Trace Determination of Zirconium(Ⅳ) by Anodic Adsorptive Voltammetry at a Carbon Paste Electrode

A new sensitive adsorptive voltammetric method was described for the determination of zirconium at a carbon paste electrode (CPE) in the presence of alizarin complexone (ALC). Optimal analytical conditions are: 1.0?0-6 or 5.0?0-7 mol/L ALC, 0. 20 mol/L HAC-NaAc (pH 4.3), accumulation for 60 s at 0 V (vs. SCE), and linear scanning from 0 V to 1.0 V at 250 mV/s. The peak potential of the complex is at 0.81 V. By using a model JP-303 polarographic analyzer, 2.0?0-10 mol/L (S/N=3) zirconium can be detected with a 90 s accumulation, when the 2nd-order derivative linear sweep technique is used, and the linear range is 6.0?0-10-2.0?0-8 mol/L (5.0?0-7 mol/L ALC) and 2.0?0-8-2.0?0-7 mol/L (1.0?0-6 mol/L ALC), respectively. The developed method was applied to the determination of trace zirconium in the ore samples with satisfactory results.

Determination of trace amount of antimony (Ⅲ) by adsorption voltammetry on carbon paste electrode

A sensitive method is described for the determination of trace antimony based on the antimony-bromopyrogallol red (BPR) adsorption at a carbon paste electrode (CPE). Three steps were involved in the overall analysis: preconcentration,reduction and stripping. Optimal conditions were found to be an electrode containing 25% paraffin oil and 75% high purity graphite powder as working electrode;a 0.10 mol/L HCl solution containing 40 μmol/L BPR as accumulation medium;a 0.20 mol/L HCl solution as reduction and stripping electrolyte;accumulation time,150 s;reduction potential and time,-0.50 V,60 s;scan range from -0.50 to 0.20 V. Interferences by other ions were studied as well. The detection limit was found to be 0.5 nmol/L for 150 s preconcentration. The linear range was from 1.0 nmol/L to 0.50 μmol/L. Application of the proposed method to the determination of antimony in water and human hair samples gave good results.

Trace Determination of Scandium Using Adsorption Voltammetry of Mix-Polynuclear Complex of Scandium-Calcium-Alizarin Red S at Carbon Paste Electrode

A novel method was described for the determination of ultra trace amount of scandium based on the cathodic adsorptive voltammetry of the mix-polynuclear complex of scandium-calcium-alizarin red S at a carbon paste electrode (CPE). The 2nd-order derivative linear scan voltammograms of the adsorbed complex were recorded by model JP-303 polarographic analyzer from 0.0 to -1.0 V (vs. SCE). The experimental conditions of the working procedure were optimized. The results show that the complex can be adsorbed on the surface of the CPE, yielding one peak at -0.61 V, corresponding to the reduction of the alizarin red S in the mix-polynuclear complex at the electrode. The detection limit of Sc^(3+) is 1.0×10^(-10) mol·L^(-1) for 3 min of accumulation time. The procedure was successfully applied to the determination of trace amount of scandium in the sample ores.

Determination of Lead in Water by Linear Sweep Anodic Stripping Voltammetry (LSASV) at Unmodified Carbon Paste Electrode: Optimization of Operating Parameters

This study presents the elaboration of a simple and cheap electrode made by carbon paste introduced into a cavity of electrode body, and used for the lead traces determination in tap water. A potentiostatic pre-electrolysis at constant voltage enables the reduction of the lead (Pb2+) and the accumulation of the metallic lead at and into the carbon paste;the reoxidation of the Pb (Linear sweep voltammetry) leads to the anodic striping peak. The effect of the main operating parameters on the shape of the peak and the magnitude of the current was examined and their optimal values were determined. Then calibration was achieved and the method was successfully applied (using all the optimized parameters) to the determination of lead in water, with a detection limit of 0.138 μg·L-1. Compared to other methods (ICP-AES for example), the proposed method offers a satisfactory detection limit of the Pb2+ (0.138 μg·L-1) because of the important specific area of the carbon paste electrode, for a significantly lower cost. Besides, there is no observed loss in the electrode answer in terms of peak current, which means that there is no any irreversible steps nor deactivation of the electrode, even after ten successive measurements;only reduction of the lead followed by the deposit oxidation was observed at the electrode.

Square-Wave Adsorptive Cathodic Stripping Voltammeteric Determination of Manganese (II) Using a Carbon Paste Electrode Modified with Montmorillonite Clay

Manganese is an essential micronutrient for all organisms;however at high concentrations it has a toxic effect. Manganese toxicity is a serious constraint to crop cultivation since it is taken-up by plants and can easily be passed into the food chain again causing symptoms of Parkinson’s disease. A fully validated square-wave adsorptive cathodic stripping voltammetry method has been developed for determination of Mn (II) as a complex with 2-(5’-bromo-2’-pyridylazo) 5-diethylaminophenol in aqueous solutions using a carbon paste electrode (CPE) modified with montmorillonite-Na clay. The results showed that the modified CPE (90% (w/w) graphite powder and 10% (w/w) montmorillonite-Na clay) exhibited excellent electrochemical activity towards the investigated Mn (II) complex in acetate buffer of pH = 5.0. Factors affecting the performance of the modified carbon paste electrode and the sensitivity of the described square- wave stripping voltammetry method, including the electrode composition, concentration of ligand, pulse parameters and preconcentration conditions were examined. A detection limit (S/N = 3) of 0.015μg·L-1 (2.73 × 10-10 mol·L-1) Mn (II) was achieved when a preconcentration time of 240 s was applied. Insignificant interferences from various inorganic and organic species were estimated. The described square-wave adsorptive cathodic stripping voltammetry method coupled with the modified carbon paste electrode has been successfully applied to Mn (II) analysis in different water samples.

Adsorptive Stripping Voltammetric Determination of Mangiferin Using an Activated Chitosan Modified Carbon Paste Electrode

A medium molecular weight powdered chitosan modified carbon paste electrode was used to investigate the electrochemical behaviour by cyclic voltammetry of the pharmacologically-active ingredient mangiferin (MG). An irreversible system was observed, with a peak at ﹢0.55 V (vs Ag/AgCl). The peak current increases about fourfold, at the modified electrode in comparison with that recorded at the chitosan free carbon paste electrode. This allowed the use of adsorptive stripping voltammetry to develop a simple and sensitive electroanalytical method for the determination of MG. The influence of key parameters was investigated, including the electrolysis potential, the preconcentration time, the pH of supporting electrolyte and MG concentration. Upon optimisation of these parameters, the electrode response was found to be directly proportional to the concentration of MG in the range from 2.06 × 10﹣6 M to 6.74 × 10﹣5 M, leading to a detection limit of 1.84 μM for 240 s preconcentration at ﹣0.1 V. A mechanism was also proposed for the electrochemical oxidation of MG.

Mixed Binder Carbon Paste Electrode for Quantitation of Isoniazid in Serum

This paper covers the construction and behaviour of a mixed binder carbon paste electrode system appropriate for the cathodic stripping voltammetric quantitation of iso-niazid. The mixed binder consisted of glycerol and liquid paraffin. At the mixed binder carbon paste electrodes in a pH 3.0 buffer solution, isoniazid showed two sensitive cathodic stripping voltammetric wave at-0. 75 V (p1) and-0. 88 V (p2) , respectively. The p2 can be used for the determination of trace amounts of isoniazid, the linear range of the peak current to the isoniazid concentration being from 5. 0×10-7 to 5.0×10-5 mol/L, and the limit of detection being 1. 0×10-7 mol/L with a relative standard deviation of 6. 0%(n=10). The proposed method was directly used to determine the drug in blood serum without the pretreatment of blood serum.

Carbon Paste Electrodes for the Analysis of Some Agricultural Pollutants and Trace Metals

The present work is concerned with the voltammetric application of unmodified tricresyl phosphate carbon paste electrode （TCP-CPE） and in situ bismuth-film modified tricresyl phosphate-based carbon paste electrode （BiF-TCP-CPE）. The TCP-CPE was examined with the main objective of using it for the differential pulse voltammetric analysis of some neonicotinoid insecticides in aqueous Britton-Robinson buffer solution pH 7.0 as supporting electrolyte. After comparing the performance of the TCP-CPE with that of silicone oil carbon paste electrode, quantitative analysis of imidacloprid, thiamethoxam and clothianidin was performed in model solutions and real samples （river water and commercial insecticide formulations）. The in situ prepared BiF-TCP-CPE was tested for a simultaneous detection of selected heavy metal ions （Cd^2＋ and Pb^2＋） at a μg/dm^3 concentration level, using square wave anodic stripping voltammetric technique. The influence of different electrochemical pretreatments of the working electrode on the bismuth deposition and analyte signals were investigated. Film formation was studied at untreated, pre-cathodized and pre-anodized TCP-CPEs in the acetic buffer solution pH 4.6, containing 1 μg/cm^3 Bi （III）.

Trace determination of zirconium using anodic adsorptive voltammetry at a carbon paste electrode modified with multi-walled carbon nanotubes

A carbon paste electrode modified with multi-walled carbon nanotubes (MWCNT) was prepared and the determination of ultra trace amount of zirconium based on the anodic adsorptive voltammetry of the zirconium-calcium-alizarin red S mix-polynuclear complex is described in this paper for the first time. The results showed that the sensitivity and the selectivity of the method are excellent. The second de-rivative linear scan voltammograms of the complex were recorded by polarographic analyzer from 200 to 1200 mV (vs. SCE) and it was found that the complex can be adsorbed on the surface of the electrode, yielding a peak at about 840 mV, corresponding to the oxidation of ARS in the complex. The peak cur-rent increases linearly with Zr (IV) concentration in the range of 6.0×10-12―6.0×10-11 mol·L-1 (accumu-lation time 120 s), 6.0×10-11―2.0×10-9 mol·L-1 (accumulation time 90 s) and 2.0×10-9―1.0×10-7 mol·L-1 (accumulation time 60 s) and the detection limit (S/N = 3) is 2.0×10-12 mol·L-1 (accumulation time 180 s). The procedure has been successfully applied to the determination of zirconium in the ore samples.

Electrochemical determination of catechol in tea samples using anthraquinone modified carbon paste electrode

Electrochemical investigation of catechol using square wave voltammetry with anthraquinone modified carbon paste electrode was found to be very sensitive. Compared with the unmodified carbon paste electrode, the anthraquinone modified electrode remarkably increases the peak currents of catechol, and greatly lowers the peak potential separation. Two varieties of tea, namely green, and black variety: Wush Wush tea, from Ethiopia, known by its brand name were investigated. Responses for the extracts using ethanol: water (1:4) % v/v showed green tea to be superior in catechol content. Optimization of different variables such as pH of working solution, modifier composition and square wave parameters such as frequency, amplitude and step potential were made to improve the method efficiency during the experiment. The reproducibility for the nine repeated analysis of 80 μmol·L-1 of catechol gave a relative standard deviation of 3.65% and linear calibration plots were obtained in the range 6 to 80 μmol·L-1 with (R = 0.998) and the detection limit with (S/N = 3) was as low as 2.155 x 10-7 mol·L-1.

Anodic Stripping Voltammetric Determination of Nitrite Using Carbon Paste Electrode Modified with Chitosan

A simple method for anodic stripping voltammetric determination of nitrite using carbon paste electrode modified with biomolecular chitosan, is described. In this method, the electrode is activated electrochemically by scanning 5 replicates over the potential range from +500 to +1400 mV immersing in 0.5 M HCl solution. Following this step, the nitrite sample containing 0.1 M KCl is preconcentrated on the activated electrode at +500 mV for 30 s. The deposited anions are then oxidized by different modes of sweep in the oxidation direction. Chemical and electrical parameters affecting the voltammetric measurements are optimized. The peak current is linear proportional to the NO2- concentration within the range 0.41 - 4.1 μg/ml, with detection limit 0.187 μg/m using differential pulse mode. The relative standard deviation is 0.285% for 2.46 μg/ml (five replicates). No interference is observed due to oxygen dissolved in the sample so that nitrogen purging is not needed in this case. The result obtained by the modified electrode is more accurate and selective than the unmodified electrode.

Electrochemical Determination of Melamine on Static Mercury Drop Electrode and on Gold Nano Particle Modified Carbon Paste Electrode

An electrochemical method was developed for the determination of melamine (2,4,6 triamino- 1,3,5-triazine) on static mercury drop electrode (SMDE) and on gold nano particle modified carbon paste electrode. Interaction of melamine with Cu2﹢ ion was investigated and the decrease of Cu stripping peak was measured for the determination of melamine using SMDE. Oxidation property of melamine was improved using gold nano particle modified carbon paste electrode. Direct determination of melamine was proposed from the oxidation peak with three sigma detection limit of 0.43 μML﹣1. Recovery in milk powder sample has shown good recovery of melamine using the modified carbon paste electrode.

Stripping Voltammetric Determination of Uranium in Water Samples Using Hg-Thin Film Modified Multiwall Carbon Nanotube Incorporated Carbon Paste Electrode

The variables affecting determination of ultra trace levels of uranium (VI) in aqueous samples by differential pulse cathodic stripping voltammetry were examined in detail using Hg-thin film modified carbon paste and multiwall carbon nanotube (MWCNT) incorporated carbon paste electrode. Carbon paste electrode prepared in the laboratory was modified with Hg thin film and used as the working electrode. MWCNT was incorporated into the carbon paste for enhancement in sensitivity of the measurements. Electrochemical response for the uranium (VI) reduction peak was found to be well resolved on the thin mercury film modified carbon paste surface and also with the MWCNT modification. Characteristics of the adsorption preconcentration process were investigated using electrochemical impedance measurements. Electrochemical signals were observed to be enhanced on MWCNT modification of the carbon paste.

Catalytic Adsorptive Stripping Voltammetry at a Carbon Paste Electrode for the Determination of Amiodarone

Voltammetry using solid electrodes usually suffers from the contamination due to the deposition of the redox products of analytes on the electrode surface. The contamination has resulted in poor reproducibility and overelaborate operation procedures. The use of the chemical catalysis of oxidant on the reduction product of analyte not only can eliminate the contamination of analyte to solid electrodes but also can improve the faradaic response of analyte. This work introduced both the catalysis of oxidant K2S2O8 and the enhancement of surfactant Triton X-100 on the faraday response of amiodarone into an adsorptive stripping voltammetry at a carbon paste electrode for the determination of amiodarone. The method exhibits high sensitivity, good reproducibility and simple operation procedure. In 0.2 mol·L^-1 HOAc-NaOAc buffer （pH=5.3） containing 2.2×10^-2 mol·L^-1 K2S2O8 and 0.002% Triton X-100, the 2.5th-order derivative stripping peak current of the catalytic wave at 0.3 V （vs. Ag/AgCl） is rectilinear to amiodarone concentration in the range of 2.0×10^-10-2.3×10^-8 mol·L^-1 with a detection limit of 1.5×10^-10 mol·L^-1 after accumulation at 0 V for 30 s.

Adsorptive Stripping Voltammetry of Ultra Trace Lanthanum（Ⅲ） Using an Alizarin S as Complexing Agent and Carbon Paste as Working Electrode

Ultra trace determination of lantanum（Ⅲ） has been studied by adsorptive stripping voltammetry methods using an alizarin S as complexing agent and carbon paste electrode as working electrode. The electrode was made from mixed of carbon powder and paraffin in micropipette tip with diameter of 4 ram. This method consists of two steps. The first step is the formation and adsorptive accumulation of metal ion with chelator at the electrode surface. The second step is stripping the complex from the electrode surface into the solution. The stripping step generates current which is recorded as voltammogram. The optimum conditions of instrumental parameter obtained were accumulation potential of 600 mV, accumulation time of 120 seconds, and pH of solution of 5.5. In this research, the limit detection obtained was 2.3348 × 10^-12 M （3.24× 10^-11μg/L） with sensitivity of 16.52 （nA/10u M） and the precision of standard solution of La3＋ with concentration of 2 × 10^-12 M, 4× 10^-12 M, 6 × 10^-12 M, 8 × 10^-12 M, and 10 × 10^-12M were 3.50%, 9.88%, 7.19%, 7.48% and 1.85% respectively. The linierity of this method is very good with correlation coefficient is 0.9780. Recovery percentage from La3＋ with concentration of 6× 10^-12 M and 10 × 10^-12 M are 108.84% and 91.51%, respectively.

Study on the adsorptive catalytic voltammetry of aloe-emodin at a carbon paste electrode

A new catalytic voltammetric method for the determination of anthraqunone medi-cines at a carbon paste electrode (CPE) was described for the first time. The mechanism of the catalytic reaction was investigated by using linear sweep voltammetry, cyclic voltammetry, con-stant potential electrolysis and so on. The experiment results indicate that aloe-emodin was effi-ciently accumulated at a CPE by adsorption. In the following potential scan, aloe-emodin was reduced to homologous anthrahydroquinone compound, then the compound was immediately oxidized to aloe-emodin by the dissolved oxygen, and the aloe-emodin was again reduced at the CPE. As a result, a cyclic catalytic reaction was established. But a reversible redox reaction of aloe-emodin can only be observed at a mercury electrode, no catalytic reaction occurs there. A sensitive catalytic voltammetric peak of aloe-emodin was obtained at about ?0.60 V (vs. SCE) in 0.56 mol/L NH3-NH4Cl buffer (pH 8.9). The proposed method was applied to the determination of aloe-emodin in the Radix Rhei with satisfactory results. The determination results were in good agreement with reference values obtained by the HPLC. The adsorptive catalytic voltammetry for the determination of organic compound at CPE, chemically modified electrode and other solid electrodes could be significant in the studies on pharmacology, pharmacodynamics, toxicity of medicine, clinical medicine and biochemistry.

CuO-nanoparticles modified carbon paste electrode for square wave voltammetric determination of lidocaine: Comparing classical and Box–Behnken optimization methodologies

In this research, copper oxide nanoparticles modified carbon paste electrode was developed for the voltammetric determination of lidocaine. The square wave voltammogram of lidocaine solution showed a well-defined peak between ＋0.5 and ＋1.5 V. Instrumental and chemical parameters influencing voltammetric response were optimized by both one at a time and Box–Behnken model of response surface methodology. The results revealed that there was no significant difference between two methods of optimization. The linear range was 1–2500 μmol L^-1（Ip= 0.11 C（LH）＋ 17.38, R^2= 0.999）. The LOD and LOQ based on three and ten times of the signal to noise（S/N） were 0.39 and 1.3 μmol L^-1（n = 10）,respectively. The precision of the method was assessed for 10 replicate square wave voltammetry（SWV）determinations each of 0.05, 0.5 and 1 μmol L^-1 of lidocaine showing relative standard deviations 4.1%,3.7% and 2.1%, respectively. The reliability of the proposed method was established by application of the method for the determination of lidocaine in two pharmaceutical preparations, namely injection and gel.

Carbon Paste Electrode Modified by Surfactant for Anodic Stripping Voltammetric Determination of Sulphadiazine

he present paper covers the construction and behaviour of a mixed binder car-bon paste electrode modified by surfactant system appropriate for the anodic strip-ping voltammetric quantitation of sulphadiazine. The mixed binder consisted ofglycerol and liquid paraffin. On this electrode in a PH 8. 20 buffer solution sulpha-diazine yields a sensitive anodic stripping voltammetric wave at 0. 82 V. It can beused for the determination of trace amounts of drug, the linear range of the peakcurrent to the sulphadiazine concentration being from 1. 0 x 10-7 to 5. 0 x 10-5mol/L, and the detection limit being 6. 6 x 10-9 mol/L with a relative standard de-viation of 2. 6% (n= 15).The proposed method was used to determine the drug inurine samples.

An Ionic Liquid Bulk-Modified Carbon Paste Electrode and Its Electrocatalytic Activity toward p-Aminophenol

An ionic liquid bulk-modified carbon paste electrode （M-CPE） has been fabricated by using 1-heptyl-3-methylimidazolium bromide as a modifier. Cyclic voltammetry （CV） and differential pulse voltammetry （DPV） were used to evaluate the electrocatalytic activity of the proposed electrode by choosing p-aminophenol （p-AP） as a model compound. Both at a bare carbon paste electrode （CPE） and the M-CPE, p-AP yielded a pair of redox peaks in 0.1 mol·L^-1 phosphate buffer solution （PBS, pH 7.0）. At the CPE, the peak-to-peak potential separation （AEp） was 0.233 V, while at the M-CPE the AEp was decreased to 0.105 V. Furthermore, the current response to p-AP at the M-CPE was 10.2 times of that at the CPE by DPV. The electron transfer rate constant （ks） ofp-AP at the M-CPE was 13.3 times of that at the CPE. Under the optimal condition, a linear dependence of the catalytic current versus p-AP concentration was obtained in the range of 2.0× 10^- 6 to 3.0× 10^- 4 mol·L^-1 with a detection limit of 6.0× 10^-7 mol·L^-1 by DPV. In addition, compared to other modified method the proposed electrode exhibited distinct advantages of simple prapartion, surface renewal, good reproducibility and good stability. It has been used to determine p-AP in simulated wastewater samples.

Determination of captopril in patient human urine using ferrocenemonocarboxylic acid modified carbon nanotubes paste electrode

In this work,we describe a new strategy for the electrochemical determination of captopril（CA） using ferrocenemonocarboxylic acid as a mediator and multiwall carbon nanotubes as sensors in aqueous solution at pH 7.0.The diffusion coefficient（D）,and the kinetic parameters such as electron transfer coefficient（α）.and heterogeneous rate constant（kh）,for CA were also determined using electrochemical approaches.Under the optimized conditions,the electrocatalytic oxidation peak current of captopril showed two linear dynamic ranges with a detection limit of 0.3×10^-6 mol L^-1 captopril.The linear calibration range was 0.8×10^（-6） to 65×10^-6 mol L^-1 using cyclic voltammetry.Finally,this modified electrode was also examined as a selective,simple and precise new electrochemical sensor for the determination of captopril in real samples such as drug and patient human urine.