Voltammetric Determination of Phenoxybenzyl‐Type Insecticides at Chemically Modified Conducting Polymer‐Carbon Nanotubes Coated Electrodes

The electrochemical reduction of three common insecticides such as cypermethrin (CYP), deltamethrin (DEL) and fenvalerate (FEN) was investigated at glassy carbon electrode (GCE), multiwalled carbon nanotubes modified GCE (MWCNT‐GCE), polyaniline (herein called as modifier M₁) and polypyrrole (herein called as modifier M₂) deposited MWCNT/GCE using cyclic voltammetry. Influences of pH, scan rate, and concentration were studied. The surface morphology of the modified film was characterized by scanning electron microscopy (SEM) and X‐ray diffraction analysis (XRD). A systematic study of the experimental parameters that affect differential pulse stripping voltammetry (DPSV) was carried out and the optimized experimental conditions were arrived at. The calibration plots were linear over the insecticide's concentration range 0.1–100 mg L^?1 and 0.05–100 mg L^?1 for all the three insecticides at MWCNT‐GCE and MWCNT(M₁)‐GCE respectively. The MWCNT(M₂)‐GCE performed well among the three electrode systems and the determination range obtained was 0.01–100 mg L^?1 for CYP, DEL and FEN. The limit of detection (LOD) was 0.35 μg L^?1, 0.9 μg L^?1 and 0.1 μg L^?1 for CYP, DEL and FEN respectively on MWCNT(M₂)‐GCE modified system. Suitability of this method for the trace determination of insecticide in spiked soil sample was also determined.     

Electrochemical Determination and in silico Studies of Fludarabine on NH2 Functionalized Multiwalled Carbon Nanotube Modified Glassy Carbon Electrode

A sensitive voltammetric technique has been developed for the determination of Fludarabine using amine‐functionalized multi walled carbon nanotubes modified glassy carbon electrode (NH₂‐MWCNTs/GCE). Molecular dynamics simulations, an in silico technique, were employed to examine the properties including chemical differences of Fludarabine‐ functionalized MWCNT complexes. The redox behavior of Fludarabine was examined by cyclic, differential pulse and square wave voltammetry in a wide pH range. Cyclic voltammetric investigations emphasized that Fludarabine is irreversibly oxidized at the NH₂‐MWCNTs/GCE. The electrochemical behavior of Fludarabine was also studied by cyclic voltammetry to evaluate both the kinetic (k_s and E_a) and thermodynamic (ΔH, ΔG and ΔS) parameters on NH₂‐MWCNTs/GCE at several temperatures. The mixed diffusion‐adsorption controlled electrochemical oxidation of Fludarabine revealed by studies at different scan rates. The experimental parameters, such as pulse amplitude, frequency, deposition potential optimized for square‐wave voltammetry. Under optimum conditions in phosphate buffer (pH 2.0), a linear calibration curve was obtained in the range of 2×10^?7 M–4×10^?6 M solution using adsorptive stripping square wave voltammetry. The limit of detection and limit of quantification were calculated 2.9×10^?8 M and 9.68×10^?8 M, respectively. The developed method was applied to the simple and rapid determination of Fludarabine from pharmaceutical formulations.     

Fabrication of an Electrochemical Sensor Based on Multiwalled Carbon Nanotubes for Almotriptan

In the present work, the electrochemical behavior of an antimigraine drug, almotriptan malate (ALM), on a multiwalled carbon nanotube (MWCNT) film modified glassy carbon electrode under cyclic voltammetry was described for the first time. A significant enhancement in the oxidation peak current of ALM was noticed at MWCNT‐GCE. This property was exploited to develop a simple, sensitive and time‐saving differential pulse voltammetric method for the determination of ALM in bulk and pharmaceutical samples. A linear relationship was observed between concentration and peak current with a correlation coefficient of 0.9915 in the range of 0.25–37.5 µM ALM.     

Determination of Copper(II) Through Anodic Stripping Voltammetry in Tartrate Buffer Using an Antimony Film Screen-printed Carbon Electrode

The voltammetric performance of an in situ plated antimony film screen-printed carbon electrode in hydrochloric acid, acetate buffer, and tartrate buffer was evaluated for the detection of copper(II) with differential pulse anodic stripping voltammetry. The tartrate buffer was superior, providing high sensitivity and good separation of copper and antimony stripping peaks. The analytical conditions for the determination of copper(II) were optimized. The detection limit was estimated to be 0.14?µg?L^?1 copper(II) and the relative standard deviation for 2.5?µg?L^?1 copper(II) was 3%. The applicability of the method was illustrated by the analysis of soil conditioner samples.     

A Selective Simultaneous Determination of Levodopa and Serotonin Using a Glassy Carbon Electrode Modified with Multiwalled Carbon Nanotube/Chitosan Composite

A glassy carbon electrode (GCE) modified with carbon nanotube/chitosan (MWCNTs‐CHT/GCE) was used for the sensitive voltammetric determination of levodopa (Lev) and serotonin (Ser). The measurements were carried out using cyclic voltammetry (CV), differential pulse voltammetry (DPV) and chronoamperometry (CA). Under the optimum conditions the electrode provides a linear response versus Lev and Ser concentrations in the range of 2.0–220.0 µM and 0.5–130.0 µM, respectively, using DPV. The modified electrode was satisfactorily used for determination of Lev and Ser in human serum and urine with satisfactory results.     

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.     

Development of Electrochemical Biosensor Based on Nanostructured Carbon Materials for Paracetamol Determination

This work describes the development of a biosensor for paracetamol (PAR) determination based on a glassy carbon electrode (GCE) modified with multiwalled carbon nanotubes (MWCNT) and laccase enzyme (LAC), which was immobilized by means of covalent crosslinking using glutaraldehyde. Voltammetric investigations were carried out by cyclic voltammetry (CV), differential pulse voltammetry (DPV) and square wave voltammetry (SWV). The biosensor was characterized by Scanning Electron Microscope (SEM) and Fourier Transform Infrared Spectroscopy (FT‐IR). The results showed that the use of MWCNT/LAC composite increased the sensor sensitivity, compared to bare glassy carbon electrode. Factors affecting the voltammetric signals such as pH, ionic strength, scan rate and interferents were assessed. Linear range, limit of detection (LOD) and limit of quantitation (LOQ) obtained were 10–320 μmol L^?1, 7 μmol L^?1 and 10 μmol L^{? 1}, respectively. The developed biosensor was successfully applied to PAR determination in urine and pharmaceutical formulations samples, with recovery varying from 99.96 to 106.20 % in urine samples and a relative standard deviation less than 1.04 % for PAR determination in pharmaceutical formulations. Therefore, the MWCNT‐LAC/GCE exhibits excellent sensitivity and can be used to PAR determination as a viable alternative in clinical analyzes and quality control of pharmaceutical formulations, through a simple, fast and inexpensive methodology.     

Electroanalysis of some common pesticides using conducting polymer/multiwalled carbon nanotubes modified glassy carbon electrode

The cyclic voltammetric behaviour of three common pesticides such as isoproturon (ISO), voltage (VOL) and dicofol (DCF) was investigated at glassy carbon electrode (GCE), multiwalled carbon nanotubes modified GCE (MWCNTs/GCE), polyaniline (PANI) and polypyrrole (PPY) deposited MWCNT/GCE. The modified electrode film was characterized by scanning electron microscopy (SEM) and X-ray diffraction analysis (XRD). The electroactive behaviour of the pesticides was realized from the cyclic voltammetric studies. The differential pulse voltammetric principle was used to analyze the above-mentioned pesticides using MWCNT/GCE, PANI/MWCNT/GCE and PPY/MWCNT/GCE. Effects of accumulation potential, accumulation time, Initial scan potential, amplitude and pulse width were examined for the optimization of stripping conditions. The PANI/MWCNT/GCE performed well among the three electrode systems and the determination range obtained was 0.01-100 mgL(-1) for ISO, VOL and DCF respectively. The limit of detection (LOD) was 0.1 microgL(-1) for ISO, 0.01 microgL(-1) for VOL and 0.05 microgL(-1) for DCF on PANI/MWCNT/GCE modified system. It is significant to note that the PANI/MWCNT/GCE modified system results in the lowest LOD in comparison with the earlier reports. Suitability of this method for the trace determination of pesticide in spiked samples was also realized.     

Lead ion sensor with electrodes modified by imidazole-functionalized polyaniline

Glassy carbon electrodes (GCE) and carbon paste electrodes (CPE) were modified with imidazole functionalized polyaniline with the aim to develop a sensor for lead (II) in both acidic and basic aqueous solution. The electrodes were characterized by cyclic voltammetry and differential pulse adsorptive stripping voltammetry. The limit of detections obtained with glassy carbon electrode and carbon paste electrode are 20?ng?mL^-1 and 2?ng?mL^-1 of lead ion, respectively. An interference study was carried out with Cd(II), As(III), Hg(II) and Co(II) ions. Cd(II) ions interfere significantly (peak overlap) and As(III) has a depressing effect on the lead signal. The influence of pH was investigated indicating that bare and modified GCE and CPE show optimum response at pH?4.0 ± 0.05.

Bismuth and Bismuth-Chitosan modified electrodes for determination of two synthetic food colorants by net analyte signal standard addition method

In this paper, an electrochemical application of bismuth film modified glassy carbon electrode for azo-colorants determination was investigated. Bismuth-film electrode (BiFE) was prepared by ex-situ depositing of bismuth onto glassy carbon electrode. The plating potential was ?0.78 V (vs. SCE) in a solution of 0.15 mg mL^?1 Bi(III) and 0.05 mg mL^?1 KBr for 180 s. In the next step, a thin film of chitosan was deposited on the surface of bismuth modified glassy carbon electrode, thus the bismuth-chitosan thin film modified glassy carbon electrode (Bi-CHIT/GCE) was fabricated and compared with bare GCE and bismuth modified GCE. Azo-colorants such as Sunset Yellow and Carmoisine were determined on these electrodes by differential pulse voltammetry. Due to overlapping peaks of Sunset Yellow and Carmoisine, simultaneous determination of them is not possible, so net analyte signal standard addition method (NASSAM) was used for this determination. The results showed that coated chitosan can enhance the bismuth film sensitivity, improve the mechanical stability without caused contamination of surface electrode. The Bi-CHIT/GC electrode behaved linearly to Sunset Yellow and Carmoisine in the concentration range of 5×10^?6 to 2.38×10^?4 M and 1×10^?6 to 0.41×10^?4 M with a detection limit of 10 µM (4.52 µg mL^?1) and 10 µM (5.47 µg mL^?1), respectively      

Sensitive Quantification of Fe(III) in Food Samples at Screen Printed Carbon Electrode Modified with Graphene and Piroxicam by Catalytic Adsorptive Voltammetry

A new disposable sensitive voltammetric sensor for the determination of Fe(III) based on a graphene (G) and piroxicam (Pir) modified screen printed carbon electrode (Pir/G/SPCE) has been developed. The developed method is based on accumulation of Fe(III) on the surface of the prepared sensor strip, formation a complex with Pir and subsequent reduction the adsorbed chelated Fe(III) at ?0.03 V (vs. Ag/AgCl) coupled with the catalytic enhancement of bromate. Characterizations of the modified electrode surface were performed by field emission scanning electron microscopy (FE‐SEM), energy dispersive X‐ray spectroscopy (EDX) and electrochemical impedance spectroscopy (EIS). Electrochemical behavior of the modified SPCEs was investigated by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Under the optimum conditions, the catalytic voltammetric method exhibited linear calibration plot in the concentration ranges of 1–100 ng mL^?1 and 100–3500 ng mL^?1 Fe(III) with a limit of detection of 0.3 ng mL^?1. The sensor strip displayed good reproducibility with 1.7 % relative standard deviation (RSD%). The developed method was successfully applied for the determination of iron in food samples such as vegetables, fruit, and cereal.     

Sensitive voltammetric assay of etoposide using modified glassy carbon electrode with a dispersion of multi-walled carbon nanotube

A sensitive electroanalytical method for the determination of anticancer drug etoposide (ETP) using adsorptive stripping differential pulse voltammetry (AdSDPV) at a multi-walled carbon nanotube-modified glassy carbon electrode (MWCNT-modified GCE) is presented. The surface morphology of modified electrode was characterized by scanning electron microscopy. The effects of accumulation time and potential, pH, scan rate, and amount of MWCNT suspension were investigated. The calibration curve was linear in the concentration range of 2.0?×?10^?8–2.0?×?10^?6 M with the detection limit of 5.4?×?10^?9 M. The reproducibility of the peak current was found at 1.55 % (n?=?5) RSD value in pH 6.0 Britton–Robinson buffer for the MWCNT-modified GCE. The method was then successfully utilized for the determination of ETP in pharmaceutical dosage form, and a recovery of 99.55 % was obtained. The possible oxidation mechanism of ETP was also discussed. The proposed electroanalytical method using MWCNT-modified GCE is the most sensitive method for the determination of ETP with lowest limit of detection in the previously published electrochemical methods.     

Sensitive voltammetric determination of paracetamol by poly (4-vinylpyridine)/multiwalled carbon nanotubes modified glassy carbon electrode

A novel glassy carbon electrode (GCE) modified with a composite film of poly (4-vinylpyridine) (P4VP) and multiwalled carbon nanotubes (P4VP/MWCNT GCE) was used for the voltammetric determination of paracetamol (PCT). This novel electrode displayed a combined effect of P4VP and MWCNT on the electro-oxidation of PCT in a solution of phosphate buffer at pH 7. Hence, conducting properties of P4VP along with the remarkable physical properties of MWCNTs might have combined effects in enhancing the kinetics of PCT oxidation. The P4VP/MWCNT GCE has also demonstrated excellent electrochemical activity toward PCT oxidation compared to that with bare GCE and MWCNT GCE. The anodic peak currents of PCT on the P4VP/MWCNT GCE were about 300 fold higher than that of the non-modified electrodes. By applying differential pulse voltammetry technique under optimized experimental conditions, a good linear ratio of oxidation peak currents and concentrations of PCT over the range of 0.02–450 μM with a limit of detection of 1.69 nM were achieved. This novel electrode was stable for more than 60 days and reproducible responses were obtained at 99% of the initial current of PCT without any influence of physiologically common interferences such as ascorbic acid and uric acid. The application of this electrode to determine PCT in tablets and urine samples was proposed.     

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.     

Carbon‐Based Electrodes for Sensitive Electroanalytical Determination of Aminonaphthalenes

The electroanalytical performance of bare glassy carbon electrodes (GCE) for the determination of 1‐aminonaphthalene (1‐AN) and 2‐aminonaphthalene (2‐AN) was compared with GCE modified by a Nafion permselective membrane or multiwalled carbon nanotubes and with other types of carbon‐based materials, carbon film and boron doped diamond. Nafion‐modified GCE gave the highest sensitivity and lowest detection limit (0.4 µmol L^?1) for differential pulse voltammetric determination of 1‐AN. Electrochemical impedance spectroscopy gave information about the processes at the electrode surface. Simultaneous determination of 1‐AN and 2‐AN in a mixture at GCE and their determination in model samples of river water is presented.     

Characterization of electrodes modified with nanocomposites of cobalt tetraaminophenoxyphthalocyanine,reduced graphene and multi-walled carbon nanotubes

Abstract

Glassy carbon electrodes or plates were modified with nanocomposites consisting of cobalt tetraaminophenoxyphthalocyanine (CoTAPhPc), reduced graphene oxide nanosheets (rGONs) and multi-walled carbon nanotubes (MWCNTs). The modified electrodes were characterized using cyclic voltammetry, scanning electrochemical microscopy (SECM) and time-of-flight-secondary ion mass spectrometer (TOF-SIMS). The electrocatalytic activity of the modified electrode was tested for detection of L-cysteine. The presence of CoTAPhPc on sequential layers of MWCNT and rGONs resulted in improved detection currents compared to CoTAPhPc alone or when MWCNT/rGONs are mixed in CoTAPhPc–MWCNT/rGONs (mix)–glassy carbon electrode (GCE). CoTAPhPc–MWCNT–GCE (without rGONS) showed higher sensitivity toward l-cysteine as compared to the probes incorporating rGONs with a catalytic rate constant of 4.62?×?10⁴ M^?1s^?1 and a detection limit of 30?nM. The presence of rGONs improved the stability of the electrode.     

Adsorptive Stripping Voltammetric Detection of Single‐Stranded DNA at Electrochemically Modified Glassy Carbon Electrode

Electrochemically modified glassy carbon electrode (GCE) was used to study the electrochemical oxidation and detection of denatured single‐stranded (ss) DNA by means of adsorptive stripping voltammetry. The modification of GCE, by electrochemical oxidation at +1.75 V (vs.SCE) for 10 min and cyclic sweep between +0.3 V and ?1.3 V for 20 cycles in pH 5.0 phosphate buffer, results in 100‐fold improvement in sensitivity for ssDNA detection. We speculated that the modified GCE has a high affinity to single‐stranded DNA through hydrogen bond (specific static adsorption). Single‐stranded DNA can accumulate at the GCE surface at open circuit and produce a well‐defined oxidation peak corresponding to the guanine residues at about +0.80 V in pH 5.0 phosphate buffer, while the native DNA gives no signal under the same condition. The peak currents are proportional to the ssDNA concentration in the range of 0–18.0 μg mL^?1. The detection limit of denatured ssDNA is ca. 0.2 μg mL^?1 when the accumulation time is 8 min at open circuit. The accumulation mechanism of ssDNA on the modified GCE was discussed.     

Alumina Polished Glassy Carbon Electrode as a Simple Electrode for Lower Potential Electrochemical Detection of Dopamine in its Sub‐micromolar Level

The electrochemical behaviour of dopamine (DA) at a cleaned and alumina polished glassy carbon electrode (GCE) was studied using cyclic voltammetry (CV). The CV studies revealed that alumina polished GCE (AGCE) shows an enhanced oxidation peak current response with 217 mV negative potential shift towards DA than that of cleaned GCE. The differential pulse voltammetry result shows that the AGCE detects the DA in the linear concentration ranges from 0.15 to 25.25 µmol L^?1. The limit of detection was calculated as 0.046 µmol L^?1 with a sensitivity of 3.74 µA µmol L^?1 cm^?2 for the determination of DA. The fabricated AGCE shows a satisfactory selectivity, practicality along with appreciable repeatability and reproducibility.     

Electrochemical Sensor Based on Multi‐walled Carbon Nanotube/Gold Nanoparticle Modified Glassy Carbon Electrode for Detection of Estradiol in Environmental Samples

We report a rapid and simple method for sensing estradiol by electro‐oxidation on a multi‐walled carbon nanotube (MWCNT) and gold nanoparticle (AuNP) modified glassy carbon electrode (GCE). Compared with a bare GCE, AuNP/GCE and MWCNT/GCE, the composite modified GCE shows an enhanced response to estradiol in 0.1 M phosphate buffer solution. Experimental parameters, including pH and accumulation time for estradiol determination were optimised at AuNP/MWCNT/GCE. A pH of 7.0 was found to be optimum pH with an accumulation time of 5 minutes. Estradiol was determined by linear sweep voltammetry over a dynamic range up to 20 %mol L^?1 and the limit of detection was estimated to be 7.0×10^?8 mol L^?1. The sensor was successfully applied to estradiol determination in tap water and waste water.     

Simultaneous determination of dopamine and serotonin by use of covalent modification of 5-hydroxytryptophan on glassy carbon electrode

An electrochemical biosensor was fabricated by covalent modification of 5-hydroxytryptophan (5-HTP) on the surface of glassy carbon electrode (GCE). The electrode, denoted as 5-HTP/GCE, was characterized by X-ray photoelectron spectroscopy, cyclic voltammetry and differential pulse voltammetry. For comparison, tryptophan modified GCE (TRP/GCE) and serotonin modified GCE (5-HT/GCE) were prepared by the same method. It was found that electrocatalytic ability of these electrodes was in the order of 5-HTP/GCE?>?TRP/GCE?>?5-HT/GCE for the oxidation of dopamine (DA) and 5-HT. The sensor was effective to simultaneously determine DA and 5-HT in a mixture. It can resolve the overlapping anodic peaks into two well-defined voltammetric peaks at 0.24 and 0.39 V (versus SCE). The linear response is in the range of 5.0?×?10^?7–3.5?×?10^?5 mol L^?1 with a detection limit of 3.1?×?10^?7 mol L^?1 for DA, and in the range of 5.0?×?10^?6–3.5?×?10^?5 mol L^?1 with a detection limit of 1.7?×?10^?6 mol L^?1 for 5-HT (s/n?=?3), respectively.