Determination of nifuroxazide with polarography and adsorptive stripping voltammetry at mercury and carbon paste electrodes

A simple method for the determination of the urinary tract antibiotic nifuroxazide has been developed. The electrochemical reduction of the nitro group at mercury and carbon paste electrodes can be used for the determination with and without adsorptive preconcentration. The influence of parameters like pH of the background electrolyte, preconcentration potential and preconcentration time on the sensitivity of the method has been studied. Modification of the carbon paste by addition of nonpolar polystyrene/divinylbenzene particles has been investigated to enhance the adsorption properties of the surface. Concentrations as low as 10 ng/mL could be determined in urine without interferences.     

掺杂硒碳糊电极阳极溶出法测定铋

建立了一种测定痕量铋的新方法,即利用掺杂硒碳糊电极作为工作电极的阳极溶出法.在0.1 mol/L的HCl底液中,Bi3+于+0.05V(vs.Ag/AgCl)出现灵敏的氧化溶出峰,铋离子的浓度在1.0×10-5～1.0×10-9 mol/L范围内其对数值lgc与铋的氧化峰电流值呈线性关系,检出限达1.0×10 -10 ...     

Determination of Bentazepam by differential pulse polarography and adsorptive stripping voltammetry

Summary A method is described for the determination of Bentazepam using DPP and ADSV with DP. Bentazepam is determined in buffer Britton-Robinson 0.04 mol l^-1 at pH 9 with detection limits of 3.1×10^-9 mol/l and a relative standard deviation of 0.8 DPP was used to determine Bentazepam in Tiadipona, the commercial product. ADSV was used to determine Bentazepam in urine with a detection limit of 2.7 ng ml^-1 (accumulation time 5 min) and a relative standard deviation of 1.5%.     

碳糊修饰电极吸附伏安法测定食品中的锑

研制了溴邻苯三酚红 (BPR)作修饰剂的碳糊修饰电极 ,并用此电极作工作电极建立了测定痕量锑的吸附伏安法。在选定的实验条件下 ,峰电流与Sb(Ⅲ )浓度在 8.0× 1 0 -9～ 2 .0× 1 0 -7mol L范围内呈线性关系 ,检出限为 2 .0×1 0 -9mol L ,1 0次测定相对标准偏差为 2 .0 % ,不用分离 ,可直接测定食品中痕量Sb(Ⅲ ) ,测定的回收率为 90 %～ 1 0 3%。     

Determination of nickel by anodic adsorptive stripping voltammetry with a cation exchanger-modified carbon paste electrode

The behavior of a modified carbon paste electrode (CPE) for nickel determination by anodic adsorptive stripping voltammetry (AAdsSV) was studied. The electrode was built incorporating the Dowex 50W x 12 (H(+) form) ion exchanger to a Nujol-graphite base paste. Ni(2+) was preconcentrated on the electrode surface in open circuit conditions, with the reduction (-1300 mV)/reoxidation step carried out in HCl solution (pH 3). During deposition time (5 min), the hydrogen evolution did not present obstacle in the quantification of nickel. For 12 min of accumulation and 5 min of deposition, nickel can be quantified up to 600 mug l(-1). The detection limit was 0.005 mug l(-1) at a linear potential scan rate of 200 mV s(-1). Interferences from Hg(2+) and Ag(2+) up to a concentration of 1 and 0.6 mg l(-1), respectively, were eliminated with the aid of the anion exchanger Dowex-2 (mesh 200-400) which was added to the sample in the preconcentration step. The tolerance for some metal ions such as Cu(2+), Cd(2+), Fe(3+), Zn(2+), Co(2+) and Pb(2+) was improved in the same way. The method was applied for the determination of nickel in samples of tap and mineral water. At the concentration level of 50 mug l(-1) of Ni (2+), the results were in good agreement with those obtained using Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES). For a Ni(2+) concentration of 5 mug l(-1), the results obtained showed better accuracy than those obtained by ICP-AES.     

Determination of lamotrigine by adsorptive stripping voltammetry using silver nanoparticle-modified carbon screen-printed electrodes

Carbon screen-printed electrodes (CSPE) modified with silver nanoparticles present an interesting alternative in the determination of lamotrigine (LTG) using differential pulse adsorptive stripping voltammetry.Metallic silver nanoparticle deposits have been obtained by electrochemical deposition. Scanning electron microscopy measurements show that the electrochemically synthesized silver nanoparticles are deposited in aggregated form.The detection limit for this analytical procedure was 3.72 × 10⁻⁷ M. In terms of reproducibility, the precision of the above mentioned method in %R.S.D. values was calculated at 2.58%.The method was applied satisfactorily to the determination of LTG in pharmaceutical preparations.     

Glassy carbon electrodes coated with cellulose acetate for adsorptive stripping voltammetry

The utility of glassy carbon electrodes coated with cellulose acetate for adsorptive stripping voltammetry of oxidizable organic compounds is evaluated. This surface modification alleviates the co-adsorption problem commonly encountered at conventional electrodes. Interferences from electro-inactive surfactants and, in certain situations, from adsorbable electroactive substances, are minimized. Quantitation of the drugs, chlorpromazine and trimipramine, is not affected by the presence of up to 120 mg 1^?1 albumin or gelatin. The chlorpromazine response is not affected by the bilirubin or perphenazine peaks which overlap at uncoated electrodes. The adsorptive stripping response at the coated electrode is evaluated with respect to hydrolysis time, preconcentration time, concentration dependence, reproducibility, and other variables. The detection limit for chlorpromazine is 1.3 × 10^?8 M (5-min preconcentration). Applicability to assays of urine and serum samples is illustrated.     

Determination of tannic acid by adsorptive anodic stripping voltammetry at porous pseudo-carbon paste electrode

A novel and sensitive electrochemical sensor based on porous pseudo-carbon paste electrode (PPCPE) for tannic acid detection is described. PPCPE is fabricated by mixing calcium carbonate microspheres as the template, graphite powders as the filler, and pyrrole as the precursor of polymer which actually acted as the paste. After the polymerization of pyrrole catalyzed by Fe³⁺, the template calcium carbonate microspheres are removed with 0.1 M hydrochloric acid to form PPCPE. The diameters of these pores are in the range from 2 to 5 μm by SEM observations and the specific surface area of PPCPE is 59.26 m²/g by the Brunauer–Emmet–Teller (BET) method. A linear relationship between the anodic stripping peak current and the concentration of tannic acid from 0.02 to 1 μM and a limit of detection as low as 0.01 μM are obtained using PPCPE.     

Determination of trace amount of bismuth(III) by adsorptive anodic stripping voltammetry at carbon paste electrode

A sensitive method is described for the determination of trace bismuth based on the bismuth-bromopyrogallol red (BPR) adsorption at a carbon paste electrode (CPE). The overall analysis involved a three-step procedure: accumulation, reduction, and anodic stripping. Optimal conditions were found to be an electrode containing 25% paraffin oil and 75% high purity graphite powder, a 0.30 mol l⁻¹ HCl solution containing 2.0×10⁻⁵ mol l⁻¹ BPR as supporting medium; accumulation potential and time, −0.10 V, 3 min; reduction potential and time, −0.35 V, 60 s; scan rate 100 mV s⁻¹; scan range from −0.35 to 0.15 V. It was found that the Bi(III)-BPR complex could be accumulated on the electrode surface during the accumulation period. Then the Bi(III) in the Bi(III)-BPR complex on the CPE surface was reduced to Bi(0) during reduction interval and finally reoxidized during the anodic stripping step for voltammetric quantification. Factors affecting the accumulation, reduction, and stripping steps were investigated. Interferences by other ions were studied as well. The detection limit was found to be 5×10⁻¹⁰ mol l⁻¹ with a 3 min accumulation time. The linear range was from 1.0×10⁻⁹ to 5.0×10⁻⁷ mol l⁻¹. Application of the procedure to the determination of bismuth in water and human hair samples gave good results.     

The determination of cysteine at Bi-powder carbon paste electrodes by cathodic stripping voltammetry

The determination of cysteine by means of square wave cathodic stripping voltammetry (SWCSV) is reported here for the first time at Bi-modified carbon paste electrodes (CPEs). The modified electrodes are 17% w/w metallic Bi powder mixed with CP (Bi-CPEs) and the technique is based on the enhancement of Bi surface oxidation in the presence of cysteine at a carefully chosen accumulation potential and the subsequent reduction-stripping of the product (proposed to be bismuth(III) cysteinate) by potential scanning to more negative values. The wide concentration range of 1 × 10⁻⁶–5 × 10⁻⁵ M for cysteine can be assessed by SWCSV using Bi-CPEs and, by appropriate choice of accumulation times, two linear response concentration regimes could be identified: 1 × 10⁻⁶–1 × 10⁻⁵ M (accumulation for 600 s) and 1 × 10⁻⁵–5 × 10⁻⁵ M (accumulation for 100 s), with estimated detection limits of 3 × 10⁻⁷ and 2 × 10⁻⁶ M, respectively.     

碳糊电极阳极吸附伏安法测定洛美沙星

报道了碳糊电极阳极吸附伏安法测定洛美沙星的新方法。在0.096mol L的KHP NaOH(pH5.4)缓冲液中,用碳糊电极为工作电极,在0.3V(vs.SCE)富集一定时间,然后从0.3～1 3V以300mV s扫速线性扫描,记录其在1 02V的二次导数阳极溶出峰。溶出峰电流与洛美沙星浓度在8.0×10-9～8.0×10-8mol L(富集90s)和8.0×10-8～8.0×10-7mol L(富集30s)范围内呈良好的线性关系,相关系数分别为0.9844和0.9967,检出限为9.0×10-10mol L(S N=3)。探讨了洛美沙星在碳糊电极上的伏安性质和电极反应机理,并且成功地应用于人体尿液中洛美沙星的测定,结果与紫外光度法基本吻合。     

Pre-concentration of vitamin K1 (phylloquinone) at carbon paste electrodes and its determination in plasma by adsorptive stripping voltammetry

Linear sweep voltammetry was used to study the accumulation behaviour of vitamin K1 at carbon paste electrodes prepared with different types of graphite and pasting agents. The vitamin was found to undergo strong accumulation, but this depended on the type of graphite and pasting agent used. A carbon paste electrode containing Nujol - Ultra Carbon Ultra Superior Purity graphite (25 + 75 m/m) gave the highest sensitivity with adsorptive stripping voltammetry; the optimum accumulation time was 15 min at an open circuit. A variety of procedures were investigated in order to separate vitamin K1 from plasma prior to adsorptive stripping analysis. These procedures were evaluated for plasma levels of the vitamin that are likely to be encountered in pharmacokinetic studies. A solvent extraction method using hexane and ethanol gave the best recovery (91%) and detection limits [180 ng ml-1 in the supporting electrolyte (450 ng ml-1 in plasma)]. However, the analysis time could be reduced by 50% (with some loss of sensitivity) by using ethanol to deproteinate the plasma with the measurement being made directly on the resulting supernatant. As the calibration graphs are linear, quantification can be performed by the method of single standard additions; therefore, relatively short analysis times are feasible.     

Determination of rutin and other flavonoids by flow-injection/adsorptive stripping voltammetry using nujol-graphite and diphenylether-graphite paste electrodes

The possibility of determination of twelve flavonoids (fisetin, galangin, hesperetin, hesperidin, kaempherol, morin, myricetin, naringin, quercetin, quercitrin, rutin, rhamnetin) using adsorptive stripping voltammetry in a flow injection system is examined. Carbon paste electrodes based on mixtures of nujol-graphite and diphenylether-graphite were used and compared as working electrodes and measurements were made using both 'direct' and 'medium-exchange' procedures. The effect of experimental parameters such as pH, accumulation potential and period, presence of various compounds was examined. Sample size (typically 0.33 ml) is greatly reduced by applying a reciprocating flow of the sample plug through the detector during the preconcentration step. The instrumental sensitivities and lower detection limits were calculated for all flavonoids in all cases. In some cases the differences are so high that determination of certain flavonoids in the presence of excess of others is allowed. Depending on the flavonoid, the electrode type, and the measurement procedure the analytical range and the reproducibility (RSD%) were 10(-5)-10(-8) M and 2.5-10%, respectively. A simple procedure is developed for the electrochemical determination of rutin in a multivitamin preparation.     

Voltammetric study of nifuroxazide at unmodified and Sephadex-modified carbon paste electrodes

The electrooxidation of nifuroxazide was investigated by cyclic and differential-pulse voltammetry at carbon paste and Sephadex-modified carbon paste electrodes. Nifuroxazide is irreversibly oxidized at all pH values and gives rise to a well-defined oxidation peak. The modification of the carbon paste surface with Sephadex allowed a preconcentration process to take place for nifuroxazide such that higher sensitivity was achieved compared with the bare surface. The influence of the scan rate, time of accumulation, modifier loading, solution conditions and pH on the adsorptive step at the modified carbon paste electrodes was investigated. The direct determination of the drug in urine is also discussed. Received: 2 June 1998 / Revised: 29 January 1999 / Accepted: 2 February 1999     

Voltammetric study of nifuroxazide at unmodified and Sephadex-modified carbon paste electrodes

The electrooxidation of nifuroxazide was investigated by cyclic and differential-pulse voltammetry at carbon paste and Sephadex-modified carbon paste electrodes. Nifuroxazide is irreversibly oxidized at all pH values and gives rise to a well-defined oxidation peak. The modification of the carbon paste surface with Sephadex allowed a preconcentration process to take place for nifuroxazide such that higher sensitivity was achieved compared with the bare surface. The influence of the scan rate, time of accumulation, modifier loading, solution conditions and pH on the adsorptive step at the modified carbon paste electrodes was investigated. The direct determination of the drug in urine is also discussed.     

Determination of folic acid by adsorptive stripping voltammetry at the static mercury drop electrode

Folic acid can be determined at nanomolar concentrations by controlled adsorptive accumulation of folic acid on a static mercury drop electrode held at ?0.3 V vs. Ag/AgCl followed by reduction of the surface species. In 0.1 M sulfuric acid, a cathodic scan gives peaks at ?0.47 v and ?0.75 V vs. Ag/Agcl; the latter peak provides greater sensitivity. Differential-pulse stripping is shown to be superior to normal-pulse and d.c. stripping. After a 5-min preconcentration, the detection limit is about 1 × 10^?10 M folic acid. The adsorptive stripping response is evaluated with respect to concentration dependence, preconcentration time and potential, solution acidity and the presence of gelatin and bromide. The relative standard deviation at the 5 × 10^?8 M level is 1.2%. This method is applied to the determination of folic acid in pharmaceutical tablets.     

Indirect measurement of brucine by adsorptive stripping voltammetry at mercury electrode

After reaction with nitric acid, brucine can be transformed into cacotheline, and then measured indirectly by adsorptive stripping voltammetry. This method is based on the adsorptive accumulation of cacotheline at a hanging mercury drop electrode, followed by cathodic linear sweep voltammetry. The cathodic peak potential is about -0.35 V (vs. saturated Ag AgCl ). The detection limit of 2.0 x 10(-9) M is obtained under optimized conditions. The electrochemical behaviour of cacotheline and the mechanism of the electrode reactions are discussed.     

Automatic adsorptive stripping voltammetry at thin-mercury film electrodes (TMFE)

A procedure for the automated on-line determination of nickel in aquatic samples was developed. It is based upon adsorptive stripping voltammetry of the dimethylglyoxime complex at a thin-mercury film electrode (TMFE) on glassy carbon substrate. The severe problem of reproducibly renewing the TMFE was solved by the choice of an appropriate electrolyte and a special potential program. With the developed procedure automatic on-line nickel determinations are possible over extended periods of time with standard deviations not higher than 5% and down to 1.3 ppb nickel.Dedicated to Professor Dr. W. Fresenius on the occasion of his 80th birthday     

Determination of dinoseb by adsorptive stripping voltammetry using a mercury film electrode

An adsorptive stripping voltammetric method for the determination of the pesticide dinoseb (2-sec.-butyl-4,6-dinitrophenol) at the mercury film electrode is described. The deposition of the mercury film on a glassy carbon disk electrode was optimized. The temperature, at which the mercury film was deposited, was demonstrated to have a strong influence on the stripping peaks, the first one being much more intense than the second. A systematic study of the variables affecting the stripping response was carried out by differential pulse voltammetry. The results obtained have been compared with those at the HMDE; a significant improvement in the sensitivity of the method developed with the MFE was observed. Using a 300 s accumulation time, the limits of determination and detection were 3.6 × 10^–10 and 1.1 × 10^–10 mol L^–1, respectively. The effect of the presence of several herbicides on the dinoseb response was also tested. The method has been applied to the determination of the pesticide in spiked apple juice at two concentration levels: 12.0 and 1.2 g L^–1 of juice.