Determination of pesticides in vegetable samples using an acetylcholinesterase biosensor based on nanoparticles ZrO2/chitosan composite film

An amperometric pesticides inhibition biosensor has been developed and used for determination of pesticides in vegetable samples. To eliminate the interference of ascorbic acid, multilayer films of polyelectrolyte (chitosan/polystyrensulfonate) were coated on the glass carbon electrode. Then, acetylcholinesterase was immobilized on the electrode based on surface-treated nanoporous ZrO₂/chitosan composite film as immobilization matrix. As a modified substrate, acetylthiocholine was hydrolysed by acetylcholinesterase and produced thiocholine which can be oxidized at +700?mV vs. SCE. Pesticides inhibit the activity of enzyme with an effect of decreasing of oxidation current. The experimental conditions were optimized. The electrode has a linear response to acetylthiocholine within 9.90?×?10^?6 to 2.03?×?10^?3?M. The electrode provided a linear response over a concentration range of 6.6?×?10^?6 to 4.4?×?10^?4?M for phoxim with a detection limit of 1.3?×?10^?6?M, over a range of 1.0?×?10^?8 to 5.9?×?10^?7?M for malathion, and over a range of 8.6?×?10^?6 to 5.2?×?10^?4?M for dimethoate. This biosensor has been used to determine pesticides in a real vegetable sample.     

Differential Pulse Voltammetric Determination of Montelukast in Tablets and Human Plasma by Using Chitosan Modified Carbon Paste Electrode

Electrochemical reduction and determination of montelukast (MKS) was studied in methanol – 0.1 M HCl solution (1 : 1, v/v) by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) at chitosan modified carbon paste electrode. The linear range was 1.70×10^?7–1.83×10^?5 M for DPV analysis. Limit of detection (LOD) and limit of quantification (LOQ) were 5.32×10^?8 M and 1.61×10^?7 M, respectively. The developed method was successfully applied to the determination of MKS in tablets and spiked human plasma. The results obtained were in good agreement with those obtained using a reported spectrofluorimetric technique.     

Polarographic determination of herbicide thifensulfuron methyl/application to agrochemical pesticide,soil, and fruit juice

A novel, sensitive, simple, fast, and fully validated differential pulse polarographic (DPP) method for the determination of trace amounts of thifensulfuron-methyl in pesticide formulation, soil, and orange juice is reported. This procedure was based on a highly sensitive peak formed due to the reduction of thifensulfuron-methyl on a dropping mercury electrode over the pH range 1.00–10.00 in Britton–Robinson buffer. The polarographic reduction exhibits only a single peak in the pH ranges pH?≥?3.0 and pH?≤?6.0 and pH?=?10.0 located at potential values of ?1.010, ?1.350, and ?1.610?V (vs. SCE), respectively. The single peak appeared as a maximum at pH 3.0 (?1.010?V) was well resolved and suitable to be investigated for analytical use. This peak showed quantitative increments with the additions of standard thifensulfuron-methyl solution under the optimal conditions, and the cathodic peak current was linearity proportional to the thifensulfuron-methyl concentration in the range of 2?×?10^?7–5?×?10^?5?M. The limit of detection (LOD) and limit of quantification (LOQ) were obtained as 1.05?×?10^?7 and 3.50?×?10^?7?M, respectively, according to the relation k ?×?SD/b (where k?=?3 for LOD, k?=?10 for LOQ, SD is the standard deviation of the blank, and b is the slope of the calibration curve). The proposed method was applied to pesticide formulation (Harmony® Extra), and the average percentage recovery was in agreement with that obtained by the spectrophotometric comparison method, 97.82 and 102.6%, respectively. The method was extended to determination of thifensulfuron-methy in spiked soil and orange juice, showing a good reproducibility and accuracy with a relative standard deviation of 4.55 and 1.40%, and relative errors of +2.80 and +1.90%, respectively.     

Using 2,4 DNPH-PVC membrane sensors for indirect determination of formaldehyde in urea glue and wastewater

Three simple, rapid, and sensitive ion-selective electrodes for indirect determination of free formaldehyde in urea glue and wastewater have been developed. The methods are based on the formation of the membrane sensors 2,4-dinitrophenylhydrazine-phosphtungestic acid (DNPH-PTA), 2,4-dinitrophenylhydrazine-phosphomolybdic acid (DNPH-PMA), and 2,4-dinitrophenylhydrazine-tetraphenylborate (DNPH-TPB) as neutral carriers. The sensors are stable and show fast potential responses of 30?s, and near-Nernstian cationic slopes of 56.2?±?0.5, 54.3?±?0.5, and 53.8?±?0.4?mV per decade of activity between pH 0.5 and 3.5 over a wide range of 2,4-dinitrophenylhydrazine concentrations (1?×?10^?5 to 1?×?10^?2?M). These sensors were used for indirect determination of formaldehyde over concentration range (1?×?10^?4 to 1?×?10^?1?M). The selectivity coefficients of the developed sensors indicate excellent selectivity for 2,4 DNPH over a large number of organic and inorganic species. The mediator o-nitrophenyloctyl ether has a significant affect on the lifetime of the fabricated sensors. The analytical applications of the proposed sensors showed good results for indirect determination of formaldehyde in formaldehyde solutions, wastewater solutions, and free formaldehyde in urea-formaldehyde liquid and powder glues. The results were compared favourably with that obtained by ASTM, colorimetric, and British Standard methods.     

Hemin Modified Carbon Fat Electrode for Analyzing Antimalarial Endoperoxide Artemisinin in Artemisia annua

A hemin bulk modified carbon electrode with Adeps neutralis (solid fat) as binder was developed for the determination of antimalarial endoperoxide artemisinin in plant matrix. The hemin modified electrode showed significant catalytic activity for the electrochemical reduction of artemisinin at about ?380 mV vs. Ag/AgCl in phosphate buffer solution of pH 7 by using cyclic and differential pulse voltammetry. Under optimized conditions strict linearity between artemisinin concentration and height of the cathodic catalytic current peak was observed in 4.8×10^?6–7.8×10^?5 M concentration range (R=0.9991) when using differential pulse voltammetry. The detection limit was calculated as 1.4×10^?6 M of artemisinin. The developed electroanalytical device is suitable for the determination of artemisinin in Artemisia annua extracts.     

Polarographic determination of pirimicarb

A sensitive and selective polarographic method for the determination of pirimicarb is proposed. Linear calibration graphs were obtained by differential-pulse polarography in the 3.0 × 10^?7–9.0 × 10^?5 mol l^?1 range, the limit of determination being 2.8 × 10^?7 mol l^?1. No interferences were observed from other carbamate pesticides such as aminocarb, bendiocarb or carbaryl and only a matrix effect occurs in the presence of methiocarb. The method was applied to the determination of Pirimicarb in water samples with good recoveries.     

Cobalt(II)-selective membrane electrode based on N,N′-di(thiazol-2-yl)formimidamide

A new PVC-membrane electrode for Co²⁺ ions based on N,N′-di(thiazol-2-yl)formimidamide (TF) as membrane carrier has been developed. The electrode resulted in Nernstian response (29.5?±?0.4?mV decade^?1) for Co²⁺ ion over a wide concentration range (2.5?×?10^?7 ?1.0?×?10^?1?M) with a detection limit of 6.1?×?10^?8?M. The sensor has a response time of about 10?s, and can be used for at least 2 months without observing any deviation from the Nernstain response. The electrode revealed good selectivity towards cobalt(II) ion over a wide variety of alkali, alkaline earth, transition, and heavy metal ions and could be used in the pH range 2.0–7.0. The electrode was used for determination of Co²⁺ in real samples.     

Determination of Hydrogen Peroxide by Electrochemiluminescence Using a Chitosan–graphene Composite Film Doped Cadmium-Tellurium Quantum Dot Modified Glassy Carbon Electrode

Here is reported the novel determination of hydrogen peroxide by electrochemiluminescence using a chitosan–graphene composite film doped cadmium-tellurium quantum dot modified glassy carbon electrode. The cadmium-tellurium quantum dots were studied by absorption and fluorescence spectroscopy. Scanning electron microscopy and electrochemical impedance spectroscopy were used to characterize the structure morphology of the composite matrix. The electrochemiluminescence emission was linear with the concentration of hydrogen peroxide in the range of 3.5?×?10^?7 to 1.1?×?10^?5?M with a determination limit of 2.1?×?10^?7?M. Furthermore, the modified electrode showed excellent reproducibility and stability.     

Electrochemical study of vinylsulphone azo dye Reactive Black 5 and its determination at a glassy carbon electrode

The electrochemical oxidation of vinylsulphone azo dye, Reactive Black 5 (RB5), at a glassy carbon electrode has been carried out in phosphate buffer solutions in the pH range 2.85?C11.79 employing cyclic voltammetry (CV) and differential pulse voltammetry (DPV). RB5 showed one well-defined oxidation peak at 0.560 V vs. Ag-AgCl using DPV. The oxidation process was shown to be irreversible over the pH range 2.85?C8.39 and was diffusion controlled. The linear relationship between the peak current height and RB5 concentrations allowed the differential pulse voltammetric determination of the dye over a wide concentration range, from 6.0 × 10^?7 to 1.5 × 10^?6 M with a detection limit of 4.0 × 10^?7 M. The precision and recovery did not exceed 4.9 and 98.2%, respectively. A UV-Vis spectrophotometry method was also proposed for the determination of the RB5 in concentration range from 5.0 × 10^?6 M to 1.0 × 10^?5 M at ??_max = 600 nm with limit of detection of 4.7 × 10^?6 M and RSD of 1.8% for RB5 concentration of 1.0 × 10^?5 M.     

Sensitive spectrophotometric detection of dopamine,levodopa and adrenaline using surface plasmon resonance band of silver nanoparticles

A simple and effective procedure is proposed for spectrophotometric determination of catecholamines; Dopamine (1), L-Dopa (2) and Adrenaline (3). It was found that the reduction of Ag⁺ to silver nanoparticles (Ag-NPs) by these catecholamines in the presence of polyvinylpyrrolidone (PVP) as a stabilizing agent produced very intense surface plasmon resonance peak of Ag-NPs. The plasmon absorbance of the Ag-NPs allows the quantitative spectrophotometric detection of the catecholamines. The calibration curves derived from the changes in absorbance at λ = 440 nm were linear with concentration of Dopamine, Levodopa and Adrenaline in the range of 3.2×10^?6? 2.0×10^?5 M, 1.6×10^?7 ? 1.0×10^?5 M, 1.5×10^?6? 4.0×10^?5 M, respectively. The detection limits (3σ) were 1.2×10^?6 M, 8.6 ×10^?8 M, 9.7 ×10^?7 M for the Dopamine, L-Dopa and Adrenaline, respectively. The method was applied successfully to the determination of catecholamines in Ringer’s injection serum.     

Determination of Tetracycline by Microdroplet Hydrodynamic Adsorptive Voltammetry Using a Multiwalled Carbon Nanotube Paste Rotating Disk Electrode

A novel and simple method is proposed for the determination of tetracycline by adsorptive voltammetry in a droplet using a carbon nanotube paste rotating disk electrode (CNTP-RDE). An enhanced electrochemical oxidation response of tetracycline was observed in pH 8.2 supporting electrolyte by the addition of a long-chain cationic surfactant, such as benzyldimethyltetradecylammonium chloride (zephiramine). Under the optimized experimental conditions, the calibration curve was linear across a tetracycline concentration range from 1.0?×?10^?7 to 2.0?×?10^?6 M. The limit of detection and sensitivity were 4.0?×?10^?8 M and 0.9358?A M^?1, respectively. This method was successfully employed for the determination of tetracycline in milk samples.     

Simultaneous Square‐Wave Voltammetric Determination of Paracetamol,Caffeine and Orphenadrine in Pharmaceutical Formulations Using a Cathodically Pretreated Boron‐Doped Diamond Electrode

An electroanalytical method for the simultaneous determination of paracetamol (PAR), caffeine (CAF), and orphenadrine (ORPH) using the square‐wave voltammetry (SWV) and a cathodically pretreated boron‐doped diamond electrode was developed. The method exhibits linear responses to PAR, CAF, and ORPH in the concentration ranges 5.4×10^?7–6.1×10^?5 M, 7.8×10^?7–3.5×10^?5 M, and 7.8×10^?7–3.5×10^?5 M, respectively, with detection limits of 2.3×10^?7 M, 9.6×10^?8 M, and 8.4×10^?8 M, respectively. The proposed method was successfully applied in the simultaneous determination of these analytes in pharmaceutical formulations.     

Voltammetric Behavior of Mifepristone (RU‐486) Using Square‐Wave and Adsortive Stripping‐Wave Techniques. Determination in Urine Samples

The behavior of Mifepristone (RU‐486) was studied by square‐wave technique, leading to two methods for its determination in aqueous samples and urine samples at pH 2. The application of the square‐wave (SW) without the adsorptive accumulation and stripping voltammetric (AdSV) show the maximum response at ?0.896 V using an accumulation potential of ?0.5 V. The effect of experimental parameters that affect this determination are discussed. For the stripping technique, Mifepristone proved to be more sensitive, yielding signals four times larger than those obtained by applying a square‐wave scan without the previous accumulation. The calibration plot to determine Mifepristone was linear in the range 2.4×10^?8 and 5.4×10^?7 M by stripping mode with an accumulation time t_acc of 30 s. The relative standard deviation obtained for concentration levels of Mifepristone as low as 2.0×10^?7 M with square‐wave was 1.17% (n=10) and with stripping square‐wave 2.02% (n=10) in the same day. The two proposed methods (SW and SWAdSV) were applied to the determination of Mifepristone in urine.     

Ionic liquids with an anion of N-lauroyl sarcosinate in membranes of ion-selective electrode

The study considers solubility in water, extractivity, and electrode properties of ionic liquids (IL), lauroyl tetrahexylammonium (THALS) and tetraoctylammonium lauroyl sarcosinate (TOALS). The values of solubility, found by potentiometry using ion-selective membranes of PVC-electrodes (ISE) have appeared to be 3.0 ± 0.4 mM and 0.011 ± 0.005 mM, for THALS and TOALS, respectively. Both IL quantitatively recover nitrophenol (99.9%) into chloroform from aqueous solutions in the pH range from 2 to 12. The application of IL as the active components of PVC-ISE enables the determination of lauroyl sarcosinate anion in the concentration range 1 × 10^?2?C1 × 10^?4 M for THALS and 1 × 10^?2?C1 × 10^?5 M for TOALS and the determination of mononitrophenols, 2,4-dinitrophenols and picrates (1 × 10^?2 M?C1 × 10^?5 M). A solid-state sensor based on screen-printed electrode modified by TOALS IL has been proposed. The electrode has been used for the determination of 4-nitrophenol in the concentration range 1 × 10^?2?C1 × 10^?5 M, the operational stability of the electrode is 10 days.     

Spectrofluorometry study of β-cyclodextrin and N-phenyl-1-naphthylamine inclusion complex and its analytical application via artificial neural network

The interaction between β-cyclodextrin (βCD) and N-phenyl-1-naphthylamine has been studied spectrofluorimetrically and found to form a 1:1 (βCD:NPN) inclusion complex at optimum conditions of pH 8 with the formation time of 120?s. The association constant of the complex was established to be 6.0?×?10²?M, while a remarkable enhancement in fluorescence intensity was also observed at 445?nm with excitation of 334?nm. A spectroflurometric method for the detection of N-phenyl-1-naphthylamine has been developed having a dynamic range linear up to 4.67?×?10^?7?M with a limit of detection of 0.58?nM. The repeatability study at two different βCD concentrations of 1.0?×?10^?4 and 4.0?×?10^?4?M was found to give RSD values of 2.40 and 1.42%, respectively. Artificial neural network (ANN) has been utilised to model the analytical system and successfully extended the analytical dynamic range up to 8.0?×?10^?7?M from the original 4.67?×?10^?7?M, brief network training and the optimum parameters of are described in this work.     

Voltammetric determination of selenosulfate ions at a mercury-film electrode

A procedure is proposed for the voltammetric determination of selenium as selenosulfate (SO₃Se^2?) ions at a mercury-film electrode (MFE). Selenosulfate ions are determined in the range from 2 × 10^?4 to 1.0 × 10^?3 M without analyte accumulation, using peak current at ?0.92 ± 0.02 V and in the range from 1 × 10^?7 to 2 × 10^?4 M after analyte accumulation with the open circuit, using peak current at ?1.18 ± 0.03 V as the analytical signal. The mechanisms of SO₃Se^2? reduction at an MFE under the conditions of direct voltammetry and stripping voltammetry with accumulation are proposed and discussed.     

Potentiometric sensors based on organic ion exchangers for determining tetraalkylammonium salts

Potentiometric sensors with plasticized polymer membranes based on organic ion exchangers, tetraalkylammonium dodecyl sulfates (benzyldimethyldodecylammonium, benzyldimethyltetradecylammonium, dimethyldistearylammonium), have been proposed for the determination of quaternary ammonium salts in model solutions and KATAPAV technical solutions. The thermal stability, composition, and solubility product have been estimated. It has been shown that ion associates are stable to 60?C70°C, K _S varies in the range from 2 × 10^?8 to 5 × 10^?10. The basic electrochemical parameters of the sensors have been determined as well, such as linearity ranges of the electrode function (5 × 10^?5 (5 × 10^?6)?1 × 10^?2 (1 × 10^?3) M) and slopes of the electrode functions (47?C59 mV/pc), response time (60?C90 sec), potential drift (2?C3 mV/day), operation period (3?C4 months), limits of detection for tetramethylammonium salts (1 × 10^?5?4 × 10^?7 M).     

A nafion/crown ether film electrode and its application in the anodic stripping voltammetric determination of traces of silver

Glassy carbon electrodes are modified by coating with dicyclohexyl-18-crown-6 in Nafion-117. The electrode is used for a very sensitive anodic stripping voltammetric determination of silver. High sensitivity is obtained owing to the release of crown molecules from the silver-crown complex during the deposition. The detection limit is 2×10^?12 M after electrodeposition for 30 min. The recommended supporting electrolyte is 4×10^?3–7×10^?3 M potassium chloride in 0.01 M nitric acid with a deposition potential of ?0.30 V vs. SCE and a linear potential scan. Three typical calibration graphs were linear over the range 2×10^?11–1×10^?8 M for deposition times of 30, 20 and 8 min, respectively. The silver content of reagent-grade ammonium nitrate was found to be 0.48×10^?4% with a relative standard deviation of 3.7% (n=7) for parallel determinations.     

Flow injection determination of hydrogen peroxide using diperiodatoargentate- and diperiodatonickelate-luminol chemiluminescence

A novel chemiluminescence (CL) method for the determination of hydrogen peroxide is described. Method is based on the transition metals in highest oxidation state complex, which include diperiodatoargentate (DPA) and diperiodatonickelate (DPN) and show excellent sensitisation on the luminol-H₂O₂ CL reaction with low luminol concentration in alkaline medium. In particular, the sensitiser which was previously reported (such as Co²⁺, Cu²⁺, Ni²⁺, Mn²⁺, Fe³⁺, Cr³⁺, KIO₄, K₃Fe(CN)₆ etc.) to be unobserved CL due to poor sensitisation with such low concentration of luminol which makes the method hold high selectivity. Based on this observation, the detection limits were 6.5?×?10^?9?mol?L^?1 and 1.1?×?10^?8?mol?L^?1 hydrogen peroxide for the DPN- and DPA-luminol CL systems, respectively. The relative CL intensity was linear with the hydrogen peroxide concentration in the range of 2.0?×?10^?8–6.0?×?10^?6?mol?L^?1 and 4.0?×?10^?8–4.0?×?10^?6?mol?L^?1 for the DPN- and DPA-luminol CL systems, respectively. The proposed method had good reproducibility with a relative standard deviation of 3.4% (8.0?×?10^?7?mol?L^?1, n?=?7) and 1.0% (2.0?×?10^?6?mol?L^?1, n?=?7) for the DPN- and DPA-luminol CL systems, respectively. A satisfactory result has been gained for the determination of H₂O₂ in rainwater and artificial lake water by use of the proposed method.     

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%.