Electroanalytical Study of the Pesticide Ethiofencarb

Abstract

A detailed study of voltammetric behavior of ethiofencarb (ETF) is reported using glassy carbon electrode (GCE) and hanging mercury drop electrode (HMDE). With GCE, it is possible to verify that the oxidative mechanism is irreversible, independent of pH, and the maximum intensity current was observed at +1.20 V vs. AgCl/Ag at pH 1.9. A linear calibration line was obtained from 1.0×10^?4 to 8.0×10^?4 mol L^?1 with SWV method. To complete the electrochemical knowledge of ETF pesticide, the reduction was also explored with HMDE. A well‐defined peak was observed at –1.00 V vs. AgCl/Ag in a large range of pH with higher signal at pH 7.0. Linearity was obtained in 4.2×10^?6 and 9.4×10^?6 mol L^?1 ETF concentration range.

An immediate alkaline hydrolysis of ETF was executed, producing a phenolic compound (2‐ethylthiomethylphenol) (EMP), and the electrochemical activity of the product was examined. It was deduced that it is oxidized on GCE at +0.75 V vs. AgCl/Ag with a maximum peak intensity current at pH 3.2, but the compound had no reduction activity on HMDE.

Using the decrease of potential peak, a flow injection analysis (FIA) system was developed connected to an amperometric detector, enabling the determination of EMP over concentration range of 1.0×10^?7 and 1.0×10^?5 mol L^?1 at a sampling rate of 60 h^?1. The results provided by FIA methodology were performed by comparison with results from high‐performance liquid chromatography (HPLC) technique and demonstrated good agreement with relative deviations lower than 4%. Recovery trials were performed and the obtained values were between 98 and 104%.     

Photometric Determination of Iron in Pharmaceutical Formulations Using Double-Beam Direct Injection Flow Detector

In this work, an innovative, flow-through, double-beam, photometric detector with direct injection of the reagents (double-DID) was used for the first time for the determination of iron in pharmaceuticals. For stable measurement of the absorbance, double paired emission-detection LED diodes and a log ratio precision amplifier have been applied. The detector was integrated with the system of solenoid micro-pumps. The micro-pumps helped to reduce the number of reagents used and are responsible for precise solution dispensing and propelling. The flow system is characterized by a high level of automation. The total iron was determined as a Fe(II) with photometric detection using 1,10-phenanthroline as a complexing agent. The optimum conditions of the propose analytical procedure were established and the method was validated. The calibration graph was linear in the range of 1 to 30 mg L⁻¹. The limit of detection (LOD) was 0.5 mg L⁻¹. The throughput of the method was 90 samples/hour. The repeatability of the method expressed as the relative standard deviation (R.S.D.) was 2% (n = 10). The method was characterized by very low consumption of reagents and samples (20 μL each) and a small amount of waste produced (about 540 µL per analysis). The proposed flow method was successfully applied for determination of iron in pharmaceutical products. The results were in good agreement with those obtained using the manual UV-Vis spectrophotometry and with values claimed by the manufacturers. The flow system worked very stably and was insensitive to bubbles appearing in the system.     

Quantitative Analysis of Irbesartan in Pharmaceuticals and Human Biological Fluids by Voltammetry

Abstract

A differential pulse (DP) and square wave (SW) voltammetric techniques were developed for the determination of irbesartan. The electrochemical behavior of irbesartan was investigated by cyclic voltammetry (CV), differential pulse voltammetry (DPV), and square wave voltammetry (SWV) at the hanging mercury drop electrode (HMDE). Different parameters were tested to optimize the conditions of the determination. It was found that in the range of 8 × 10^?6–1 × 10^?4 M, the currents measured by both of methods presented a good linear property as a function of the concentration of irbesartan. In addition, validation parameters, such as reproducibility, sensitivity, and recovery were evaluated as well. The slope of the log Ip- log ν linear plot was 0.58 indicating the diffusion control for 0.5 M sulphuric acid without the need for separation or complex sample preparation, since there was no interference from the excipients and endogenous substances.

The methods were successfully applied to the analysis of irbesartan in the pharmaceutical tablet formulations and in human serum samples.     

Improvement of Pulse Amperometric Detection Integrated Automated Flow Injection Analysis of Ethylenethiourea Determination

Improvement of pulse amperometric detection (PAD) method is demonstrated in determination of ethylenethiourea (imidazolidine‐2‐thione, ETU). The anodic detection of ETU will produce polymeric film on an electrode leading to an inactive electrode surface. Here, the PAD method was used to remove the polymeric film formed on the electrode surface between ETU detection. Further, the scheme was integrated with automated flow injection analysis (AFIA) for determining ETU. The operational parameters of PAD in the AFIA system were discussed thoroughly. The analytical characteristics of the system were evaluated at optimum conditions. The linear range of calibration plot was between 20 to 300 μM (the correlative coefficient, r = 0.999) and the detection limit was 0.9 μM (S/N = 3). The relative standard deviations of detection of 50 μM ETU were 0.82% with and 9.07% without PAD scheme. The results indicate the system is a very promising tool for ETU determination. Finally, the matrix effects of two water samples that were collected from a campus and a farm show good recoveries of 92% and 96%.     

Electrochemical Determination of Citalopram by Adsorptive Stripping Voltammetry–Determination in Pharmaceutical Products

Abstract

The electrochemical behavior of citalopram was studied by square‐wave and square‐wave adsorptive‐stripping voltammetry (SWAdSV). Citalopram can be reduced and accumulated at a mercury drop electrode, with a maximum peak current intensity being obtained at a potential of approximately ?1.25 V vs. AgCl/Ag, in an aqueous electrolyte solution of pH 12. A SWAdSV method has been developed for the determination of citalopram in pharmaceutical preparations. The method shows a linear range between 1.0×10^?7 and 2.0×10^?6 mol L^?1 with a limit of detection of 5×10^?8 mol L^?1 for an accumulation time of 30 s. The precision of the method was evaluated by assessing the repeatability and intermediate precision, achieving good relative standard deviations in all cases (≤2.3%). The proposed method was applied to the determination of citalopram in five pharmaceutical products and the results obtained are in good agreement with the labeled values.     

Electrochemical study of butylate: application to the analysis of water

A biochemical gas-sensor (bio-sniffer) was constructed for convenient measurement of odourless hydrogen peroxide (H₂O₂) vapour, which is harmful to skin and mucous membranes. An enzyme-immobilized membrane was fabricated by spreading the mixture of catalase and photo-crosslinkable polymer on a dialysis membrane. An H₂O₂ biosensor was constructed by attaching this catalase-immobilized membrane to the sensitive top of a Clark-type oxygen electrode, and the oxygen generation from the decomposition of H₂O₂ catalysed by catalase was measured amperometrically. This biosensor was first applied to the measurement of H₂O₂ solution and was able to quantify the concentrations of H₂O₂ solution from 0.02 to 10.0?mmol?L^?1. Then, this biosensor was applied to gaseous phase as a bio-sniffer and was able to detect the odourless H₂O₂ vapour with the calibration range from 0.5 to 30?ppm, where the threshold limit value assigned by the American Conference of Governmental Industrial Hygienists (1?ppm) is covered.     

Adsorptive Stripping Voltammetric Determination of Albendazole at a Hanging Mercury Drop Electrode

ABSTRACT

Albendazole is determined by differential-pulse adsorptive cathodic stripping voltammetry at a hanging mercury drop electrode using the reduction peak of its copper(II) complex at ?0.28V at an accumulation potential 0.0V vs. Ag/AgCl electrode. The optimum conditions of pH, accumulation potential and accumulation time were studied. The calibration graph for the determination of albendazole was linear in the range 3.0X10^?8 - 9X10^?7M with a relative standard deviation of 2.8%. The detection limit was 1.0X10^?8M after 180s accumulation at 0.0V. The effect of common excipients and metal ions on the peak height of albendazole was studied. The presence of Cu²⁺ ions forms a stable complex with albendazole which is strongly adsorbed at the mercury electrode surface. The method was applied to the determination of the drug in commercially available dosage forms.     

Determination of Ethanol in Alcoholic Drinks: Flow Injection Analysis with Amperometric Detection Versus Portable Raman Spectrometer

A flow injection analysis with integrated amperometric alcohol dehydrogenase biosensor and a handheld Mira‐DS Raman spectrometer have been compared for the determination of ethanol in different samples of alcoholic drinks. The biosensor was constructed from the commercial screen‐printed carbon electrode as amperometric transducer and covered by a thin layer comprising alcohol dehydrogenase, reduced single‐layer graphene oxide, rhodium(IV) dioxide, and glutaraldehyde. Both assemblies were tested on analysis of plum brandy, white rum, vodka, white and red wines, strong dark beer, and non‐alcoholic beer. The two principally different analytical methods were critically compared and some limitations found, especially in case of analysis of red wine and beers. Finally, some future improvements of both analytical tools under test outlined.     

Electroanalytical Study of the Antioxidant and Antitumor Agent Curcumin

Curcumin (CU) shows a wide range of pharmacological properties including antioxidant, anti‐inflammatory, and antitumor effects. In order to understand the chemical basis of different activities of curcumin, we have studied the oxidation and reduction of curcumin. Based on cyclic and differential pulse voltammetric methods, using carbon paste and hanging mercury drop electrodes, in the present study we tested different parameters to optimize the conditions for the determination of curcumin and its electrochemical characteristics. Better results were obtained via differential pulse voltammetry using carbon paste electrode. Curcumin yields well‐defined differential pulse voltammetric responses with well‐defined oxidation (in the potential region of 0.3–0.6 V, vs. Ag/AgCl) and reduction (at 0.3 V) peaks using carbon paste electrode.     

Electroanalytical Detection of the Pesticide Paraquat by Batch Injection Analysis

Abstract

The Batch‐Injection Analysis (BIA) technique has been applied to the electroanalytical detection of the herbicide paraquat by square wave voltammetry (SWV) during sample injection. The results obtained showed that the herbicide can be detected at µg l^?1 levels with small injection volumes (<100 µl). The time of each measurement was less than two seconds. The BIA method presents many advantages such as being extremely fast, with high reproducibility, good sensitivity and simple without pre‐addition of or changing the supporting electrolyte.     

A New Poly (Vinyl Chloride) Matrix Membrane Electrode for Manual and Flow Injection Determination of Pilocarpine in Some Pharmaceutical Preparations

Abstract

A novel pilocarpinium ion selective membrane electrode is prepared, characterized and used in pharmaceutical analysis. The electrode system incorporates a PVC membrane with pilocarpine-reineckatc ion pair complex as an electroactive material. The electrode exhibits a fast near-Nernstian response for 10^?1-4x10^?5M pilocarpine over the pH range 4-6.5. The electrode displays a good selectivity for pilocarpine with respect to a number of foreign cations. Pilocarpine in various pharmaccutical preparations is determined either by direct potentiometry or potentiometric titration with NaTPB using the proposed sensor. Pilocarpinereineckate membrane is also used in a flow through sandwich cell as a detector for flow injection determination of pilocarpine. Results with an average recovery of 99% and a relative standard deviation of ± 0.3% are obtained. The data compare favorably with those obtained by the standard US Pharmacopeia method.     

Determining Trace Concentrations of Copper in Water by Cathodic Film Stripping Voltammetry with Adsorptive Collection

Abstract

A technique is presented for the determination of trace concentrations of copper (II) in natural water samples by cathodic stripping voltammetry of a film of copper-catechol complex ions adsorbed on the hanging mercury drop electrode. The peak height of the copper-catechol reduction peak is linearly dependent upon the copper (II) concentration between 10^?10 and 10^?7 M. The detection limit of the technique is below 10^?10 M copper (II) for a collection time of 3 minutes, but the sensitivity can be further increased four-fold by collecting for 15 minutes. The sensitivity is reduced by high concentrations of competing trace metals and of surfactants, which necessitate the use of standard additions to the sample.     

Electrochemical Determination of Boron in Natural Waters

Abstract

A sensitive voltammetric method for the determination of trace boron, based on the formation of the complex of boric acid with 4‐hydroxy‐5‐[salicylideneamino]‐2‐7‐naphthalenedisulfonic acid (azomethine H) is described. The reduction of the boric acid‐azomethine H complex at a hanging mercury drop electrode was exploited by square wave voltammetry (SWV) and cyclic voltammetry to determine boron in natural water samples, which were collected in the regions surrounding the boron mines of Central Anatolia. A reduction peak that belongs to the boric acid‐azomethine H complex at this electrode was observed at ?1.05 V vs. Ag/AgCl/KCl_(sat.). The effects of various parameters, such as ligand concentration, boric acid concentration, and formation time of the boric acid‐azomethine H complex, were investigated. Electrochemical experiments were conducted in 1.0 M HOAc/0.5 M NH₄OAc buffer at pH of 4.4±0.2. Linear working range was established by regression analysis between 5.0×10^?8 M and 1.0×10^?4 M. The probable metal cation interferences in water samples were eliminated by adding EDTA (ethylenediaminetetraacetic acid) to the samples. Data obtained using the square wave voltammetric (SWV) technique was compared statistically with inductively coupled plasma mass spectroscopy (ICP‐MS) data. Evaluation of the method based on statistical data was performed and the values of the limit of detection (LOD) and limit of quantitation (LOQ) were found to be 4.17×10^?6 M and 1.39×10^?5 M, respectively.     

Determination of Cobalt Ions in Natural Waters Using Differential Pulse Adsorptive Stripping Voltammetry

Abstract

Differential pulse adsorptive stripping voltammetry using dimethylglyoxime complexes in the presence of triethanolamine and ammonium chloride can be applied to the determination of cobalt (II) ions in natural waters with high sensitivity. The limit of detection is about 3 ppt. Actual analysis of estuary water are reported. In this particular case of natural water, the factors influencing the use of differential pulse adsorptive stripping voltammetry for the determination of cobalt are described in detail.     

Rapid Determination of Fluoride in Potable Waters by Potentiometric Flow Injection Analysis

Abstract

A potentiometric flow injection analysis system is described, enabling tap water and other fluoride-bearing matrices of low interferent level to be determined at the rate of 360 samples per hour using an electrode polished with slurried alumina. Important parameters, such as carrier stream composition, sample volume and detector cell design are discussed with respect to this system, Fluoride electrodes regenerated with silver fluoride and silver epoxy are evaluated in flow injection mode, both before and after polishing.     

Imprinted Polymer – Modified Hanging Mercury Drop Electrode for Differential Pulse Adsorptive Stripping Voltammetric Analysis of a Diquat Herbicide

An imprinted polymer modified hanging mercury drop electrode (HMDE) in Model 303A system in conjunction with a PAR Model 264A Polarographic Analyzer/Stripping Voltammeter has been used for the selective analysis of a diquat herbicide viz., 5,6‐dihydropyrazino[1,2,3,4‐[lmn]‐1,10‐phenanthrolinium dichlorides in differential pulse cathodic stripping voltammetry mode. Complex aqueous samples (drinking water and agricultural soil suspension), spiked with a diquat herbicide, were directly analyzed by the adsorptive accumulation of the analyte over the working electrode (accumulation potential ?0.8 V (vs. Ag/AgCl), accumulation time 120 s, pH 7.0, supporting electrolyte 0.1 M KCl, scan rate 10 mV s^?1, pulse amplitude 25 mV). The limit of detection for diquat herbicide was found to be 0.34 nmol L^?1 (0.1 ppb, RSD 2%, S/N=2).     

Study of the voltammetric behaviour of metam and its application to an amperometric flow system

The electrochemical behaviour of the pesticide metam (MT) at a glassy carbon working electrode (GCE) and at a hanging mercury drop electrode (HMDE) was investigated. Different voltammetric techniques, including cyclic voltammetry (CV) and square wave voltammetry (SWV), were used. An anodic peak (independent of pH) at +1.46 V vs AgCl/Ag was observed in MT aqueous solution using the GCE. SWV calibration curves were plotted under optimized conditions (pH 2.5 and frequency 50 Hz), which showed a linear response for 17–29 mg L⁻¹. Electrochemical reduction was also explored, using the HMDE. A well defined cathodic peak was recorded at −0.72 V vs AgCl/Ag, dependent on pH. After optimizing the operating conditions (pH 10.1, frequency 150 Hz, potential deposition −0.20 V for 10 s), calibration curves was measured in the concentration range 2.5×10⁻¹ to 1.0 mg L⁻¹ using SWV. The electrochemical behaviour of this compound facilitated the development of a flow injection analysis (FIA) system with amperometric detection for the quantification of MT in commercial formulations and spiked water samples. An assessment of the optimal FIA conditions indicated that the best analytical results were obtained at a potential of +1.30 V, an injection volume of 207 μL and an overall flow rate of 2.4 ml min⁻¹. Real samples were analysed via calibration curves over the concentration range 1.3×10⁻² to 1.3 mg L⁻¹. Recoveries from the real samples (spiked waters and commercial formulations) were between 97.4 and 105.5%. The precision of the proposed method was evaluated by assessing the relative standard deviation (RSD %) of ten consecutive determinations of one sample (1.0 mg L⁻¹), and the value obtained was 1.5%.     

A New Voltammetric Approach for Electrochemical Determination of Lamotrigine in Pharmaceutical Samples

A new linear sweep voltammetric method for quantitative lamotrigine (LMT) determination based on an electrochemically pre-treated pencil graphite electrode (PGE*) is presented. Response characteristics of the PGE* toward the mentioned compound were investigated by cyclic voltammetry and linear sweep voltammetry. The quantitative determination of LMT revealed a wide linear range of 2.5 ⋅ 10⁻⁵–1.0 ⋅ 10⁻³ M with a detection limit of 1.94 ⋅ 10⁻⁵ M. The method was used successfully for LMT determination in a pharmaceutical formulation.     

流动注射在线光化学荧光法测定药物制剂中叶酸的含量

叶酸接受紫外光照后可转变成最大激发波长为274nm、最大发射波长为466nm的强荧光化合物。对光化学反应介质进行考察，发现在NaC03—NaHC03缓冲体系中所产生的光化学荧光最强，据此建立了流动注射在线光化学荧光分析法。试样在水载流的携带下与PH9．5的Na2C03—NaHC03缓冲溶液汇流后，通过一个盘绕在6—W低压汞灯上的PTFE编结式光化学反应器。在反应器中所生成的荧光化合物直接通入荧光计的流通池测定荧光强度。在最佳条件下，动态线性范围可达0．001-4mg／L，检测限为0．16μg/L，采样速率达80／h，11次测定浓度分别为0．01和0．1mg／L的叶酸标准溶液所得到的RSD分别为1．0％和0．2％。所建立的方法已成功地用于片剂中叶酸含量的测定。     

流动注射光化学荧光法测定药物制剂中的盐酸氯丙嗪

氯丙嗪的流动注射光化学反应在一编结反应器中进行，该反应器盘绕在一荧光灯上并接受由该灯发生出的最大幅波长为３６５ｎｍ的紫外线照射。用２５３．０ｎｍ的激发波长和３７４．５ｎｍ的荧光波长在线测定光化学反应产物的荧光强度。在最佳条件下，检测限为５．４μｇ／Ｌ，采样速度为９０次／ｈ，１ｍｇ／Ｌ的分析物１１次测定的相对标准偏差为０．５％，动态线性范围为０．０１－６．００ｍｇ／Ｌ。所建立的方法已成功地地用于片剂