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.     

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.     

Sensor Modified with Gold Nanoparticles Stabilized in Dialdehyde Starch/DMSO Matrix for Methyldopa Detection

In this study, gold nanoparticles (AuNP) were synthesized using a novel stabilizer based on dialdehyde starch polymer (DAS) and dimethyl sulfoxide (DMSO) and the nanomaterial was applied to develop a sensor for methyldopa detection. The nanoparticles were characterized by transmission electron microscopy and the proposed sensor was electrochemically characterized by electrochemical impedance spectroscopy, chronocoulometry and square-wave voltammetry. Under optimized conditions (0.1 mol L⁻¹ McIlvaine buffer solution at pH 3.5 and 50 μL AuNP/DAS-DMSO), using square-wave voltammetry, the calibration curve presented a linear range of 0.99 to 19.60 μmol L⁻¹, with a detection limit of 0.50 μmol L⁻¹. The sensor showed good accuracy, with coefficients of variation of 7.8 % (inter-day; n=6) and 5.9 % (intra-day; n=3), and recovery values in the range of 95.3 to 105.2 %. The methyldopa content in a pharmaceutical sample was determined and the results show good correlation with the label value and the method recommended by the Pharmacopoeia, representing a fast and accurate alternative for detecting methyldopa in pharmaceutical products.     

Nanoporous Gold Microelectrode: A Novel Sensing Platform for Highly Sensitive and Selective Determination of Arsenic (III) using Anodic Stripping Voltammetry

A home‐made gold microelectrode (Au‐μE) was fabricated and its surface was modified with nanoporous gold structures via a facile electrochemical approach (anodization followed by electrochemical reduction method). The fabricated nanoporous Au microelectrode (NPG‐μE) was used as a sensor probe for the determination of As(III) in 1.0 mol L⁻¹ HCl solution using square wave anodic stripping voltammetry (SWASV) technique. Field emission scanning electron microscopy (FE‐SEM) and cyclic voltammetry were used to characterize the surface morphology and assess the electrochemical surface area and the roughness factor of the NPG‐μE. SWASVs recorded with the NPG‐μE in As(III) solutions indicated linear behaviour in the concentration ranges of 10–200 μg L⁻¹ and 2–30 μg L⁻¹, with regression coefficients of 0.996 and 0.999 at a deposition time of 120 s, respectively. The limit of detection (LOD) was found to be 0.62 μg L⁻¹ with high sensitivity of 29.75 μA (μg L⁻¹)⁻¹ cm⁻². Repeatability and reproducibility were also examined and values were determined as 3.2 % and 9.0 %. Negligible interference from major interfering copper ion was noticed, revealing the excellent anti‐interference property of the proposed sensing platform. The developed NPG‐μE was successfully used for As(III) determination in tap water samples.     

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.     

Bismuth Nanoparticles@Porous Silicon Nanostructure,Application as a Selective and Sensitive Electrochemical Sensor for the Determination of Thioridazine

A bismuth@porous silicon (Bi/PSi) nanostructure is fabricated and used as a new highly sensitive electrochemical sensor for measurement of thioridazine. For this purpose, commercial silicon powder is converted to porous silicon using metal‐assisted chemical etching method. Then, bismuth nanoparticles are deposited on the surface of the porous silicon that synthesized in the previous step. The effects of pH and instrumental parameters are studied on the sensor response. After optimization of the parameters, differential pulse voltammetry is used to determine sub‐micro molar amounts of thioridazine. The Linear region of the electrochemical sensor is in the range of 0.1 to 260 μmol L⁻¹ thioridazine with a detection limit of 0.03 μmol L⁻¹, when Bi/PSi/CNTPE is used as an electrochemical sensor. The precision and accuracy of the sensor is evaluated. The Bi/PSi/CNTPE is used as an appropriated tool for accurate measurement of low amounts of thioridazine in real samples with satisfactory results.     

A new Approach for the Voltammetric Sensing of the Phytoestrogen Genistein at a Non-modified Boron-doped Diamond Electrode

An effective electrochemical sensor was constructed using an unmodified boron-doped diamond electrode for determination of genistein by square-wave voltammetry. Cyclic voltammetric investigations of genistein with HClO₄ solution indicated that irreversible behavior, adsorption-controlled and well-defined two oxidation peaks at about +0.92 (P_A1) & +1.27 V (P_A2). pH, as well as supporting electrolytes, are important in genistein oxidations. Quantification analyses of genistein were conducted using its two oxidation peaks. Using optimized experiments as well as instrumental conditions, the current response with genistein was proportionately linear in the concentrations range of 0.1 to 50.0 μg mL⁻¹ (3.7×10⁻⁷−1.9×10⁻⁴ mol L⁻¹), by the detection limit of 0.023 μg mL⁻¹ (8.5×10⁻⁸ mol L⁻¹) for P_A1 and 0.028 μg mL⁻¹ (1.1×10⁻⁷ mol L⁻¹) for P_A2 in 0.1 mol L⁻¹ HClO₄ solution (in the open circuit condition at 30 s accumulation time). Ultimately, the developed method was effectively applied to detect genistein in model human urine samples by using its second oxidation peak (P_A2).     

Copper‐based Metal‐organic Framework Applied in the Development of an Electrochemical Biomimetic Sensor for Catechol Determination

In this study, the synthesis and characterization of a Cu‐based metal‐organic framework (MOF) [Cu₃(BTC)₂(H₂O)₃]_n (where BTC=benzene‐1,3,5‐tricarboxylate), known as HKUST‐1, were performed. The Cu‐MOF was applied in the modification of a carbon paste to obtain a biomimetic sensor for the electrochemical determination of catechol. Kinetic assays confirmed that the Cu‐MOF acts as a catalyst for the oxidation of catechol and it can be considered as a catechol oxidase mimetic. Under optimized conditions, the calibration curve for catechol presented a linear range of 8.0×10⁻⁷ to 3.2×10⁻⁵ mol L⁻¹, with detection limit of=1.0×10⁻⁷ mol L⁻¹. The sensor demonstrated good intra‐day repeatability and inter‐electrode reproducibility (relative standard deviations of 3.8 % (n=10) and 4.3 % (n=6), respectively). In the selectivity study, an adequate peak‐to‐peak separation was observed for hydroquinone and uric acid in relation to catechol, demonstrating that this sensor has the potential for use in the simultaneous determination of these compounds. This sensor was successfully applied in the determination of catechol in water samples.     

Development of Electrochemical Platform Based on Molecularly Imprinted Poly(methacrylic acid) Grafted on Iniferter-modified Carbon Nanotubes for 17β-Estradiol Determination in Water Samples

This paper describes the development of a new electrochemical sensor for 17β-estradiol (E2) determination based on glassy carbon electrode (GCE) modified with molecularly imprinted polymer grafted onto iniferter-multiwall carbon nanotubes surface (MIP-MWCNT) and dihexadecyl-hydrogen-phosphate (DHP). The electrochemical method was based on closed-circuit preconcentration of E2 in 0.1 mol L⁻¹ phosphate buffer (pH 7.0) during 500 s. Upon preconcentration, E2 was determined by differential pulse voltammetry (DPV) exhibiting a limit of detection of 0.01 μmol L⁻¹. The sensor exhibited higher selectivity toward E2 and it was applied for E2 determination in natural water samples, with accuracy attested by HPLC-DAD.     

Competitive Host-guest Electrochemical Detection of Ivermectin Drug Using a β-Cyclodextrin/Graphene-based Electrode

The present study describes the novel development and application of an ivermectin (IVM) sensing electrochemical platform based on reduced graphene oxide (rGO) and the macrocyclic host β-cyclodextrin (β-CD) molecule. The sensing method was based in the host-guest characteristics of β-CD and competitive interaction between the target analyte and the methylene blue (MB) redox probe. Differential pulse voltammetry (DPV) was employed for the detection of IVM and a linear response between 0.5 and 40.0 μmol L⁻¹ with a limit of detection of 0.25 μmol L⁻¹ was obtained using the glassy carbon (GC)/rGO/β-CD electrode. The sensing platform was successfully applied for the detection of IVM in tap water samples, which may expand the applications of β-CD towards the analysis of other chemical species.     

Electrochemical Sensor Based on Multiwalled Carbon Nanotube,Alizarine Red S and Chitosan for Simultaneous Determination of Oxomemazine Hydrochloride,Paracetamol and Guaifenesin

A simple and highly sensitive sensor has been used for the determination of oxomemazine hydrochloride (OXO) in presence of paracetamol (PAR) and guaifenesin (GU). Carbon paste electrode was modified with multiwalled carbon nanotube (MWCNT), alizarine red S (AZ) and chitosan (CH). Scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV) and differential pulse voltammetry (DPV) were used to characterize the nanostructure and performance of the sensor. Under the optimized experimental conditions OXO gave linear response over the range of 2.00×10⁻⁶–1.00×10⁻⁴ mol L⁻¹. The detection limit was found to be 4.35×10⁻⁷ mol L⁻¹. The practical application of the modified electrode was demonstrated by measuring the concentration of OXO in pharmaceutical samples and urine. This revealed that suggested sensor shows excellent analytical performance for the determination of OXO in terms of a very low detection limit, high sensitivity and selectivity.     

Cost-effective and Facile Production of a Phosphorus-doped Graphite Electrode for the Electrochemical Determination of Pyridoxine

In this study; a sensitive, selective, and simple electrochemical sensor was developed to determine low concentration pyridoxine (Py) using a phosphorus-doped pencil graphite electrode (P-doped/PGE). Electrode modification was implemented using the chronoamperometry method at +2.0 V constant potential and 100 seconds in 0.1 mol L⁻¹ H₃PO₄ supporting electrolyte solution. The characterization processes of the P-doped/PGE were carried out using electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDX), and atomic force microscope (AFM) methods. In the concentration study, using the differential pulse voltammetry (DPV) method, a linear calibration plot was acquired in the concentration range of 0.5 to 300 μmol L⁻¹ Py. The limit of quantification (LOQ) and limit of detection (LOD) of the developed method were calculated as 0.219 μmol L⁻¹ and 0.0656 μmol L⁻¹, respectively. Detection of Py has been successfully performed on the P-doped/PGE in the beverage samples. As a result, the method developed has been shown to have fast, low cost, and simple for the sensitive and selective detection of Py as an effective electrode.     

Voltammetric Detection of Captopril in a Commercial Drug Using a Gold-Copper Metal-organic Framework Nanocomposite Modified Electrode

We report the application of an electrochemical sensor based on gold-copper metal-organic framework immobilized on the surface of a glassy carbon electrode to the detection of captopril (CAP), an angiotensin-converting enzyme inhibitor. Cyclic voltammetric studies showed that the joint action of gold nanoparticles and copper-1,3,5-benzenetricarboxylate (Cu−BTC) enhanced the electrochemical response to the Cu-captopril complex that is adsorbed onto the surface of the electrode. Release of gold nanoparticles from Au@Cu−BTC not only increased the conductivity of the electrode but also provided a more favorable environment for the deposition of reduced Cu that is catalytically renewed on the electrode surface. The anodic current of the Cu^(II)−CAP oxidation peak varied linearly within two concentration ranges, namely 0.5 to 7.0 μmol L⁻¹ and 10 to 2500 μmol L⁻¹, with a limit of detection of 0.047 μmol L⁻¹. The mean recovery for the determination of captopril in commercial tablets was 100.3 % suggesting that the method has considerable potential for future industrial applications.     

Square-wave Anodic Stripping Voltammetric Method for Novelty Detection of Bismuth Extracted by Aqueous Two-phase Systems

In this work, a voltammetric sensor was used to monitor the concentration of bismuth extracted from an eutectic alloy of BiSn by aqueous two-phase system. This strategy is a sustainable and economically viable way of recovering bismuth from secondary sources. In the aqueous two-phase system (ATPS), biodegradable and non-toxic constituents dispersed in water (major constituent) are used. For monitoring the extraction, bismuth was determined in the upper phase of the aqueous two-phase system, which is rich in L35 copolymer, that causes attenuation of the electrochemical signal (anodic peak current). The electrode and operational parameters of the square-wave anodic stripping voltammetry (SWASV) were evaluated according to the deposition and stripping processes of the bismuth on the surface of the carbon paste electrode (CPE). It was observed a similarity between the electrochemical response of the bismuth extracted by ATPS and with the standard solution of bismuth. The proposed method shows a linear range of 1.29–8.94 μmol L⁻¹, limit of detection (1.07 μmol L⁻¹) and limit of quantification (3.57 μmol L⁻¹) and good precision (RSD%=2.27 %). This method was validated by comparing the results with Flame Atomic Absorption Spectroscopy (FAAS), using statistical tests to verify precision and accuracy. In conclusion, using a voltammetric sensor to monitor the concentration of bismuth extracted by ATPS proved to be an efficient method, in agreement with the concentrations of the referenced method.     

Development of a New Voltammetric Methodology for the Determination of Ciprofloxacin in Beef Samples Using a Carbon Paste Electrode Modified with Nafion and Fullerenes

A sensitive, selective, and low cost electrochemical new methodology was developed for the quantification of ciprofloxacin (Cip) in beef samples by cyclic voltammetry and differential pulse voltammetry, using a CPE electrode modified with Nafion and Fullerenes (N−F/CPE). The optimum parameters for the composition of the N−F/CPE electrode are 0.19 g mineral oil, 0.01 g Nafion, 50 μL fullerene, and graphite powder 0.3 g. The electrochemical characterization was carried out by obtaining maximum anodic peak current associated with the oxidation of ciprofloxacin at 1.1 V, where the electrochemical process resulted to be irreversible and diffusion-controlled. The analytical characterization of the proposed methodology was carried out resulting in a LOD of 1.0 μmol L⁻¹, a LOQ of 3.0 μmol L⁻¹, a sensitivity of 0.37±0.006 μA/μmolL⁻¹, and repeatability of 5.38 %.     

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.     

A MnOOH‐Polyaniline Nanocomposite Modified Gold Electrode for Electrochemical Sensing of Nitrite

A novel non‐enzymatic nitrite sensor was fabricated by immobilizing MnOOH‐PANI nanocomposites on a gold electrode (Au electrode). The morphology and composition of the nanocomposites were investigated by transmission electron microscopy (TEM ) and Fourier transform infrared spectrum (FTIR ). The electrochemical results showed that the sensor possessed excellent electrocatalytic ability for NO₂⁻ oxidation. The sensor displayed a linear range from 3.0 μmol•L⁻¹ to 76.0 mmol•L⁻¹ with a detection limit of 0.9 μmol•L⁻¹ (S/N = 3), a sensitivity of 132.2 μA •L•mol⁻¹•cm⁻² and a response time of 3 s. Furthermore, the sensor showed good reproducibility and long‐term stability. It is expected that the MnOOH‐PANI nanocomposites could be applied for more active sensors and used in practice for nitrite sensing.     

A new voltammetric sensor for the determination of sulfite in water and wastewater using modified-multiwall carbon nanotubes paste electrode

The electrochemical response of a modified-carbon nanotubes paste electrode with p-aminophenol was investigated as an electrochemical sensor for sulfite determination. The electrochemical behaviour of sulfite was studied at the surface of the modified electrode in aqueous media using cyclic voltammetry and square wave voltammetry. It has been found that under the optimum condition (pH 7.0) in cyclic voltammetry, the oxidation of sulfite occurs at a potential about 680?mV less positive than that of an unmodified-carbon nanotubes paste electrode. Under the optimized conditions, the electrocatalytic peak current showed linear relationship with sulfite concentration in the range of 2.0?×?10^?7–2.8?×?10^?4?mol?L^?1 with a detection limit of 9.0?×?10^?8?mol?L^?1 sulfite. The relative standard deviations for ten successive assays of 1.0 and 50.0?µmol?L^?1 sulfite were 2.5% and 2.1%, respectively. Finally, the modified electrode was examined as a selective, simple and precise new electrochemical sensor for the determination of sulfite in water and wastewater samples.     

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.     

Photoelectrochemical Sensor for Isoniazid: Application in Drugs Used in the Treatment of Tuberculosis

The present work describes the development of a photoelectrochemical sensor based on titanium dioxide, cadmium telluride quantum dots and the tris (2,2′-bipyridyl) ruthenium(II) chloride complex for detection of Isoniazid (INH). The Ru(bpy)₃²⁺/CdTe-QDs/TiO₂/FTO photoelectrochemical platform was characterized by scanning electrochemical microscopy, electrochemical impedance spectroscopy and amperometry. The photoelectrochemical sensor presented two linear ranges for INH concentrations ranging from 0.5 to 150 μmol L⁻¹ and 150 to 1270 μmol L⁻¹, with a theoretical detection limit of 0.02 μmol L⁻¹. The sensor was successfully applied for the determination of INH in drugs samples used in the treatment of tuberculosis.