Cathodic Adsorptive Voltammetry of the Gallium‐Alizarin Red S Complex at a Carbon Paste Electrode

The adsorptive voltammetric behavior of the gallium‐alizarin red S (ARS) complex in NH₄OAc‐HCl buffer at a carbon paste electrode(CPE) was investigated. The results showed that the complex can be adsorbed on the surface of the CPE, yielding one reduction peak at ?0.52 V(vs. SCE), corresponding to the irreversible reduction of the ligand, ARS, bonded in the complex. The optimal experimental conditions include the use of 0.10 mol L^?1 ammonium acetate buffer(pH 4.5), 1.0×10^?5 mol L^?1 ARS, an accumulation potential of ?0.05 V, an accumulation time of 180 s ,a rest time of 10 s, a scan rate of 200 mV s^?1and a second‐order derivative linear scan mode. The peak current is proportional to the concentration of gallium(III) over the range 0.02–6.0 μg L^?1, with the detection limit of 0.01 μg L^?1 for an accumulation time of 180 s. The method was applied to the determination of gallium in food samples with satisfactory results.     

Carbon paste electrode for trace zirconium(IV) determination by adsorption voltammetry.

A very sensitive and selective procedure was developed for trace measurement of zirconium based on the cathodic adsorptive stripping voltammetry of the zirconium-alizarin red S(ARS) complex at a carbon paste electrode (CPE). The 2nd-order derivative linear scan voltammograms of the zirconium-ARS complex were recorded by a model JP-303 polarographic analyzer from 0.0 to -1.0 V (vs. SCE). Optimal analytical conditions were found to be: an acetic acid (0.1 mol l(-1))-potassium biphthalate (0.08 mol l(-1)) buffer solution (pH 4.8) containing 4.0 x 10-6 mol l(-1) ARS; accumulation potential, 0.0 V; accumulation time, 180 or 90 s; rest time, 10 s; scan rate, 250 mV s(-1). The results showed that the complex can be adsorbed on the surface of the CPE, yielding one peak at -0.51 V, corresponding to the reduction of ARS in the complex at the electrode. The detection limit was found to be 1.0 x 10(-10) mol l(-1) (S/N = 3) for 240 s accumulation. The linear range was 2.0 x 10(-10)-4.0 x 10(-7) mol l(-1). The developed method was applied to the determination of trace zirconium in the ore samples with satisfactory results.     

Catalytic Adsorptive Stripping Voltammetry of Germanium(IV) in the Presence of Gallic Acid and Vanadium(IV)‐EDTA

A highly sensitive and selective catalytic adsorptive cathodic striping procedure for the determination of trace germanium is presented. The method is based on adsorptive accumulation of the Ge(IV)‐gallic acid (GA) complex onto a hanging mercury drop electrode, followed by reduction of the adsorbed species. The reduction current is enhanced catalytically by addition of vanadium(IV)‐EDTA. The optimal experimental conditions include the use of 0.03 mol/L HClO₄ (pH1.6), 6.0×10^?3 mol/L GA, 3.0×10^?3 mol/L V(IV), 4.0×10^?3 mol/L EDTA, an accumulation potential of ?0.10 V(vs. Ag/AgCl), an accumulation time of 120 s and a differential pulse potential scan mode. The peak current is proportional to the concentration of Ge(IV) over the range of 3.0×10^?11 to 1.0×10^?8 mol/L and the detection limit is 2×10^?11 mol/L for a 120 s adsorption time. The relative standard deviation at 5.0×10^?10 mol/L level is 3.1%. No serious interferences were found. The method was applied to the determination of germanium in ore, mineral water and vegetable samples with satisfactory results.     

Determination of Trace Tin by Anodic Stripping Voltammetry at a Carbon Paste Electrode

A sensitive and selective procedure for the determination of trace tin at a carbon paste electrode was described. Each measurement cycle consisted of three steps: accumulation, reduction and stripping. The tin complex with bromopyrogallol red (BPR) was accumulated on the electrode surface in 0.10 mol/L acetate buffer (pH 4.5). After electrochemical reduction of Sn(II) had been carried out, the reoxidation wave of Sn(0) appeared at ?0.69 V (vs. SCE) on scanning the potential in the positive direction in 4.0 mol/L HCl. For a preconcentration time of 2 min, the detection limit was 0.06 μg/L (5×10^?10 mol/L ) and the linear range was from 0.1 to 50 μg/L. The proposed method was applied to the determination of tin in canned food and waste water samples with satisfactory results.     

Determination of Trace Copper by Adsorptive Voltammetry Using a Multiwalled Carbon Nanotube Modified Carbon Paste Electrode

A new method for the determination of trace copper was described. A multiwalled carbon nanotube modified carbon paste electrode was prepared and the adsorptive voltammetric behavior of copper‐alizarin red S (ARS) complex at the modified electrode was investigated. By use of the second‐order derivative linear sweep voltammetry, it was found that in 0.04 mol/L acetate buffer solution (pH 4.2) containing 4×10^?6 mol/L ARS, when accumulation potential is 0 mV, accumulation time is 60 s and scan rate is 100 mV/s, the complex can be adsorbed on the surface of the electrode, yielding one sensitive reduction peak at ?172 mV (vs. SCE). The peak current of the complex is proportional to the concentration of Cu(II) in the range of 2.0×10^?11–4.0×10^?7 mol L^?1 with a detection limit (S/N=3) of 8.0×10^?12 mol/L (4 min accumulation). The proposed method was successfully applied to the determination of copper in biological samples with satisfactory results, the recoveries were found to be 96%–102%.     

Adsorptive anodic stripping voltammetry of zirconium(IV)-alizarin red S complex at a carbon paste electrode

A sensitive adsorptive anodic stripping procedure for the determination of trace zirconium at a carbon paste electrode (CPE) has been developed. The method is based on adsorptive accumulation of the Zr(IV)-alizarin red S(ARS) complex onto the surface of the CPE, followed by oxidation of adsorbed species. The optimal experimental conditions include the use of 0.10 mol · L⁻¹ ammonium acetate buffer (pH 4.3), ARS, an accumulation potential of 0.20 V (versus SCE), an accumulation time of 2 min, a scan rate of 200 mV · s⁻¹ and a second-order derivative linear scan mode. The oxidation peak for the complex appears at 0.69 V. The peak current is proportional to the concentration of Zr(IV) over the range of 1.0 × 10⁻⁹–2.0 × 10⁻⁷ mol · L⁻¹, and the detection limit is 3 × 10⁻¹⁰ mol · L⁻¹ for a 2 min adsorption time. The relative standard deviations (n = 8) for 5.0 × 10⁻⁸ and 5.0 × 10⁻⁹ mol · L⁻¹ Zr(IV) are 3.3 and 4.8%, respectively. The proposed method was applied to the determination of zirconium in ore samples with satisfactory results.     

Indirect Determination of Trace Copper(II) by Adsorptive Stripping Voltammetry with Zincon at a Carbon Paste Electrode

Traces of copper(II) can be determined by adsorptive stripping voltammetry using 2‐carboxy‐2′‐hydroxy‐5′‐sulfoformazyl benzene (Zincon) as complex forming reagent. First in phosphate buffer pH 6.4, copper(II)‐Zincon complex was adsorbed on carbon paste electrode (CPE) with an accumulation potential of 0.6 V. Following this, adsorbed complex was oxidized and detected by differential pulse voltammetric (DPV) scan from 0.6 to 1.0 V. The effective parameters in sensor response were examined. The detection limit (DL) of copper(II) was 1.1 μg/L and relative standard deviations (RSDs) for 10 and 200 μg/L Cu(II) were 1.81 and 1.03%, respectively. The calibration curve was linear for 2–220 μg/L copper(II). The resulting CPE does not use mercury and therefore, has a positive environmental benefit. The method, which is reasonably sensitive and selective, has been successfully applied to the determination of trace amount of copper in water and human hair samples.     

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 ofzirconium at a carbon paste electrode (CPE) in the presence of alizarin complexone (ALC).Optimal analytical conditions are: 1.0~ l0“6 or 5.0x l0“7 mol/L ALC, 0.20 mol/L HAC-NaAc (pH4.3), 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~ l0l~ mol/L (S/N=3) zirconium can be detected with a 90 s accumulation, when the 2nd-orderderivative linear sweep technique is used, and the linear range is 6.0~ 10l~-2.0~ l0s mol/L (5.0~ l07mol/L ALC) and 2.0~108-2.0~ l07 mol/L (1.0~ 10.6 mol/L ALC), respectively. The developedmethod was applied to the determination of trace zirconium in the ore samples with satisfactoryresults.     

Carbon paste electrode based on surface activation for trace adriamycin determination by a preconcentration and voltammetric method.

A voltammetric determination of adriamycin (ADM) at a carbon paste electrode (CPE) in the presence of cetyltrimethylammonium bromide (CTAB) is described. ADM strongly adsorbs on the surface of the electrode by the adsorption of CTAB, thereby affecting the reduction current. This method provides a detection limit below 10(-10) mol/L for ADM. The experimental parameters, which influence the voltammetric responses of ADM, e.g. the pH value, variety and concentration of surfactants and the scan rate, were optimized. The reduction peak current changes linearly with the ADM concentration over the range from 2.5 x 10(-8) mol/L to 5 x 10(-6) mol/L. The detection limit is 4 x 10(-10) mol/L for an accumulation time of 3 min. The coefficient of variation, determined at 4 x 10(-6) mol/L ADM, is 3.0% (n = 8). Using this method, ADM in the patient's urine samples, which undergoes active ADM chemotherapy, was determined.     

茜素修饰碳糊电极吸附伏安法测定痕量铜

报道了采用茜素修饰碳糊电极测定痕量铜的阳极溶出伏安法。在浓度为0 .1 mol/L 的 HAc- Na Ac缓冲溶液 (p H4.5)中 ,于 +0 .1 0 V处富集 ,- 0 .30 V还原后再进行阳极化扫描 ,于 - 0 .0 5V处获得一灵敏的铜的溶出峰 ,二次导数峰电流与铜浓度在 1 .6× 1 0 -9mol/L～ 4.7× 1 0 -7mol/L范围内呈线性关系 ,检出限达 8.0× 1 0 -10 mol/L。同时 ,对电极反应机理进行了讨论。方法应用于锌合金中铜的测定。     

Determination of Trace Amount of Lead(II) in Sweet Fruit‐Flavored Powder Drinks by Differential Pulse Adsorptive Stripping Voltammetry at Carbon Paste Electrode

A new method is described for the determination of lead based on the cathodic adsorptive stripping of the lead–nuclear fast red (NFR) at a carbon paste electrode (CPE). The differential pulse voltammograms of the adsorbed complex of lead–NFR are recorded from ?0.10 to ?0.60 V (versus Ag/AgCl electrode). Optimal conditions were found to be an electrode containing 25% paraffin oil and 75% high purity graphite powder, 4.0×10^?5 mol L^?1 NFR; buffer solution (pH of 3.0), accumulation potential and time, ?0.20 V, 60 and 120 s (for high and low concentration of lead), respectively. The results show that the complex can be adsorbed on the surface of the CPE, yielding one peak at ?0.34 V, corresponding to reduction of NFR in the complex at the electrode. The detection limit was found to be 0.2 ng mL^?1 with a 120s accumulation time. The linear ranges are from 0.5 to 50 (t_acc=120 s) and 50 to 200 ng mL^?1 (t_acc=60 s). Application of the procedure to the determination of lead in lake water, bottled mineral water, synthetic samples and sweet fruit‐flavored powder drinks samples gave good results.     

Trace determination of vanadium(V) using anodic adsorptive voltammetry at a glassy carbon electrode modified with multi-walled carbon nanotubes

A glassy carbon electrode modified with multi-walled carbon nanotubes (MWCNT) was prepared and the determination of trace amount of vanadium(V) based on the anodic adsorptive voltammetry of the vanadium-alizarin red S (ARS) complex is described for the first time. The results show that the sensitivity and the selectivity of the method are excellent. The second derivative linear scan voltammograms of the complex were recorded using a polarographic analyzer in the range from 0 to 1,000 mV (vs. SCE). It was found that the complex can be adsorbed on the surface of the electrode, yielding a peak at about 706 mV, corresponding to the oxidation of ARS in the complex. The peak current increases linearly with the V(V) concentration in the range of 6.0 nM to ∼1.0 μM (4.0 μM ARS), 2.0 μM∼10 μM (40 μM ARS) and the detection limit (at S/N = 3) was 2.0 nM (accumulation time 120 s). The method was successfully applied to the determination of trace amounts of vanadium in water samples.

     

铋膜电极方波吸附溶出伏安法测定纺织品中痕量钴和镍

本文建立了在铋膜修饰电极上采用方波吸附溶出伏安法同时测定纺织品中痕量Co2+和Ni2+的方法.以NH3-NH4Cl作为缓冲液,在丁二酮肟浓度为10 μmol/L的体系中,Co2和Ni2+的还原峰电位分别为-1.13 V和-1.03 V.当缓冲溶液pH为9.2,富集电位为-0.7V,富集时间为200 s时,C02 +和Ni2+在0.5～50 μg/L范围呈现良好的线性关系,相关系数R2＞0.99,其检出限分别为0.79 μg/L和0.96 μg/L,其它金属离子的干扰较小.采用标准加入法测定纺织品中Co>和Ni2+,回收率在94.88％～104.14％之间.     

Anodic stripping voltammetric determination of silver ion at a carbon paste electrode modified with carbon nanotubes

A carbon paste electrode (CPE) was modified with multi-wall carbon nanotubes and successfully applied to the determination of silver ion by differential pulse anodic stripping voltammetry. Compared to a conventional CPE, a remarkably improved peak current response and sensitivity is observed. The analytical procedure consisted of an open circuit accumulation step for 2?min in ?0.4?V, this followed by an anodic potential scan between +0.2 and?+?0.6?V to obtain the voltammetric peak. The oxidation peak current is proportional to the concentration of silver ion in the range from 1.0?×?10^?8 to 1.0?×?10^?5?mol?L^?1, with a detection limit of 1.8?×?10^?9?mol?L^?1 after an accumulation time of 120?s. The relative standard deviation for 7 successive determinations of Ag(I) at 0.1???M concentration is 1.99%. The procedure was validated by determining Ag(I) in natural waters.

三辛胺修饰碳糊电极测定电子引脚中的Cr(Ⅵ)

采用三辛胺(TOA)修饰碳糊电极(TOA/CPE)测定了Cr(Ⅵ)含量,并考察了最佳的实验条件。当富集时间为10 min,富集介质为0.15 mol/L H2SO4时,TOA/CPE能够有效地富集Cr(Ⅵ)。以溶出伏安法测定Cr(Ⅵ),在-0.45 V(vs.SCE)处有灵敏的还原峰,峰电流与Cr(Ⅵ)浓度在5.0×10-7~1.0×10-3mol/L范围内呈现良好的线性关系。干扰试验显示TOA/CPE对Cr(Ⅵ)具有高选择性,能够在Cr(Ⅲ)浓度是Cr(Ⅵ)600倍时准确测定Cr(Ⅵ),检出限达3.4×10-9mol/L(S/N=3)。TOA/CPE测定了实际样品电子引脚中的Cr(Ⅵ),实验结果与紫外分光光度法结果一致。     

催化动力学极谱法测定痕量钒

在硫酸介质中,以酒石酸为活化剂,痕量钒对溴酸钾氧化甲基橙的反应有极强的催化作用,以极谱法监测催化反应过程中甲基橙及其氧化产物浓度的变化,建立了双峰指示催化动力学极谱法制定痕量钒的新方法,方法的线性范围为0.23-3.70μg/L,检出限为0.17μg/L。方法已用于食品及水样中痕量钒的测定。     

Selective Determination of Verapamil in Pharmaceutics and Urine Using a Boron‐doped Diamond Electrode Coupled to Flow Injection Analysis with Multiple‐pulse Amperometric Detection

This work presents a simple and low‐cost method for fast and selective determination of Verapamil (VP) in tablets and human urine samples using a boron‐doped diamond working electrode (BDD) coupled to a flow injection analysis system with multiple pulse amperometric detection (FIA‐MPA). The electrochemical behaviour of VP in 0.1 mol L⁻¹ sulfuric acid showed three merged oxidation peaks at around +1.4 V and upon reverse scan, one reduction peak at 0.0 V (vs. Ag/AgCl). The MPA detection was performed applying a sequence of three potential pulses on BDD electrode: (1) at +1.6 V for VP oxidation, (2) at +0.2 V for reduction of the oxidized product and (3) at +0.1 V for cleaning of the working electrode surface. The FIA system was optimized with injection volume of 150 μL and flow rate of 3.5 mL min⁻¹. The method showed a linear range from 0.8 to 40.0 μmol L⁻¹ (R>0.99) with a low limit of detection of 0.16 μmol L⁻¹, good repeatability (RSD<2.2 %; n=10) and sample throughput (45 h⁻¹). Selective determination of VP in urine was performed at+0.2 V due to absence of interference from ascorbic and uric acids in this potential. The addition‐recovery tests in both samples were close to 100 % and the results were similar to an official method.     

Sensing System Integrating Lanthanum Hydroxide Nanowires with Copper(II) Ion for Uracil and its Application

Abstract

A sensing system for uracil was constituted by using lanthanum hydroxide nanowires (LNW) as a modifier to obtain LNW modified carbon paste electrode (LNW/CPE) and by introducing copper(II) ion into supporting electrolyte to transform electroinactive uracil to electroactive uracil‐Cu(II) complex. The voltammetric behaviors of uracil in the presence of Cu(II) ion at LNW/CPE were investigated. A reduction peak of the uracil‐Cu(II) complex at ?0.18 V was the two‐electron reduction of Cu(II) ion in the uracil‐Cu(II) complex; while a new oxidation peak at 0.22 V was the one‐electron oxidation of the uracil‐Cu(I) complex. Additionally, the voltammetric responses of all the complexes at LNW/CPE were more sensitive than that at carbon and multiwall carbon nanotube paste electrodes, which resulted from both the large surface effect of LNW and the chemical coordination of uracil with La(III) ion in LNW. With the sensitive oxidation peak of the uracil‐Cu(I) complex at LNW/CPE, a linear range of 4.0×10^?9?3.0×10^?8 mol/l for uracil was obtained along with a detection limit of 2.0×10^?10 mol/l. The proposed system was evaluated by the determination of uracil derivatives, anticancer drug 5‐flurouracil, in pharmaceutical preparations.     

Adsorptive Stripping Voltammetric Measurements of Trace Molybdenum at the Bismuth Film Electrode

Bismuth‐film electrodes on glassy‐carbon substrates have been successfully applied for adsorptive‐stripping voltammetric measurements of trace molybdenum in the presence of chloranilic acid (CAA). The procedure is based on the preconcentration of the molybdenum‐chloranilic acid complex at a preplated bismuth film electrode held at ?0.55 V (vs. Ag/AgCl), followed by a negatively‐sweeping square‐wave voltammetric scan. Factors influencing the adsorptive stripping performance, including different ligands, solution pH, CAA concentration, preconcentration time and potential, have been optimized. The response compares favorably with that observed at mercury film electrodes, and is linear over the 5–50 μg/L Mo concentration range (one min preconcentration). A detection limit of 0.2 μg/L molybdenum is obtained following a 10 min accumulation. High stability is indicated from the reproducible response of a 100 μg/L molybdenum solution (n= 60; RSD=2.6%). Applicability to seawater samples is demonstrated.     

Voltammetric Detection of the Herbicide Metamitron at a Bismuth Film Electrode in Nondeaerated Solution

In this work, we present a novel application of bismuth film electrodes (BiFE) for the direct analysis of the herbicide metamitron (4‐amino‐3‐methyl‐6‐phenyl‐1,2,4‐triazin‐5one) in nondeaerated solutions by square‐wave voltammetry (SWV) and differential pulse amperometry. Bismuth films were plated ex‐situ onto carbon paste electrodes (CPE) by 240 s deposition at ?0.600 V from a 0.10 M acetate buffer (pH 4.5) containing 0.50 mM bismuth nitrate. Metamitron SWV analytical signals were registered in 0.10 M acetate buffer (pH 4.5) solutions, where the herbicide reduction takes place at ?0.675 V. The metamitron signals obtained with BiFE have the double sensitivity and a 50 mV positive potential shift when compared to those obtained with plain CPE. Under these conditions, the dynamic linear range of concentrations is comprised between 10 and 200 μM and the detection limit is 2 μM.