Stripping Voltammetric Determination of Methyl Parathion at Activated Carbon Nanopowder Modified Electrode

An activated carbon nanopowder modified glassy carbon electrode (AC-GCE) was constructed for the sensitive determination of methyl parathion by adsorptive differential pulse anodic stripping voltammetry. The simple and rapid modification procedure included only drop-coating the electrode surface with a laponite stabilized activated carbon nanopowder suspension and drying. The modifier high adsorption ability, combined with its large electroactive surface area allowed a 30-fold signal increase to be achieved, compared to bare GCE. Under optimized experimental conditions (activated carbon to laponite ratio, pH and accumulation time), the AC-GCE exhibited a linear response to methyl parathion in two concentration ranges: from 0.01 μmol L⁻¹ to 1 μmol L⁻¹ and from 1 μmol L⁻¹ to 6 μmol L⁻¹. The LOD of 2.5 nmol L⁻¹ (S/N=3) achieved fitted with regulatory norms. It was demonstrated that the as-prepared AC-GCE is suitable for routine real samples analysis.     

Visible Light Photoelectrochemical Sensor for Acetaminophen Determination using a Glassy Carbon Electrode Modified with BiVO4 Nanoparticles

A new and simple photoelectrochemical (PEC) sensor using a glassy carbon electrode (GCE) modified with bismuth vanadate (BiVO₄) nanoparticles and dihexadecyl phosphate (DHP) film was useful for acetaminophen (AC) determination. In 0.2 mol L⁻¹ phosphate buffer (pH=9), the GCE without modification exhibited the smaller photocurrent (0.86 μA) when compared with GCE modified with 1.0 mg mL⁻¹ or 2.0 mg mL⁻¹ BiVO₄ nanoparticles suspension (5.9 and 34 μA, respectively). Based on the photocurrent signal generated through the interaction between GCE, BiVO₄ and the energy of visible light a chronoamperometric method for AC determination was developed. The AC linear range concentration from 0.099 to 0.99 μmol L⁻¹ and limits of detection and quantification of 0.027 and 0.091 μmol L⁻¹, respectively, was obtained. The proposed method was applied to the AC determination in commercial drugs and tap water with satisfactory accuracy and precision. Moreover, the PEC construction was easy and had a short response time, which might confer higher sample throughput for the method.     

Simultaneous Determination of Lipophilic Vitamin Esters Using Square-wave Voltammetry at the Glassy Carbon Electrode

Simple and rapid voltammetric method for simultaneous determination of all-trans-retinyl acetate (RAc) or all-trans-retinyl palmitate (RPa) and α-tocopheryl acetate (α-TOAc) has been proposed. The respective method was based on the anodic oxidation of the compounds of interest by square-wave voltammetry in acetone with 0.1 mol L⁻¹ LiClO₄ at the glassy carbon electrode. The procedure was also beneficial with respect to simple dissolution of sample directly in the supporting electrolyte. The all-trans-retinyl acetate could be quantified in two linear ranges (3.1–140 μmol L⁻¹ and 140–400 μmol L⁻¹) and α-tocopheryl acetate in linear range 5.3–400 μmol L⁻¹ with detection limits of 0.9 μmol L⁻¹ RAc (or 0.8 μmol L⁻¹ RPa) and of 1.6 μmol L⁻¹ α-TOAc. Selected commercial cosmetic products were analysed achieving satisfactory recoveries.     

Application of a Tetraamino Cobalt(II) Phthalocyanine Modified Screen Printed Carbon Electrode for the Sensitive Electrochemical Determination of L-Dopa in Pharmaceutical and Biological Samples

A novel synthesized tetraamino cobalt(II) phthalocyanine monomer was used for the fabrication of a sensor by electrochemical polymerization. A disposable electrochemical sensor based on the use of a screen printed carbon electrode covered with an electropolymerized film of tetraamino cobalt(II) phthalocyanine for the determination of L-dopa in pharmaceutical tablets and biological samples was described. Cyclic voltammetry and electrochemical impedance spectroscopy were performed for the characterization of the bare and modified electrode. For the electrochemical detection of L-dopa differential pulse voltammetry was used. The proposed method exhibits a good response towards electrooxidation of L-dopa in the linear concentration range: from 0.1 to 1000.0 μmol L⁻¹ in BRB pH=2.0, with a detection limit of 0.03 μmol L⁻¹ and from 1 to 1000 μmol L⁻¹ in PBS pH=7.4, with a detection limit of 0.33 μmol L⁻¹. Due to the fact that the developed sensor was applied in two different types of real samples, two buffer media were used, BRB pH=2.0 for pharmaceutical and urine samples and PBS pH=7.4 for whole blood samples. The proposed pCoTAPc/SPCE was successfully applied for the determination of L-dopa in pharmaceutical tablets, urine and in whole blood samples with satisfactory results.     

Development of a Sensor Based on Modified Carbon Paste with Com Iron(III) Protoporphyrin Immobilized on SiNbZn Silica Matrix for L‐tryptophan Determination

In this work, SiO₂/Nb₂O₅/ZnO prepared by the sol‐gel processing method was used as substrate base for immobilization of the protoporphyrin‐IX ion. Iron(III) ion was inserted into the porphyrin ring (SiNbZn‐PPFe). A simple square wave voltammetry method based on a composite sensor carbon paste electrode of this material,designed as EPC‐SiNbZn‐PPFe, was developed and validated successfully for the determination of L‐tryptophan (Trp). The optimum conditions were obtained by using sensor modified with 18.00 mg SiNbZn‐PPFe material, 12.00 mg graphite powder and 6.0 μL mineral oil and phosphate buffer 0.3 mol L⁻¹ pH 7.0. The sensitivity of the sensor was found to be 0.523 AL mol ⁻¹, linear range from 10 to 70 μmol L⁻¹ and limit of detection of 3.28 μmol L⁻¹. Therefore, the developed method was successfully applied for the Trp determination in real samples of pharmaceutical formulation and can be used for routine quality control pharmaceutical formulations containing Trp.     

Simultaneous Electrochemical Determination of Hydroquinone and Bisphenol A using a Carbon Paste Electrode Modified with Silver Nanoparticles

In this paper, a rapid and sensitive modified electrode for the simultaneous determination of hydroquinone (HQ) and bisphenol A (BPA) is proposed. The simultaneous determination of these two compounds is extremely important since they can coexist in the same sample and are very harmful to plants, animals and the environment in general. A carbon paste electrode (CPE) was modified with silver nanoparticles (nAg) and polyvinylpyrrolidone (PVP). The PVP was used as a reducing and stabilizing agent of nAg from silver nitrate in aqueous media. The nAg‐PVP composite obtained was characterized by transmission electron microscopy and UV‐vis spectroscopy. The electrochemical behavior of HQ and BPA at the nAg‐PVP/CPE was investigated in 0.1 mol L⁻¹ B−R buffer (pH 6.0) using cyclic voltammetry (CV) and square wave voltammetry (SWV). The results indicate that the electrochemical responses are improved significantly with the use of the modified electrode. The calibration curves obtained by SWV, under the optimized conditions, showed linear ranges of 0.09–2.00 μmol L⁻¹ for HQ (limit of detection 0.088 μmol L⁻¹) and 0.04–1.00 μmol L⁻¹ for BPA (limit of detection 0.025 μmol L⁻¹). The modified electrode was successfully applied in the analysis of water samples and the results were comparable to those obtained using UV‐vis spectroscopy.     

Electrochemical sensing platform based on the use of ZnONPs and MWCNTs as CPE modifiers for a selective and sensitive determination of polyamine spermine in the urine sample

A simple electroanalytical procedure has been developed for the determination of polyamine spermine using the ZnONPs-MWCNTs-CPE sensor. Spermine has been irreversibly oxidized on a modified electrode at a potential of +0.92 V versus Ag/AgCl (KCl, 3.5 mol L⁻¹). The developed sensor demonstrated a respective linear response in borate buffer pH 8.5 from 2 μmol L⁻¹ to 100 μmol L⁻¹, with a detection limit of 0.300 μmol L⁻¹ and quantification limit of 0.998 μmol L⁻¹. The proposed sensor showed high reproducibility (RSD = 2.58 %), stability, robustness, and no obvious interference effects of several inorganic ions and organic molecules. The obtained results demonstrated excellent performance during the determination of the spermine in human urine samples with satisfactory recovery results (98.41–101.34 %), offering promising opportunities for practical clinical analysis.     

Voltammetric Determination of an Anti-rheumatoid Drug Acemetacin on Graphite Flake Paste Electrode and Glassy Carbon Electrode

In this study, a simple and sensitive square wave voltammetric procedure has been developed for the determination of acemetacin (ACM) at graphite flake paste electrode (GFPE) and glassy carbon electrode (GCE). Under optimized conditions, the dependence of ACM peak current on its concentration showed wide linear range: 0.03–1.0 μmol L⁻¹ and 0.7–15.0 μmol L⁻¹ at GFPE and GCE, respectively. The developed method was successfully applied for the determination of ACM in pharmaceuticals and spiked urine with satisfying recoveries. The electrochemical oxidation of ACM is an irreversible process controlled by mixed nature of the mass transfer process.     

Bi‐enzyme Electrochemical Sensor for Selective Determination of Organophosphorus Pesticides with Phenolic Leaving Groups

An amperometric bi‐enzyme sensor for detection of organophosphorus pesticides (OPs) with phenolic leaving groups, which are not electroactive, is presented in this work. The biosensing platform was created by a simple, controllable, and reproducible one‐step electrodeposition onto the surface of a glassy carbon electrode of a chitosan bionanocomposite with entrapped carboxylated multi walled carbon nanotubes, organophosphorus hydrolase (OPH), and horseradish peroxidase (HRP). The OPs determination involved a sequence of OPH and HRP‐catalyzed reactions resulting in phenolic radicals production, which were quantified by registering the current of their reduction at a potential of −50 mV vs. Ag, AgCl/KCl_sat.The developed sensor was applied for the determination of prothiofos, as an example. At optimized conditions (pH 7.25 and H₂O₂ concentration 200 μmol L⁻¹), a LOD as low as 0.8 μmol L⁻¹ was attained, while the linear concentration range was extended from 2.64 μmol L⁻¹ up to 35 μmol L⁻¹. The main advantage of the proposed bi‐enzyme sensor is its selectivity toward the OPs with phenolic leaving groups, excluding the interference of the nitrophenyl‐substituted OPs.     

Electrodetermination of Gallic Acid Using Multi-walled Carbon Nanotube Paste Electrodes and N-Octylpyridinium Hexafluorophosphate

In this work, the determination of gallic acid was performed using surface-renewable carbon paste electrodes fabricated with multi-walled carbon nanotubes (MWCNT) and a mixture of N-octylpyridinium hexafluorophosphate (OPyPF₆) ionic liquid with mineral oil (MO) as binder. This system shows remarkable amperometric sensor characteristics and promotes a better electronic transfer. An electroanalytical study of gallic acid shows a linear range from 4.98±0.25 to 74.1±2.2 μmol L⁻¹, with R²=0.9958 and an experiment a limit of detection of 2.70±0.08 μmol L⁻¹ (S/N=3), and a sensitivity of 0.029 μA μmol⁻¹ L.     

Glassy Carbon Electrode Modified with Layering of Carbon Black/Poly(Allylamine Hydrochloride) Composite for Multianalyte Determination

An electrochemical sensor using glassy carbon electrode modified with carbon black within a poly(allylamine hydrochloride) film is proposed in this work. The novel sensor was characterized by scanning electron microscopy, electrochemical impedance spectroscopy, and cyclic voltammetry using the redox probe Fe(CN)6^3−/4−. The sensor was applied for the simultaneous determination of dopamine (DA), paracetamol (PAR), amlodipine (AML), and rosuvastatin (RSV). The quantification of all four analytes was carried out by linear sweep voltammetry and presented a linear concentration range for all analytes from 1.0 to 90 μmol L⁻¹, with limit of detection of 0.55, 1.3, 5.7, and 3.0 μmol L⁻¹ for DA, PAR, AML, and RSV, respectively. This sensor was successfully applied in the simultaneous determination of these analytes in environmental, pharmaceutical, and biological samples.     

Magnetite Nanoparticles Bonded Carbon Quantum Dots Magnetically Confined onto Screen Printed Carbon Electrodes and their Performance as Electrochemical Sensor for NADH

Hybrid magnetite/carbon quantum dots (MagNP/C‐dots) were prepared and their characterization performed by high resolution transmission electron microscopy (HR‐TEM), X‐ray diffraction (XRD) and X‐ray photoelectron spectroscopy (XPS). Because of their suitable magnetization and electrochemical properties, they were used as versatile electrode modifiers after magnetically confining onto screen printed carbon electrodes (SPE), with the aid of a miniature external magnet. The reported strategy introduces a convenient procedure for assembling modified electrodes, since the nanoparticles can be easily released by removing the magnet. The non‐enzymatic magnetic biosensor showed excellent performance in the determination of NADH at the concentration range 2×10⁻⁷ to 5×10⁻⁶ mol L⁻¹, exhibiting a sensitivity of 0.15 μmol L⁻¹ and detection limit of 20 nmol L⁻¹. The MagNP/C‐dots/SPE sensor was also successfully applied for the determination of NADH in serum samples. The interference of typical biological molecules has also been investigated.     

Tellurium Film Electrodes Deposited on Carbon and Mesoporous Carbon Screen‐printed Substrates for Anodic Stripping Voltammetric Determination of Copper

The performance of screen‐printed electrodes modified in situ with tellurium film for the anodic stripping voltammetric (ASV) determination of Cu(II) is reported. It was found that two types of screen‐printed substrates, namely carbon and mesoporous carbon, were optimal for this application. The selected in situ tellurium film modified electrodes were applied for the square wave ASV determination of copper at μg L⁻¹ concentration levels. Well‐defined and reproducible Cu oxidation stripping peaks were produced at a potential more negative than the anodic dissolution of tellurium. The highest sensitivity of Cu determination was achieved in 0.05 M HCl containing 50 μg L⁻¹ Te(IV) after 300 s of accumulation at −0.5 V. Using the optimized procedure, a linear range from 2 to 35 μg L⁻¹ of Cu(II) was obtained with a detection limit of 0.5 μg L⁻¹ Cu(II) (S/N=3) for 300 s of deposition time. Both sensors, carbon TeF‐SPE and mesoporous carbon TeF‐SPE, were successfully applied for the quantification of Cu in a certified reference surface water sample.     

Carbon‐nanotube Modified Screen‐printed Electrode for the Simultaneous Determination of Nitrite and Uric Acid in Biological Fluids Using Batch‐injection Amperometric Detection

A portable electroanalytical system applied for rapid and simultaneous determination of uric acid (UA) and nitrite (NIT) in human biological fluids (urine, saliva and blood) is reported. The system is based on batch‐injection analysis with multiple‐pulse amperometric (BIA‐MPA) detection using screen‐printed electrodes (SPEs) modified with multi‐walled carbon nanotubes. Sample dilution in optimized electrolyte (0.1 mol L⁻¹ Britton‐Robinson buffer pH 2) followed by injection of 100 μL on the electrode surface using an electronic micropipette is performed. UA is detected at +0.45 V and both UA+NIT at +0.70 V. Linear calibration plots for UA and NIT were obtained over the range of 1–500 μmol L⁻¹ with detection limits of 0.05 and 0.06 μmol L⁻¹, respectively. For comparison, a differential‐pulse voltammetric (DPV) method was optimized, and linear calibration plots for UA and NIT were obtained over range of 1–30 μmol L⁻¹ and 1–40 μmol L⁻¹ with detection limits of 0.1 and 0.3 μmol L⁻¹, respectively. BIA‐MPA is highly precise (RSD<1.3 %), fast (160 h⁻¹) and free from sample‐matrix interferences as recovery values ranged from 77 to 121 % for spiked samples (short contact time of sample aliquot with SPE). Contrarily, recovery tests conducted using DPV did not provide adequate recovery values (>150 %), probably due to the longer contact time of the SPE with the biological samples during analysis leading to a severe interference of sample matrices.     

Adsorptive Stripping Voltammetric Determination of 2,4-Dichlorophenol by Laponite Modified Carbon Paste Electrode

A laponite modified carbon paste electrode was prepared, characterized and applied for the 2,4-dichlorophenol (2,4-DCP) voltammetric determination. It takes advantage of the ability of laponite to adsorb phenols, as well as of its availability and very low cost. Kinetic and equilibrium data for 2,4-DCP adsorption by laponite in aqueous dispersions demonstrated that the adsorption process obeyed a pseudo first order kinetic model and was consistent with the formation of adsorbed multilayers on a surface with heterogeneous pore distribution. The composite paste electrode exhibited a heterogeneous surface with 65 % increased surface area and 27 % enhanced catalytic activity compared to the unmodified one. The adsorptive stripping voltammetric determination of 2,4-DCP at an electrode with an optimized graphite:laponite ratio of 55 : 15 w% using a 3 min accumulation time at pH 5.5 was found to be suitable for its quantification in the linear concentration range extended up to 50 μmol L⁻¹ with a sensitivity of 0.56 μA L μmol⁻¹ and a LOD of 0.2 μmol L⁻¹ (S/N=3).The 2,4-DCP electrochemical response was not affected by the presence of some structurally similar phenols, like catechol and p-nitrophenol, while resorcinol, 2-chlorophenol, and 4-chlorophenol presented interferences. The results were validated by 2,4-DCP determination in spiked tap water.     

Development of a Novel Molecularly Imprinted Polyvinylimidazole/Functionalized Carbon Black Nanocomposite-based Paste Electrode for Electrochemical Sensing of Imazethapyr in Rice Samples

This paper reports the development of a simple electroanalytical method for imazethapyr (IMT) determination in rice samples based on molecularly imprinted polymer and functionalized carbon black paste electrode (MIP-fCBPE). Carbon black (CB) was functionalized by the insertion of oxygenated functional groups upon acid treatment with HNO₃ and H₂SO₄. The functionalized carbon black (fCB) presented higher performance for IMT determination than the CB without functionalization. The insertion of molecularly imprinted polyvinylimidazole (MIP-VN) in the fCBPE promoted a significant increase in the cathodic peak current even at low proportions (7.5 % w/w) due to the specific binding sites for IMT recognition. For IMT determination, DPV parameters were optimized by the Doehlert matrix applying 0.1 V for 60 s as pre-treatment in acetate buffer solution (pH 3.0) as supporting electrolyte. The proposed method showed low limit of detection (0.03 μmol L⁻¹), a wide linear range (0.10–70.00 μmol L⁻¹), and good precision in terms of repeatability of intraday measures (RSD%=3.6). The method was applied in rice samples after microwave-assisted extraction of IMT and the accuracy of the method was evaluated by addition/recovery assays (96.3–105.7 %), being statistically attested using HPLC-DAD as reference technique.     

Fabrication of β‐Cyclodextrin/Glycine/Carbon Nanotubes Electrochemical Neurotransmitters Sensor – Application in Ultra‐sensitive Determination of DOPAC in Human Serum

In this work, an electrochemical sensor was constructed by applying two successive thin layers of glycine‐carbon nanotubes mixture and β‐cyclodextrin (CNTs‐Gly)/CD over glassy carbon electrode surface for some neurotransmitters determination. A host‐guest interaction between CD and neurotransmitters molecules is expected and resulted in enhanced sensitivity, selectivity and stability of sensor response. Other components of the sensor are crucial for the unique electrochemical response. Carbon nanotubes allowed large surface area for glycine distribution that provided hydrogen bonding to CD moieties and contributed to facilitated charge transfer. It was possible to determine 3,4‐dihydroxy phenyl acetic acid (DOPAC) in the linear range of 0.1 μmol L⁻¹ to 80 μmol L⁻¹ with detection limit of 9.40 nmol L⁻¹, quantification limit of 31.5 nmol L⁻¹ and sensitivity of 4.16 μA/μmol L⁻¹. The proposed sensor was applied in synthetic cerebrospinal fluids samples using random standard addition method. Also, the proposed sensor was used to determine DOPAC in presence of common interferences and acceptable recovery results were achieved for its analysis in real blood serum. Figures of merit for (CNTs‐Gly)/CD composite in terms of precision, robustness, repeatability and reproducibility were reported.     

Voltammetric Method for the Simultaneous Determination of Melatonin and Pyridoxine in Dietary Supplements Using a Cathodically Pretreated Boron‐doped Diamond Electrode

The simultaneous voltammetric determination of melatonin (MT) and pyridoxine (PY) has been carried out at a cathodically pretreated boron‐doped diamond electrode. By using cyclic voltammetry, a separation of the oxidation peak potentials of both compounds present in mixture was about 0.47 V in Britton‐Robinson buffer, pH 2. The results obtained by square‐wave voltammetry allowed a method to be developed for determination of MT and PY simultaneously in the ranges 1–100 μg mL⁻¹ (4.3×10⁻⁶–4.3×10⁻⁴ mol L⁻¹) and 10–175 μg mL⁻¹ (4.9×10⁻⁵–8.5×10⁻⁴ mol L⁻¹), with detection limits of 0.14 μg mL⁻¹ (6.0×10⁻⁷ mol L⁻¹) and 1.35 μg mL⁻¹ (6.6×10⁻⁶ mol L⁻¹), respectively. The proposed method was successfully to the dietary supplements samples containing these compounds for health‐caring purposes.     

Preconcentration and Successful Selective Detection of Traces of Diclofenac in Water using a Nanostructured Modified Carbon Paste Electrode

A highly sensitive, simple and low cost sensor for the quantification of the diclofenac has been constructed. This sensor consists of a carbon paste nano-structured by Multi-Walled Carbon Nanotubes (G-MWCNT)-CPE. Scanning electron microscopy (SEM) and voltammetry technique were used to characterize the electrode material and to determine the analytical performances of the sensor in comparison with those obtained at a G-CPE. The electrochemical oxidation of diclofenac on both G-CPE and (G-MWCNT)-CPE electrodes is mainly controlled by adsorption, presenting a maximum peak current intensity in H₂SO₄ 0.5 mol L⁻¹. The carbon nanotubes, as well as they provide higher conductivity of the paste, act as spacers between the flake graphite particles and avoid their stacking in order to make the surface of graphite particles more accessible to DCF adsorption. The voltammetric measurements of diclofenac on (G-MWCNT)-CPE provide a large quantification range from 0.02 to 1 μmol L⁻¹, a detection limit of 0.004 μmol L⁻¹ and quantification limit of 0.014 μmol L⁻¹ under the optimized operating conditions (H₂SO₄, 0.25 M+KCl 0.25 M, scan rate of 30 mV s⁻¹, preconcentration time 18 min. and MWNTC% (30 %)). The (G-MWCNT)-CPE sensor was successfully applied to natural water samples, just acidified with sulfuric acid (pH<1). These samples were doped with diclofenac in sub-micromolar range and the developed method was validated with excellent recoveries (within a maximum of 3 % difference from 100 %) for all samples indicating no interference effects of the water matrix.     

Fast and Simple Electrochemical Analysis Kit for Quality Control of Narrow Therapeutic Index Drugs

The use of multiple‐pulse amperometry (MPA) for the determination of narrow therapeutic index (NTI) drugs using batch injection analysis (BIA) with carbon screen‐printed electrodes (SPE) is proposed, seeking to develop a practical and low‐cost analysis kit for application in routine quality control of these drugs. The electrochemical behaviors of aminophylline, carbamazepine, clindamycin, colchicine, minoxidil, prazosin, procainamide, theophylline, warfarin and verapamil were evaluated in different electrolytes, but just one, the 0.1 mol L⁻¹ phosphate buffer, pH 7.0, was chosen for determination of all the analytes. The amperometric detection was optimized as a function of the best oxidation potential for carbon SPE for each analyte, which was in a range from 0.7 to 1.1 V. The injection conditions were determined as a function of the velocity and the volume injected by the BIA system, which were 92.5 μL s⁻¹ and 100 μL, respectively. Under these conditions, a good repeatability (RSD<3 %), high analytical frequency (>215 determinations per hour), large linear ranges and low LOD (<0.42 μmol L⁻¹) for all the NTI drugs were obtained. Furthermore, the proposed method provided an easy qualitative analysis of the investigated analytes using MPA detection. The addition‐recovery studies in pharmaceutical samples containing NTI drugs and the comparison with official methods showed that the proposed analysis Kit is a very fast, simple and efficient alternative for quantification of these analytes.