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1.
《Electroanalysis》2006,18(1):64-69
Efficient and stable electrocatalytic activity for the reduction of O2 at activated screen‐printed carbon electrodes modified with palladium nanoparticles (SPE*‐Pd) was demonstrated in this study. X‐ray photoelectron spectroscopy confirmed the formation of >C?O functional group on electrode surface during the preanodization procedure at 2.0 V (vs. Ag/AgCl). The existence of chloride moieties was also identified possibly from the organic binder of carbon ink used in SPE fabrication. Both >C?O and chloride functional groups were essential for the excellent stability of the SPE*‐Pd. Electrochemical impedance spectroscopy verified the enhanced kinetic rate of oxygen reduction reaction at the as‐prepared Pd nanoparticles. The SPE*‐Pd showed ca. 250 mV positive shift in peak potential together with twice increase in peak current compared to those observed at a SPE‐Pt. The calibration plot was linear up to 8 ppm of DO with sensitivity and regression coefficient of 4.49 μA/ppm and 0.9936, respectively. The variation coefficient of ipc for 7 DO determinations with O2‐saturated pH 7.4 PBS was 2.1%. Real sample assays for ground and tap waters gave consistent values to those measured by a commercial dissolved oxygen meter.  相似文献   

2.
Chemically modified screen printed electrodes (CM‐SPE) using [UO2(4‐MeOSalen)(H2O)] ? H2O films were employed in the voltammetric determination of cocaine. The chemical modification was performed by dip coating electrode surfaces (carbon, gold, and platinum) with methanolic solution containing the Schiff base complex with subsequent drying step at room temperature. The optimized amount of the chemical modifier over the working electrode was found to be 2.39 µg mm?2 (geometric area). The voltammetric measurements were carried out in 50 : 50 v/v methanol:water solution containing 0.05 mol L?1 KCl and 0.1 mol L?1 LiCl as a supporting electrolyte without oxygen elimination by inert gas flow. The best results were obtained with carbon electrodes. Cocaine exhibits a well defined irreversible anodic peak current (ipa) at a potential (Epa) of 0.85 V vs Ag/AgCl. The current is directly proportional to the drug concentration. An optimal accumulation potential (Eprec), and time (tprec) of ?0.80 V (vs Ag/AgCl), and 120 s, respectively, were determined. The linear dependence of ipa with square root of scan rate (υ) indicates that the mass transport at the electrode surface is controlled by diffusion. An optimized scan rate of 100 mV s?1 was obtained for analytical purposes. A limit of detection (LOD) and limit of quantification (LOQ) in 110 and 390 µmol L?1, respectively, with intra and inter‐day repeatability of 2.61 % and 3.77 %, respectively, were obtained. In interference studies the proposed method demonstrated high specificity for cocaine in the presence of morphine and 3,4‐methylenedioxymethanphetamine. The above results demonstrate that this method provides a fast and low cost procedure for determination of cocaine in trace levels.  相似文献   

3.
An ionic liquid N‐hexylpyridinium hexafluorophosphate (HPPF6) modified carbon paste electrode was fabricated for the sensitive voltammetric determination of adenosine in this paper. Carbon ionic liquid electrode (CILE) was prepared by mixing graphite powder and HPPF6 together and the CILE was characterized by scanning electron microscopy (SEM) and electrochemical methods. The electrochemical behaviors of adenosine on the CILE were studied carefully. Compared with the traditional carbon paste electrode (CPE), a small negative shift of the oxidation peak potential appeared with greatly increase of the oxidation peak current, which indicated the presence of ionic liquid in the carbon paste not only as the binder but also as the modifier and promoter. Under the optimal conditions the oxidation peak current increased with the adenosine concentration in the range from 1.0×10?6 mol/L to 1.4×10?4 mol/L with the detection limit of 9.1×10?7 mol/L (S/N=3) by differential pulse voltammetry. The proposed method was applied to the human urine samples detection with satisfactory results.  相似文献   

4.
Hemin was physically adsorbed onto porous carbon felt (CF), a microelectrode ensemble of micro-carbon fiber (ca. 7 μm in diameter) and possessing a three-dimensional random structure. The hemin-CF exhibited a well-defined redox wave that is due to Fe(III)/Fe(II) redox process in hemin, with a formal potential of ?0.32 V (vs. Ag/AgCl) in deoxygenated buffer solution of pH 7.0. The surface coverage of the electroactive hemin molecules on the surface of the CF was calculated to be 5.0?×?10?11 mol cm?2, and the apparent heterogeneous electron transfer rate constant is 3.35 s?1. The hemin-CF electrode displays excellent electrocatalytic activity for the reduction of dissolved oxygen (DO), and the magnitude of the cathodic current increases with increasing concentrations of DO in the sample solution. The electrode was used as a flow-through detector for sensitive and rapid consecutive determination of DO. Deoxygenated pH 7.0 solutions were analyzed at a flow rate of 8.0 mL min?1 at an applied potential of ?0.2 V, and highly reproducible cathodic peak current responses to DO were observed in the 0.72 to 13.3 mg L?1 concentration range. The maximum throughput is 170 samples h?1. The hemin-CF-based amperometric flow-sensor was applied to determine the concentration of DO in environmental water samples.
Graphical abstract
Hemin was physically adsorbed onto porous carbon felt (CF), a microelectrode ensemble of micro-carbon fiber (ca. 7 μm in diameter). The hemin-CF electrode was used as a flow-through detector for highly sensitive and rapid determination of dissolved oxygen.  相似文献   

5.
This paper describes the preparation of a new sensor based on Zn‐ferrite modified glassy carbon paste electrode and its electrochemical application for the determination of trace Cd(II) ions in waste waters using differential pulse anodic stripping voltammetry (DPASV). Different Zn/Ni ferrite nanoparticles were synthesized and characterized using scanning electron microscopy (SEM) and X‐ray powder diffraction (XRPD). The prepared ferrite nanoparticles were used for the preparation of Zn‐ferrite‐modified glassy carbon paste electrode (ZnMGCPE) for determination of Cd(II) at nanomolar levels in waste water at pH 5. The different parameters such as conditions of preparation, Zn2+/Ni2+/Fe2+ ratio and electrochemical parameters, percentage of modifier, accumulation time, pH and accumulation potential were investigated. Besides, interference measurements were also evaluated under optimized parameters. The best voltammetric response was observed for ZnFe2O4 modifier, when the percentage of modifier was 3 %, accumulation time 9 min, pH of supporting electrolyte 5 and accumulation potential ?1.05 V. Thus prepared electrode displays excellent response to Cd(II) with a detection limit of 0.38 ppb, and selective detection toward Cd(II) was achieved.  相似文献   

6.
Electrocatalysis of epinephrine at gold electrode pre‐modified with the self‐assembled monolayer of cysteamine and subsequently integrated with novel metallo‐octacarboxyphthalocyanine (MOCPc where M=Fe, Co and Mn) complexes (Au‐Cys‐MOCPc) was investigated. The electrodes showed response to the presence of epinephrine. The oxidation peak potential (Ep/V vs. Ag|AgCl, sat'd KCl) and charge transfer resistance (Rct (kΩ)) in epinephrine solution depend markedly on the central metal of the phthalocyanine cores: Au‐Cys‐FeOCPckch=4.1×107 M?1 s?1) which is higher than that of the Au‐cys‐CoOCPc or Au‐cys‐MnOCPc electrode. Mechanism, recognizing the mediation of the electrocatalytic process by the central M(II)/M(III) redox processes was proposed. Epinephrine electro‐oxidation at the Au‐cys‐FeOCPc electrode was studied in more details for the response characteristics. The diffusion coefficient of epinephrine was evaluated as (2.62±0.23)×10?9 cm2 s?1. It was established that Au‐Cys‐FeOCPc is suitable for sensitive determination of epinephrine in physiological pH (7.40) conditions showing linear concentration range of up to 300 nM, with excellent sensitivity (0.53±0.01 nA nM?1), and very low limits of detection (13.8 nM) and quantification (45.8 nM). The peak separation between ascorbic acid and epinephrine is large enough (190 mV) to permit simultaneous determination of both epinephrine and ascorbic acid in physiological pH 7.4 conditions using the Au‐cys‐FeOCPc electrode. Au‐cys‐FeOCPc electrode was successfully used for the determination of epinephrine in epinephrine hydrochloric acid injection with recovery of ca. 98.4%.  相似文献   

7.
A preanodized screen‐printed ring disk carbon electrode was applied to the determination of chloramphenicol (Ph? NO2, CAP) by flow injection analysis (FIA). By setting up the first irreversible reduction reaction of Ph? NO2 to Ph? NHOH at the disk electrode, the following reversible oxidation of hydroxylamine (Ph? NHOH) to the nitroso (Ph? NO) derivative can be monitored/collected at the ring electrode for CAP analysis. The interference from dissolved oxygen and others can thus be avoided by using this approach and precise CAP determination can be easily performed by FIA under aerobic conditions. Preanodization treatment helps to lower the overpotential of the electrochemical reaction of CAP and favors the selective detection in aqueous medium. Under the optimum conditions, ten repetitive determinations at 1 μM and 10 μM CAP resulted in relative standard deviations of less than 4%, indicating good reproducibility of the system. A linear calibration range of 0.1–20 μM with a detection limit of 0.074 μM (S/N=3) was obtained. Veterinary pharmaceutics were finally analyzed by this sensor to validate its practical applicability.  相似文献   

8.
《Electroanalysis》2017,29(5):1368-1376
In this work, a photoamperometric glucose biosensor based on glucose oxidase (GODx) was developed in flow injection analysis (FIA) system using ZnS‐CdS quantum dot (QD) modified multiwalled carbon nanotube/glassy carbon electrode (ZnS‐CdS/MWCNT/GCE). Cyclic voltammograms of the proposed electrode (GODx/ZnS‐CdS/MWCNT/GCE) showed a pair of well‐defined reversible redox peak attributing that direct electron transfer between the protein and electrode. The current of the reduction peak became more cathodic in the presence of O2 due to the electrocatalytic activity of the electrode towards the reduction of dissolved O2, but reduction current shifted to a less negative value upon addition of glucose in the solution. The obtained CV currents were affected by the irradiation of the electrode surface. Thus, the photoelectrochemical biosensing of glucose in the FIA system was studied by monitoring of the changes in the electrocatalyzed reduction peak current of dissolved O2 at the proposed electrode dependent on glucose concentration. The proposed photoelectrochemical FIA method has a linear response to glucose ranging from of 0.01 to 1.0 mM with detection limit of 3.0 μM under optimized conditions. Photoelectrochemical biosensor was successfully fabricated in FIA system for selective, sensitive and repeatable detection of glucose and has been satisfactorily applied to determination of glucose in real sample.  相似文献   

9.
《Electroanalysis》2006,18(11):1075-1080
The voltammetric behavior of uric acid (UA) has been studied at a multiwalled carbon nanotube‐ionic liquid (i.e., 1‐butyl‐3‐methylimidazolium hexafluorophosphate, BMIMPF6) paste coated glassy carbon electrode (MWNTs‐BMIMPF6/GC). It is found that UA can effectively accumulate at this electrode and cause a sensitive anodic peak at about 0.49 V (vs. SCE) in pH 4.0 phosphate buffer solutions. Experimental parameters influencing the response of the electrode, such as solution pH and accumulation time, are optimized for uric acid determination. Under the optimum conditions, the anodic peak current is linear to UA concentration in the range of 1.0×10?8 M to 1.0×10?6 M and 2.0×10?6 M to 2.0×10?5 M. The detection limit is 5.0×10?9 M for 180 s accumulation on open circuit. The electrode can be regenerated by successively cycling in a blank solution for about 3 min and exhibits good reproducibility. A 1.0×10?6 M UA solution is measured for eight times using the same electrode regenerated after every determination, and the relative standard deviation (RSD) of the peak current is 3.2%. As for different electrodes fabricated by the same way the RSD (i.e., the electrode to electrode deviation) is 4.2%(n=9). This method has been applied to the determination of UA in human urine samples, and the recoveries are 99%–100.6%. In addition, comparison is made between MWNTs‐BMIMPF6/GC and MWNTs/GC. Results show that the MWNTs‐BMIMPF6/GC exhibits higher sensitivity, selectivity and ratio of peak current to background current.  相似文献   

10.
In this paper the electrochemical behavior of hemoglobin (Hb) immobilized on a pencil lead electrode (PLE) was investigated. Immobilization of Hb on the pencil lead electrode was performed by nonelectrochemical and electrochemical methods. In phosphate buffer solution with pH 7.0 Hb showed a pair of well‐defined and nearly reversible redox waves (the anodic and cathodic peak potentials are located at ?0.18 V and ?0.22 V, respectively). The dependence of the anodic peak potential (Epa) on the pH of the buffer solution indicated that the conversion of Hb? Fe(III)/Hb? Fe(II) is a one‐electron‐transfer reaction process coupled with one‐proton‐transfer. In addition the effect of scan rate on peak currents and peak separation potential was investigated and electrochemical parameters such as α and ks were calculated. In the second part of this work, the ability of the electrode for determination of Hb concentration was investigated. The results showed a linear dynamic range from 0.15 to 2 µM and a detection limit of 0.11 µM. The relative standard deviation is 4.1 % for 4 successive determinations of a 1 µM Hb solution.  相似文献   

11.
A new composite electrode has been fabricated based on coating multi‐walled carbon nanotubes (MWCNTs) and n‐octylpyridinum hexafluorophosphate (OPPF6) ionic liquid composite on a glassy carbon (GC) electrode (OPPF6‐MWCNTs/GCE). This electrode shows very attractive electrochemical performances for electrooxidation of risperidone (RIS) compared to conventional electrodes using carbon and mineral oil, notably improved sensitivity and stability. The oxidation peak potentials in cyclic voltammogram of RIS on the OPPF6‐MWCNTs/GCE was occurred around 230 mV vs. SCE at Britton–Robinson (B–R) buffer (pH 4.0) at scan rate of 100 mV s?1. The electrochemical parameters such as diffusion coefficient (D), charge transfer coefficient (α) and the electron transfer rate constant (k/s) were determined using cyclic voltammetry. Under the optimized conditions, the peak current was linear to risperidone concentration over the concentration range of 10–200 nM with sensitivity of 0.016 μA/nM?1 using differential pulse voltammetry. The detection limit was 6.54 nM (S/N = 3). The electrode also displayed good selectivity and repeatability. In the presence of clozapine (CLZ) the response of RIS kept almost unchanged. Thus this electrode could find application in the determination of RIS in some real samples. The analytical performance of the OPPF6‐MWCNTs/GCE was demonstrated for the determination of RIS in human serum and pharmaceutical samples.  相似文献   

12.
A Cu(II)‐Poly(terthiophene carboxylic acid) (pTTC)/Nafion modified glassy carbon electrode has been used for the chiral recognition and discrimination of d‐ and l‐prolines by the catalytic oxygen reduction process and the shape of crystals formed on the electrode surface. The cyclic voltammetry with the modified electrode in the presence of oxygen recognized d‐ and l‐form of prolines by exhibiting a difference in the peak potential and the peak current of the oxygen reduction. The effect of pH and proline concentration on the peak current and the peak potential of oxygen have been studied. The SEM studies on the nature of crystals formed on a proline‐Cu(II)pTTC complex. The oxidation state of the copper species present at the electrode surface was characterized by ESCA.  相似文献   

13.
《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   

14.
A composition of multiwalled carbon nanotube (MWCNT), Nafion and cobalt(II)‐5‐nitrosalophen (CoNSal) is applied for the modification of carbon‐paste electrode (CPE). The pretreated MWCNT is well dispersed in the alcoholic solution of Nafion under the ultrasonic agitation, and the resulted suspension is used as modifier (with 10% w/w) in the matrix of the paste electrode. The prepared electrode further modified by addition of 3 wt% of CoNSal. The resulted modified electrode is used as a sensitive voltammetric sensor for simultaneous determination of uric acid (UA) and ascorbic acid (AA). The electrode showed efficient electrocatalytic activity in lowering the anodic overpotentials and enhancement of the anodic currents. This electrode is able to completely resolve the voltammetric response of UA and AA. The effects of potential sweep rate and pH of the buffer solution on the response of the electrode, toward UA and AA, and the peak resolution is thoroughly investigated by cyclic and differential pulse voltammetry (CV and DPV). The best peak resolution for these compounds using the modified electrode is obtained in solutions with pH 4. The ΔEp for UA and AA in these methods is about 315 mV, which is considerably better than previous reports for these compounds. A linear dynamic range of 1×10?7 to 1×10?4 M with a detection limit of 6×10?8 M is resulted for UA in buffered solutions with pH 4.0. The voltammetric response characteristics for AA are obtained as, the linear range of 5×10?7 to 1×10?4 M with the detection limit of 1×10?7 M. The voltammetric detection system was very stable and the reproducibility of the electrode response, based on the six measurements during one month, was less than 3.5% for the slope of the calibration curves of UA and AA. The prepared modified electrode is successfully applied for the determination of AA and UA in mixture samples and reasonable accuracies are resulted.  相似文献   

15.
《Electroanalysis》2004,16(17):1444-1450
The multi‐walled carbon nanotubes (MWNTs) modified glassy carbon electrode exhibited electrocatalytic activity to the reduction of oxygen in 0.1 M HAc‐NaAc (pH 3.8) buffer solution. Further modification with cobalt porphyrin film on the MWNTs by adsorption, the resulted modified electrode showed more efficient catalytic activity to O2 reduction. The reduction peak potential of O2 is shifted much more positively to 0.12 V (vs. Ag/AgCl), and the peak current is increased greatly. Cyclic voltammetry (CV), transmission electron microscopy (TEM), X‐ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM), were used to characterize the material and the modified film on electrode surface. Electrochemical experiments gave the total number of electron transfer for oxygen reduction as about 3, which indicated a co‐exist process of 2 electrons and 4 electrons for reduction of oxygen at this modified electrode. Meanwhile, the catalytic activities of the multilayer film (MWNTs/CoTMPyP)n prepared by layer‐by‐layer method were investigated, and the results showed that the peak current of O2 reduction increased and the peak potential shifted to a positive direction with the increase of layer numbers.  相似文献   

16.
The electrochemical reduction of three common insecticides such as cypermethrin (CYP), deltamethrin (DEL) and fenvalerate (FEN) was investigated at glassy carbon electrode (GCE), multiwalled carbon nanotubes modified GCE (MWCNT‐GCE), polyaniline (herein called as modifier M1) and polypyrrole (herein called as modifier M2) deposited MWCNT/GCE using cyclic voltammetry. Influences of pH, scan rate, and concentration were studied. The surface morphology of the modified film was characterized by scanning electron microscopy (SEM) and X‐ray diffraction analysis (XRD). A systematic study of the experimental parameters that affect differential pulse stripping voltammetry (DPSV) was carried out and the optimized experimental conditions were arrived at. The calibration plots were linear over the insecticide's concentration range 0.1–100 mg L?1 and 0.05–100 mg L?1 for all the three insecticides at MWCNT‐GCE and MWCNT(M1)‐GCE respectively. The MWCNT(M2)‐GCE performed well among the three electrode systems and the determination range obtained was 0.01–100 mg L?1 for CYP, DEL and FEN. The limit of detection (LOD) was 0.35 μg L?1, 0.9 μg L?1 and 0.1 μg L?1 for CYP, DEL and FEN respectively on MWCNT(M2)‐GCE modified system. Suitability of this method for the trace determination of insecticide in spiked soil sample was also determined.  相似文献   

17.
《Electroanalysis》2004,16(12):1038-1043
The polarographic behavior of gemfibrozil is investigated in 0.2 mol L?1 KH2PO4‐Na2HPO4 (pH 5.8±0.1)‐8% ethanol supporting electrolyte in the absence and the presence of dissolved oxygen. The results demonstrate that the polarographic reduction peak at ca. ?1.17 V is a catalytic hydrogen wave after deaeration, and the enhanced reduction peak in the presence of dissolved oxygen is the so‐called parallel catalytic hydrogen wave. Based on the parallel catalytic hydrogen wave, a novel method has been developed for the determination of gemfibrozil by single sweep polarography. Calibration plot is linear in the range of 1.8×10?7–2.4×10?6 mol L?1 and detection limit is 9.0×10?8 mol L?1. The proposed method is applied to the direct determination of the gemfibrozil in pharmaceutical preparations. The proposed method is simpler, faster and more sensitive than the known methods for gemfibrozil analyses.  相似文献   

18.
Litong J  Ping J  Jiannong Y  Yuzhi F 《Talanta》1992,39(2):145-147
A small size Nafion-methyl viologen chemically modified electrode (Nafion-MV CME) together with a small size electrolytic cell were constructed for the purpose of dissolved oxygen (DO) determination. The catalytic reduction of DO on Nafion-MV CME results in fast and sensitive DO determination. The mechanism of such detection is also considered.  相似文献   

19.
Polyaniline (PAn) films can be used in an electrochemical and optical combination system to amplify the optical signal for dissolved oxygen (DO) detection. To further improve the sensitivity of PAn film to DO, an oxygen‐sensitive molecule, Fe(III) meso‐tetera (4‐sulfonatophenyl) porphyrin (FeTSPP) is incorporated into PAn during the film generation. Results show that, after incorporating FeTSPP into the PAn matrix, both optical and potentiometric responses to DO are improved. The optimal optical signal is obtained under the application of ?2.5 μA to the modified electrode. Under this applied current, both optical and potentiometric signals show linear relations with the DO concentration within the range of 0.00–4.63 mg L?1, and the sensitivities for optical and potentiometric signals are 4.18 grayscale units mg?1 L and 13.39 mV mg?1 L, respectively.  相似文献   

20.
《Electroanalysis》2004,16(20):1697-1703
An amperometric glucose biosensor based on multi‐walled carbon nanotube (MWCNT) modified glassy carbon electrode has been developed. MWCNT‐modified glassy carbon electrode was obtained by casting the electrode surface with multi‐walled carbon nanotube materials. Glucose oxidase was co‐immobilized on the MWCNT‐modified glassy carbon surface by electrochemical deposition of poly(o‐phenylenediamine) film. Enhanced catalytic electroreduction behavior of oxygen at MWCNT‐modified electrode surface was observed at a potential of ?0.40 V (vs. Ag|AgCl) in neutral medium. The steady‐state amperometric response to glucose was determined at a selected potential of ?0.30 V by means of the reduction of dissolved oxygen consumed by the enzymatic reaction. Common interferents such as ascorbic acid, 4‐acetamidophenol, and uric acid did not interfere in the glucose determination. The linear range for glucose determination extended to 2.0 mM and the detection limit was estimated to be about 0.03 mM.  相似文献   

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