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.     

Enhanced Sensing of Carbendazim,a Fungicide on Functionalized Multiwalled Carbon Nanotube Modified Glassy Carbon Electrode and Its Determination in Real Samples

An electrochemical sensor was developed by modifying a glassy carbon electrode (GCE) with functionalized multiwalled carbon nanotubes (FMWCNTs). The fabricated electrode was used to examine the redox behavior of carbendazim (CAR) in different pH solutions (pH 1.0–13.0). Surface morphology of the modified film was studied by scanning electron microscopy (SEM). An electroanalytical procedure for the determination of CAR was developed by adsorptive differential pulse stripping voltammetry (DPSV) over the range 0.01–5 × 10⁴ µ g L^?1. The developed procedure was also validated in real samples such as soil and water samples, and the applicability of the reported method is highly encouraging.     

Acetylcholinesterase Based Amperometric Sensor. Inhibitor Detection.

Abstract

On the basis of the process of the acetylthiocholine iodide hydrolysis, catalysed by the enzyme acetylcholinesterase and the obtaining of an electroactive product, an amperometric sensor is created. An electrochemically modified graphite electrode is used. with covalently linked directiy on its surface dcetylcholinesterase. It is demonstrated that it can be applied to the quantitative determination of some acetylcholinesterase inhibitors – insecticides and pharmaceuticals and for establishing their influence on the acetylcholinesterase activity.     

Electrochemical Oxidation and Determination of Theophylline at a Carbon Paste Electrode Using Cetyltrimethyl Ammonium Bromide as Enhancing Agent

Abstract

The oxidation of theophylline was studied at a carbon paste electrode in the presence of cetyltrimethyl ammonium bromide by cyclic and differential pulse voltammetry. The results indicated that the electrochemical responses of theophylline are apparently improved by cetyltrimethyl ammonium bromide, due to the enhanced accumulation of theophylline at carbon paste electrode surface. Under optimal conditions the peak current was proportional to theophylline concentration in the range of 8.0 × 10^?7 to 2.0 × 10^?4 M with a detection limit of 1.85 × 10^?7 M by differential pulse voltammetry. The proposed method was applied to the determination of theophylline in tablet and urine samples.     

Differential Pulse Adsorptive Stripping Voltammetric Determination of Chlorpyrifos at a Sepiolite Modified Carbon Paste Electrode

Abstract

An adsorptive stripping voltammetric (AdSV) method for the determination of organophosphorus insecticide chlorpyrifos at a bare carbon paste electrode (CPE) and clay modified carbon paste electrode (CMCPE) was developed. A systematic study of various experimental conditions, such as the pH, accumulation variables and composition of a modifier on the adsorptive stripping response, were examined by using differential pulse voltammetry. A significant improvement was observed in the sensitivity by using the present method with CMCPE. When CMCPE was used, a linear response was obtained over the concentration range 0.0001–2.0 ppm with lower detection limit of 0.00008 ppm, at an accumulation time of 80 s. The interference from other herbicides and ions on the stripping signal of the compound was also evaluated. The described method was applied to estimate the chlorpyrifos in environmental samples.     

Nafion-graphene composite film modified glassy carbon electrode for voltammetric determination of p-aminophenol

A Nafion-graphene (Nafion-GR) nanocomposite film modified glassy carbon electrode was fabricated by a simple drop-casting method, and used in the electrochemical detection of p-aminophenol (4-AP). Owing to the large surface area, good conductivity of GR and good affinity of Nafion, the sensor exhibited excellent electrocatalytic activity for the oxidation of 4-AP. The electrochemical behaviors of 4-AP on Nafion/GR film modified glassy carbon electrodes were investigated by cyclic voltammetry and differential pulse voltammetry. A calibration curve is constructed in the same matrix, urine, as the unknown samples to be analyzed. The Nafion-GR film modified electrode was linearly dependent on the 4-AP concentration and the linear analytical curve was obtained in the ranges of 0.5–200 μM with differential pulse voltammetry (DPV) and the detection limit was 0.051 μM. The Nafion-graphene nanocomposite modified electrode exhibited good reusability than pure graphene modified GCE. This procedure can be used for the determination of p-aminophenol in the presence of its degradation products and paracetamol. Finally, the proposed method was successfully used to determine p-aminophenol in local tap water samples in urine samples and pharmaceutical preparations.     

Carbon Nanotubes‐Ionic Liquid and Chloropromazine Modified Electrode for Determination of NADH and Fabrication of Ethanol Biosensor

Potential cycling was used for oxidation of chloropromazine and producing an electroactive redox couples which strongly adsorbed on the electrode surface modified with carbon nanotubes and ionic liquid nanocomposite. The modified electrode shows excellent electrocatalytic activity toward NADH oxidation. The differential pulse voltammetry detection provided high sensitivity, 0.5835 A M^?1, low detection limit, 80 nM at concentration range up to 20 μM. An ethanol biosensor was also developed by immobilizing alcohol dehydrogenase enzyme onto nanocomposite. Differential pulse voltammetric detection of ethanol gives linear responses over the concentration range 40 μM–1.5 mM with detection limit 5 μM and sensitivity 1.97 μA mM^?1.     

A New Indirect Electrochemical Method for Determination of Ozone in Water Using Multiwalled Carbon Nanotubes

A new electrochemical methodology has been developed for the detection of ozone using multiwalled carbon nanotubes (MWCNT). The method presented here is based on the reaction of ozone with indigo blue dye producing anthranilic acid (ATN). The electrochemical profile of ATN on an electrode of glassy carbon (GC) modified with MWCNT showed an oxidation peak potential at 750 mV vs. Ag/AgCl. An analytical method was developed using differential pulse voltammetry (DPV) to determine ATN in a range of 50–400 nmol L^?1, with a detection limit of 9.7 nmol L^?1. Ozonated water samples were successfully analyzed by GC/MWCNT electrode and the recovery procedure yielded values between of 96.5 and 102.3 %.     

Anodic Oxidation of α‐Lipoic Acid at a Glassy Carbon Electrode and Its Determination in Dietary Supplements

Abstract

Direct electrochemistry of alpha‐lipoic acid (ALA) was performed at a glassy carbon electrode using cyclic, differential pulse and square wave voltammetry over a wide range of pH. The oxidation of ALA is an irreversible process, pH independent, and involves the charge transfer of one electron. The diffusion coefficient of ALA was calculated from the results obtained at pH 6.9 in 0.1 M phosphate buffer and was shown to be D ₀=1.1×10^?5 cm² s^?1. The limits of detection (LOD) and quantification (LOQ) calculated from the results obtained at this pH are 1.8 and 6.1 µM, respectively.

The lipoic acid content in two dietary supplements samples, a syrup containing ALA and capsules of ALA, has been determined directly at the glassy carbon electrode by differential pulse voltammetry using the standard addition method.     

Voltammetric Determination of Dopamine in Human Serum and Urine at a Glassy Carbon Electrode Modified by Cysteic Acid Based on Electrochemical Oxidation of L ‐cysteine

Abstract

The voltammetric behavior of dopamine was studied at a glassy carbon electrode modified by cysteic acid, based on electrochemical oxidation of L ‐cysteine. The modified electrode showed strong electrocatalytic activity towards dopamine and good selectivity. In a phosphate buffer solution (pH 7.4), the anodic peak current obtain from the differential pulse voltammetry of dopamine was linearly dependent on its concentration in the range of 5×10^?9 to 4.0×10^?6mol · L^?1, with a detection limit of 2×10^?9mol · L^?1. The low‐cost modified electrode had been applied to the determination of dopamine in human serum and urine samples with satisfactory results.     

Determination of Melphalan Using Differential Pulse Voltammetry

Abstract

The anodic oxidation of melphalan was studied on a glassy carbon disk electrode, either stationary or rotated, using a d.c. and a differential pulse potential program. The conditions have been found for a differential pulse voltammetric determination of the substance, with a detection limit of 1 × 10^?6 mol 1^?1     

Synthesis and application of a natural-based nanocomposite with carbon nanotubes for sensitive voltammetric determination of lead (II) ions

ABSTRACT

A modified carbon paste electrode has been developed for the determination of Pb(ΙΙ) ions based on Fe₃O₄/eggshell magnetic nanocomposite. The structure and morphology of Fe₃O₄/eggshell were analysed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The prepared nanocomposite was also characterized by Fourier transform infrared spectroscopy (FT-IR) and vibrating sample magnetometer (VSM). The electrochemical procedure was based on the accumulation and determination of Pb(ΙΙ) ions at the surface of the modified carbon paste electrode with Fe₃O₄/eggshell nanocomposites and carbon nanotubes by differential pulse anodic stripping voltammetry (DPASV). Various experimental parameters involved in the preconcentration of Pb(ΙΙ) ions and voltammetric stripping step were studied. Under the optimum conditions, the voltammetric peak current of Pb(ΙΙ) occurs at a potential about ?0.5 V. Also, the voltammetric peak current increased linearly with Pb(ΙΙ) concentration in the range of 0.5–200 ng mL^?1 and a detection limit of 0.15 ng mL^?1 was obtained for Pb(ΙΙ). The selectivity of the proposed electrode for Pb(ΙΙ) ions in the presence of some cations was also examined. The practical application of the proposed modified electrode was evaluated by the determination of Pb(ΙΙ) ions in human hair and water samples. The results were satisfactory for the spiked samples.     

A Determination of 6-Mercaptopurine and 6-Thio-Guanine By Anodic Differential Pulse Voltammetry

Abstract

The anodic oxidation of 6-mercaptopurine and 6-thioguanine has been studied on a rotating and stationary disk electrode of glassy carbon, using d.c. and differential pulse potential program. Conditions have been found for determination of these substances by anodic differential pulse voltammetry on a rotating disk electrode, with a detection limit of about 2 × 10^?5 mol 1^?1.     

Voltametric,Amperometric, and Chronopotentiometric Determination of Submicromolar Concentrations of Carboxin

New procedures for the determination of pesticide carboxin were developed using differential pulse voltammetry, HPLC with amperometric detection and chronopotentiometry at carbon paste electrode and reticulated vitreous carbon electrode, respectively. Developed procedures based on electrochemical oxidation of carboxin were successfully applied on the determination of carboxin in the model samples of drinking and river water. Limits of detection in samples of river water were in 10^?7 mol L^?1 concentration range for all procedures and electrodes used. All developed procedures proved to be sensitive, accurate and, due to the resistance of the electrode to the passivation, also simple to handle.     

Polarographic and Voltammetric Assays of Sulfonamides as α‐Oxo‐γ‐Butyrolactone Arylhydrazones

Abstract

2‐Acetylbutyrolactone was characterized as a novel reagent of analytical potential in polarographic and voltammetric analyses. It forms α‐oxo‐γ‐butyrolactone arylhydrazones through Japp‐Klingemann coupling reaction with primary arylamines. α‐Oxo‐γ‐butyrolactone arylhydrazones possess an electro‐active site (azomethine center) that displays a cathodic activity at the mercury electrode. The protonated azomethine center of α‐oxo‐γ‐butyrolactone arylhydrazones is reduced by 2e/2H⁺ reaction to the hydrazo form. The differential pulse polarographic behavior of α‐oxo‐γ‐butyrolactone arylhydrazones was investigated in aqueous media ranging from pH 2 to 10.5. In aqueous acidic solution, α‐oxo‐γ‐butyrolactone arylhydrazones were shown to adsorb on a hanging mercury drop electrode and to be amenable to determination by adsorptive stripping voltammetry. Procedures for applying the polarographic and voltammetric methods to determination of sulfadiazine and sulfamethoxazole in pharmaceutical preparations have been developed. An analogous study on sulfas‐azo derivatives of ethyl acetoacetate was also considered. Furthermore, the differential pulse voltammetric method was adopted for determination of sulfamethoxazole in spiked plasma and urine samples. The recoveries turned out to be satisfactory, showing relative standard deviations from 2.4 to 4.6%.     

Comparative Study of Pesticides Analysis Using Enzyme Inhibition Sensor and Gas Chromatography Methods

Pesticides are widely used in paddy field to control pests, diseases, weeds and other rice pathogens in minimizing a serious loss in rice production. The presence of pesticide residues and metabolites in rice, water, soil, currently represents a major environmental pollutant issues. It sometime will cause insect pest outbreaks in paddy field. An electrochemical enzyme inhibition sensor using screen-printed carbon working electrode with onboard carbon counter and silver–silver chloride pseudo-reference electrode for insecticides detection is described in this paper (Figure 1). The detection is based on the inhibition of insecticides used in paddy field towards acetyl-cholinesterase enzyme (AChE) with the presence of Acetylthiocholine Iodide (ATCh) substrate on the sensor surface. The mixtures of AChE enzyme (0.02 UmL^-1), electron mediator, TCNQ (1mM) and polypyrrole matrix (75 mM) were electro- polymerized on the sensor surface with a constant potential of 1.0V for 20 minutes. The sensor was soaked for 5 minutes with insecticides standard or sample containing insecticides before the electrochemical measurement was taken by adding Acetylthiocholine Iodide substrate in KCl (0.08M, pH 7.5) which acts as the enzyme mediator /substrate system. The current measurement was conducted using chronoamperometry at 100mV vs. on board screen-printed Ag-AgCl pseudo- reference electrode. Comparative analysis of spiked water samples with 0.1ppm pesticides and real samples (paddy) also were conducted using enzyme inhibition sensor and gas chromatography methods. From the data analysis, it showed very comparable results with R² = 0.96 in the correlation plot for paddy samples samples. This makes the developed sensor a potential tool for the rapid, simple and sensitive detection of insecticides residues in agriculture industry.     

Highly Sensitive Choline Oxidase Enzyme Inhibition Biosensor for Lead Ions Based on Multiwalled Carbon Nanotube Modified Glassy Carbon Electrodes

The determination of lead ions by inhibition of choline oxidase enzyme has been evaluated for the first time using an amperometric choline biosensor. Choline oxidase (ChOx) was immobilized on a glassy carbon electrode (GCE) modified with multiwalled carbon nanotubes (MWCNT) through cross‐linking with glutaraldehyde. In the presence of ChOx, choline was enzymatically oxidized into betaine at –0.3 V versus Ag/AgCl reference electrode, lead ion inhibition of enzyme activity causing a decrease in the choline oxidation current. The experimental conditions were optimised regarding applied potential, buffer pH, enzyme and substrate concentration and incubation time. Under the best conditions for measurement of the lowest concentrations of lead ions, the ChOx/MWCNT/GCE gave a linear response from 0.1 to 1.0 nM Pb²⁺ and a detection limit of 0.04 nM. The inhibition of ChOx by lead ions was also studied by electrochemical impedance spectroscopy, but had a narrower linear response range and low sensitivity. The inhibition biosensor exhibited high selectivity towards lead ions and was successfully applied to their determination in tap water samples.     

Investigations on Bioanalytical Chemistry Part I. On Differential Pulse Voltammetry of Bilirubin

Abstract

The electrochemical behaviour of the bilirubin in many kinds of supporting electrolytes on a glassy carbon electrode (GCE) and a hanging mercury drop electrode (HMDE) was investigated by means of anodic or cathodic differential pulse voltammetry. The influences of different methods of pre-treatment of the glassy carbon electrode was also discussed. In Na₂B₄.O₇-KH₂PO₄ buffer solution, the linear range was 2×10^?9-1×10^?9 mol/l and the detection limit was 3.3×10^?9 mol/l by anodic differential pulse voltammetry at GCE. A linear relationship holds between the peak current and the concentration of bilirubin in a concentration range of 1×10^?9-4×10^?7 mol/l with good precision and accuracy, and the limit of detection was 2×10^?10 mol/l, when cathodic differential pulse adsorption voltammetry at HMDE was used.     

OH functionalized Multi-Walled Carbon Nanotube modified electrode as electrochemical sensor for the detection of Aceclofenac

ABSTRACT

The rapid electrochemical determination of Aceclofenac (ACF) has been employed by cyclic voltammetry (CV), differential pulse voltammetry (DPV) using developed OH-functionalised multiwalled carbon nanotube carbon paste electrode (OH-MWCNT/CPE). Modified electrode was characterised by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDAX), X-ray diffraction spectroscopy (XRD), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The ACF exhibits two oxidation peaks at +0.4 V, +0.66 V and one reduction peak at +0.3 V. The active surface area of the bare carbon paste electrode (BCPE) and modified electrode have been characterised by using K₃[Fe(CN)₆] solution containing 0.1 M KCl. In DPV mode, variation of ACF gave the limit of detection (LOD = 3s/m) 0.246 μM over the concentration range 1.0 to 190.0 μM (R² = 0.9994). The developed electrode has good stability, reproducibility and could be successfully validated for the detection of ACF in pharmaceutical samples and biological fluids.     

Amperometric Enzyme Based Biosensor For the Detection of Xanthine Via Superoxide

Abstract

An amperometric enzyme modified carbon paste electrode for the detection of xanthinc by the xanthine oxidase catalyzed reaction is described. the product of the enzyme reaction monitored is the highly unstable radical superoxide, detected at O mV (vs SCE) poised potential. A dual working electrode configuration consisting of an enzyme modified carboa paste electrode and an unmodified glassy carbon electrode are utilized for this purpose.