. The results obtained reveal that the electrode under study could be used as an effective sensor for online monitoring of paracetomol.  相似文献   

19.
The electronics and construction for an end-column ultramicroelectrode (3–10 μm) detection system that permits the use of medium-sized capillaries (25 μm I.D.) without appreciable effects from the potential field at the end of the capillary. Normal peak-to-peak noise over 10 s was 0.01–0.1 pA. The background noise observed for a 200 × μm carbon-fiber electrode placed either 180 μm within a 25-μm capillary or at a point 500 μm away from the capillary was essentially the same. A study of detector response as a function of the position of the electrode has shown that accurate location of the electrode is important for sensitive and reproducible detection. These studies also showed that differences between the density of the electrolyte existing the capillary and the electrolyte in the detection cell could cause anomalous electrode response depending on the location of the electrode relative to the end of the capillary. Application of a carbon fiber or an Hg film electrode gave detection limits (twice the peak-to-peak noise over 10 s) of 2 · 10−8 mol/l for Pb2+, 1 · 10− 5 mol/l for NO2 and 5 · 10−10 mol/l for catechol.  相似文献   

20.
The voltammetric behavior of 2-methyl-4,6-dinitrophenol at a modified carbon paste electrode has been studied. Among the modifiers tested, hidepowder was found to give the best results. Cyclic voltammetry and differential pulse voltammetry were used to study the nature of the reaction; the possibility of accumulation of the analyte onto the electrode was studied by differential pulse voltammetry. An irreversible behavior and the adsorption of 2-methyl-4,6-dinitrophenol on the electrode were confirmed. The reduction signal shows two peaks. A linear relationship between the first peak height and the concentration of 2-methyl-4,6-dinitrophenol was obtained in the range 0.001–5 mg l−1, with a detection limit of 3.2 μg l−1 and a relative standard deviation of 3.20%. The interferences with the reduction peak of 2-methyl-4,6-dinitrophenol of several nitro- and chloro-phenols and inorganic species were tested.  相似文献   

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