Analytical Determination of N-(2-Mercapto Propionyl)Glycine (Tiopronin) by Voltammetric Methods

Abstract

The anodic processes which occur at the mercury electrode in N-(2-mercaptopropinyl)glycine (tiopronin) solutions are studied by polarographic techniques (d.c., d.p. and a.c₁.), controlled potential coulometry and cathodic stripping voltammetry. According to the observed electrochemical behaviour the overall electrode process is the formation of a mercury(II)-mercaptide. Adsorption on the electrode of both the mercaptide and the free thiol is present. The d.p.p. peak at -0.58 V or the voltammetric stripping peak at -0.56 V are used for the analytical determination of N-(2-mercaptopropionyl)glycine within the concentration ranges 7.0 10^?5 - 6.8 10^?6 mol 1^?1 or 3.0 10^?7 - 1.0 10^?9 mol I^?1, respectively. Calibration functions are reported in both cases. The interference of several organic compounds is described.     

Cathodic Stripping Voltammetric Determination of Cerium Using Indium Tin Oxide (ITO)

Due to its numerous applications in the field of metallurgy and its role as an alloying element for slowing down the biodegradation of pure magnesium typically known to have very low corrosion resistance, the need to develop simple and inexpensive methods for determination of cerium is important. Ce³⁺ was determined by cathodic stripping voltammetry (CSV) using Osteryoung square‐wave voltammetry (OSWV) for the stripping step. Indium tin oxide (ITO) was used as the working electrode because of its very good positive potential range with smooth background current. Under optimized conditions, the calibration plot was linear in the concentration range of 100 nM to 700 nM Ce³⁺. A calculated detection limit of 5.8 nM was found for a 5 min deposition time at ITO based on the 3σ method. Interference from selected metal ions was also examined, and no significant interferences were observed. The good selectivity of this sensor makes it a good candidate for practical applications such as monitoring Ce³⁺ released into solution during the biodegradation of Mg−Ce alloys being developed for resorbable biomedical implants.     

Determination of Manganese in Whole Blood by Cathodic Stripping Voltammetry with Indium Tin Oxide

Manganese (Mn) is a required trace metal in the body. In recent years however, it has garnered significant attention as a developmental neurotoxin in children with chronic exposure. It has been linked to complications such as memory loss with negatively associated IQ scores, attention deficit hyperactivity disorder (ADHD), and in extreme cases, the development of a Parkinson's disease analogue‐manganism. Cathodic stripping voltammetry (CSV) has proven to be a suitable method for electroanalytical determination of Mn. We have established Mn CSV using indium tin oxide (ITO) as the working electrode for the determination of Mn in bovine whole blood after an acid digestion. Reliable, accurate, and precise results were obtained, as only 9 % variation in the digested blood was observed. The CSV results were compared with graphite‐furnace atomic absorption spectroscopy (GF‐AAS) and inductively coupled plasma‐ mass spectrometry (ICP‐MS) and favorable agreement across the methods was observed. Due to ITO's excellent positive potential window and stability under harsh environments, this method could be applied to other oxide‐forming transition metals detectable by CSV.     

Simultaneous Determination of Antimony and Lead in Gunshot Residue by Cathodic Adsorptive Stripping Voltammetric Methods

Differential pulse cathodic adsorptive stripping (DPCAdSV) and square wave cathodic adsorptive stripping (SWCAdSV) voltammetric methods were developed for the determination of antimony and lead in gunshot residues. Linear working ranges for DPCAdSV and SWCAdSV methods were (2.0×10^?9–5.0×10^?7) M and (2.0×10^?9–7.0×10^?7) M for antimony and 2.0×10^?9–3.0×10^?7 M (both methods) for lead. The detection of antimony limits were found to be 1.3×10^?9 M for DPCAdSV and 7.3×10^?10 M for SWCAdSV while the corresponding values for lead were 3.0×10^?9 M and 5.8×10^?10 M. Antimony and lead contents obtained by these methods in gunshot residues are in good agreement with those obtained by graphite furnace atomic absorption spectrometric method within a confidence limit of 95%.     

Highly Selective Adsorptive Cathodic Stripping Voltammetric Determination of Uranium in the Presence of Pyromellitic Acid

A very sensitive and selective adsorptive cathodic stripping procedure for trace measurement of uranium is presented. The method is based on adsorptive accumulation of the uranium‐pyromellitic acid (benzene‐1,2,4,5‐tetracarboxylic acid) complex onto a hanging mercury drop electrode, followed by reduction of the adsorbed species by voltammetric scan using differential pulse modulation. Influences of effective parameters such as pH, concentration of pyromellitic acid, accumulation potential and accumulation time on the sensitivity were studied. The peak current was proportional to the concentration of U(IV) up to 40 ng mL^?1 with a limit of detection of 0.136 ng mL^?1 with an accumulation time of 120 s. The range of linearity enhanced to 71.4 ng mL^?1and the detection limit improved to 0.058 ng mL^?1with accumulation times of 60 s and 300 s respectively. The relative standard deviation for 10 replicate determination of 4.76 ng mL^?1 U(IV) was equal to 2.7%. The possible interference by major cations and anions are investigated. The method was applied to the determination of uranium in some analytical grade salts, seawater and in synthetic samples corresponding to some uranium alloys with satisfactory results.     

碳糊电极阴极溶出伏安法测定当归中阿魏酸

采用碳糊电极作工作电极,阴极溶出伏安法对阿魏酸进行测定。在0.05mol.L-1盐酸溶液中,当有0.04mmol.L-1氯化钠溶液,0.004g.L-1十二烷基硫酸钠溶液存在时,1.1V(vs.SCE)富集180s,以100mV.s-1扫描速率从1.0V扫描至0V。阿魏酸在碳糊电极上于0.46V处产生一灵敏的阴极溶出伏安峰,峰电流与阿魏酸浓度在2.2×10-7～1.1×10-5 mol.L-1范围内呈线性关系,检出限(3S/N)为4.0×10-8 mol.L-1。初步探讨了阿魏酸的电化学性质,此方法用于测定当归中阿魏酸的含量,并以此样品为基体做回收试验,测得回收率在104.0%～109.1%之间,测定值的相对标准偏差(n=6)在2.6%～5.3%之间。     

Simultaneous Adsorptive Cathodic Stripping Voltammetric Determination of Nickel(II) and Cobalt(II) at an In Situ Bismuth‐Modified Gold Electrode

A study on the simultaneous determination of Ni(II) and Co(II) dimethylglyoximates (Ni‐DMG and Co‐DMG) through adsorptive cathodic stripping voltammetry at an in situ bismuth‐modified gold electrode (Bi‐AuE) is reported. The key operational parameters, such as Bi(III) concentration, accumulation potential and accumulation time were optimized and the morphology of the Bi‐microcrystals deposited on the Au‐electrode was studied. The Bi‐AuE allowed convenient analysis of trace concentrations of solely Ni(II) or of Ni(II) and Co(II) together, with cathodic stripping voltammograms characterized by well‐separated stripping peaks. The calculated limit of detection (LOD) was 40 ng L^?1 for Ni(II) alone, whereas the LOD was 98 ng L^?1 for Ni(II) and 58 ng L^?1 for Co(II), when both metal ions were measured together. The optimized method was finally applied to the analysis of certified spring water (NIST1640a) and of natural water sampled in the Lagoon of Venice. The results obtained with the Bi‐AuE were in satisfactory agreement with the certified values and with those provided by complementary techniques, i.e., ICP‐OES and ICP‐MS.     

Electroanalytical Detection of Cr(VI) and Cr(III) Ions Using a Novel Microbial Sensor

A microbial sensor, namely carbon paste electrode (CPE) modified with Citrobacter freundii (Cf–CPE) has been developed for the detection of hexavalent (Cr(VI)) and trivalent (Cr(III)) chromium present in aqueous samples using voltammetry, an electroanalytical technique. The biosensor developed, demonstrated about a twofold higher performance as compared to the bare CPE for the chosen ions. Using cyclic voltammetry and by employing the fabricated Cf–CPE, the lowest limit of detection (LLOD) of 1x10⁻⁴ M and 5x10⁻⁴ M for Cr(VI) and Cr(III) ions respectively could be achieved. By adopting the Differential Pulse Cathodic Stripping Voltammetric technique, the LLOD could be further improved to 1x10⁻⁹ M and 1x10⁻⁷ M for Cr(VI) and Cr(III) ions respectively using the biomodified electrodes. The reactions occurring at the electrode surface‐chromium solution interface and the mechanisms of biosorption of chromium species onto the biosensor are discussed. The stability and utility of the developed biosensor for the analysis of Cr(VI) and Cr(III) ions in chromite mine water samples has been evaluated.     

Cathodic Stripping Voltammetry Of Cerium

Abstract

The experimental conditions for the accumulation of cerium as insoluble Ce₃(PO₄)₄ on a platinum indicator electrode were studied. The determination of cerium down to 0.01% in oxides of other lanthanides is described.     

用色谱膜法富集阴极吸附溶出伏安法测定空气中的镍铜铅镉

在色谱膜池中,用１．０ｍｏｌ／ＬＨＮＯ３溶液吸收富集空气中的镍、铜、铅和镉,以８－羟基喹啉络合物吸附阴极溶出伏安法测定其含量。在ｐＨ７．５０的醋酸铵溶液中,８－羟基喹啉与镍、铜、铅及镉络合物的峰电位分别为－０．３８、－０．５２、－０．６２和－０．８０Ｖ,线性范围分别为０．５～３００、０．３～５０、０．０８～１００和０．０２～１００ｎｍｏｌ／Ｌ。     

Cathodic and Adsorptive Stripping Votammetry of Naftazone

Abstract

Naftazone (1,2-naphthoquinone-2-semicarbazone) undergoes a reversible two-electron transfer in both acidic and alkaline solutions and also gives rise at pH > 7 to an anodic wave attributed to the formation of a mercury derivative. Cathodic stripping voltammetry is proposed to determine the compound down to 5 × 10^?9 M after accumulation of its mercury salt formed at -0.05V in a 0.05M sodium hydroxide solution. These results have been compared with those obtained by performing an adsorptive collection of the drug in a pH 3 sodium perchlorate solution. Concentrations ranging from 1 × 10^?7 to 2 × 10^?7M can be easily investigated, the detection limit being 7 × 10^?11M. The influence of several operational parameters has also been considered.     

Determination of Ytterbium Traces by Cathodic Stripping Voltammetry

The method of ytterbium(III) trace concentration in the presence of 2‐thenoyltrifluoroacetone (TTA) and polyethyleneglycol (PEG) in ammonium chloride is described. The adsorption was performed at the HMDE at ?1.0 V using linear scan voltammetry and square‐wave voltammetry. The relationship between properties of the SW response of the mixed ligand complex and parameters of a charge transfer were analyzed using theoretical data of SW redox processes.     

Coprecipitative Preconcentration and Differential Pulse Cathodic Stripping Voltammetric Determination of Selenium (IV)

Abstract

A DPCSV procedure for the determination of selenium (IV) with a prior preconcentrative coprecipitation on iron (III) hydroxide has been developed. The experimental conditions for coprecipitation of selenium (IV) onto iron (III) hydroxide, viz. pH, iron (III) concentration, volume of aqueous phase and selenium concentration, were optimized. The coprecipitated selenium (IV) is dissolved in 10 ml of 0.1 M HCl and analysed using DPCSV in the presence of copper (II). Selenium concentrations as low as 10–100 ng present in 500 ml of the aqueous phase could be determined. The method is precise and has been applied to the analysis of sea water and reference material samples.     

Determination of Ethylenethiourea (ETU) at Trace Levels in Water Samples by Cathodic Stripping Voltammetry

A stripping voltammetric method for the determination of ethylenethiourea in water samples is described based on its adsorptive deposition at the hanging mercury drop electrode (HMDE). In a borate buffer (pH 9.0) as supporting electrolyte, ETU is deposited at +100 mV (vs. Ag/AgCl) and stripped during the cathodic scan. The linear range for the measurements was from 2.0 to 100 μg L^?1, with a detection limit calculated as 1.4 μg L^?1 after a deposition time of 300 s and a RSD of 1.9% (n=5) for 50 μg L^?1 of ETU measured. The interferences of some organic compounds and metallic ions were tested. Recoveries between 93 and 110% were obtained using the standard addition method for spiked samples of natural and drinking waters. The method is rapid and applicable in the monitoring of ETU residues in water samples.     

Cathodic Stripping Voltammetric Determination of Tellurium(IV) with in situ Plated Bismuth-Film Electrode

Abstract

A very sensitive and reliable method is proposed for the determination of tellurium(IV) [Te(IV)] by Osteryoung square-wave cathodic stripping voltammetry. This method is based on the reduction of Te(IV) with bismuth(III) onto an edge-plane pyrolytic graphite electrode, followed by a cathodic potential scan. The reduced Te gave a well-defined catalytic hydrogen wave at ?1200 mV vs. Ag/AgCl. The peak height of the catalytic wave was directly proportional to the initial Te(IV) concentration in the concentration ranges of 0.01–0.10 and 0.1–1.0 µg L^?1 with 30 s deposition time. A 3σ detection limit of 1.0 ng L^?1 Te(IV) was obtained with the same deposition time. The relative standard deviation was 3% on replicate runs (n = 5) for the determination of 0.1 µg L^?1 Te(IV). Analytical results of natural water samples demonstrate that the proposed method is applicable to the determination of traces of Te(IV).     

Determination of Se(IV) in On‐Line System by Cathodic Stripping Voltammetry

A sensitive and selective on‐line voltammetric procedure for determination of traces of Se(IV) is presented. The pulsed potential accumulation was proposed for minimization of interferences of surface active substances and foreign ions. The calibration plot was linear from 1×10^?9 mol L^?1 to 4×10^?8 mol L^?1 for accumulation time of 180 s. The relative standard deviation was 6.1% (n=5) for a Se(IV) concentration of 1×10^?8 mol L^?1. The detection limit estimated from (3 σ) for an accumulation time of 180 s was about 4×10^?10 mol L^?1. The validation of the procedure proposed was made by a recovery tests for tap and river water samples.     

生物样品中砷的阴极溶出伏安法测定

提出了用阴极溶出伏安法测定生物样品中痕量砷 ;砷 (Ⅲ )在HCl-CuCl介质中产生一灵敏的溶出峰 ,峰电位位于 -0.804V ,砷含量在10×10 -9～500×10 -9(w)范围内与峰电流成正比 ;研究了酸度、CuCl浓度和起始电位对峰电流的影响 ;该法用于奶牛饲料和猪肾中砷的测定 ,分析结果令人满意     

靛红在碳糊电极上的阴极吸附伏安法研究

利用极谱分析仪,在0.40 mol/L的HAc-NaAc(pH 6.0)缓冲液中,发现靛红在碳糊电极(CPE)上有一灵敏的吸附伏安还原峰,峰电位为-0.44 V(vs.SCE)。该还原峰的二阶导数峰电流与靛红的浓度在4.0×10-8~1.0×10-7mol/L(富集90 s)范围内成良好的线性关系,相关系数为0.9954,检出限为8.0×10-9mol/L(S/N=3,富集110 s)。探讨了靛红在碳糊电极上的伏安性质和电极反应机理,并且成功应用于中草药青黛中靛红含量的测定。     

离子缔合富集明极溶出伏安法测定痕量碘——Ⅰ.以丁基罗丹明B为离子缔合剂

本文提出在0.1mol/LH_2SO_4,7.5×10~(-4)mol/LBr~-和6×10~(-5)mol/L丁基罗丹明B(R~+)的底液中,在+1.0V下,I~-离子于玻璃电极上被氧化生成I_2BrR离子缔合物,藉以阴极溶出伏安法测定碘、I~-离子浓度在1～50ppb范围内与峰电流呈线性关系。用于食盐中痕碘的测定。