Electrochemical Determination of Neurotransmitters at Crown Ether Modified Carbon Nanotube Composite: Application for Sub‐nano‐sensing of Serotonin in Human Serum

We propose an electrochemical sensor based on applying two successive thin layers from a mixture of multiwalled carbon nanotubes‐ionic liquid crystal and crown ether at glassy carbon electrode surface (GC/(CNTs‐ILC)/Crown). The sensor was used for sensitive determination of neurotransmitters based on effective synergism between its components. The compact conducting surface of (CNTs ‐ ILC) with large surface area allowed the assembling of stable host‐guest inclusion complexes between crown ethers and neurotransmitters. The GC/(CNTs‐ILC)/Crown exhibited excellent electro‐catalytic activity toward the determination of serotonin (ST) in a wide linear dynamic range: 0.005 μmol L^?1 to 100 μmol L^?1. In the concentration range 0.005 μmol L^?1 to 1 μmol L^?1, the detection limit is 2.03×10^?10 mol L^?1 and quantification limit is 6.78×10^?10 mol L^?1 with correlation coefficient 0.999. The sensor was successfully applied for ST detection in human serum samples with satisfied recovery results. The sensor showed excellent analytical performance for the determination of ST in terms of low detection limit, good sensitivity and reproducibility. Furthermore excellent anti‐interference ability and simultaneous determination of ST in presence of other compounds as ascorbic acid, dopamine and antidepressant drug were achieved.     

Sensitive Voltammetric Determination of Bisphenol A Based on a Glassy Carbon Electrode Modified with Copper Oxide‐Zinc Oxide Decorated on Graphene Oxide

A highly sensitive and selective chemical sensor was prepared based on metallic copper‐copper oxides and zinc oxide decorated graphene oxide modified glassy carbon electrode (Cu?Zn/GO/GCE) through an easily electrochemical method for the quantification of bisphenol A (BPA). The composite electrode was characterized via scanning electron microscopy (SEM), X‐Ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). The electrochemical behavior of BPA in Britton‐Robinson (BR) buffer solution (pH 7.1) was examined using cyclic voltammetry (CV). Under optimized conditions, the square wave voltammetry (SWV) response of Cu?Zn/GO/GCE towards BPA indicates two linear relationships within concentrations (3.0 nmol L^?1?0.1 μmol L^?1 and 0.35 μmol L^?1?20.0 μmol L^?) and has a low detection limit (0.88 nmol L^?1). The proposed electrochemical sensor based on Cu?Zn/GO/GCE is both time and cost effective, has good reproducibility, high selectivity as well as stability for BPA determination. The developed composite electrode was used to detect BPA in various samples including baby feeding bottle, pacifier, water bottle and food storage container and satisfactory results were obtained with high recoveries.     

High performance electrochemical sensor based on modified screen-printed electrodes with cost-effective dispersion of nanostructured carbon black

A novel sensor based on a screen-printed electrode (SPE) modified with a stable dispersion of commercially available carbon black (CB) N220 was developed. This probe showed significantly enhanced electrochemical activity relative to a bare SPE when tested with ferricyanide, epinephrine, norepinephrine, benzoquinone and NADH. When challenged in amperometric batch mode with NADH, the response was stable and revealed a linear dependence up to 2·10^?4 mol L^?1 with a detection limit of 3·10^?7 mol L^?1. The analytical performance, coupled with the low cost of the CB nanomaterial, suggests that this sensor holds promise for electrochemical applications.     

A Sensitive Sensor Based on Single‐walled Carbon Nanotubes: Its Preparation,Characterization and Application in the Electrochemical Determination of Drug Clorsulon in Milk Samples

Within this paper, a glassy carbon electrode modified with single‐walled carbon nanotubes (SWCNTs?GCE) was prepared, and employed for the determination of clorsulon (Clo), which is a frequently used veterinary drug against common liver fluke. The comprehensive topographical and electrochemical characterizations of bare GCE and SWCNTs?GCE were performed by atomic force microscopy, electrochemical impedance spectroscopy, and cyclic voltammetry. Significantly enhanced electrochemical characteristics of SWCNTs?GCE toward a ferrocyanide/ferricyanide redox couple was observed when compared to bare GCE. Further, the prepared sensor was applied for the voltammetric determination of Clo, which was electrochemically investigated for the first time in this work. Voltammetric experiments were performed using square‐wave voltammetry with optimized parameters in phosphate buffer solution, pH 6.8, which was selected as the most suitable medium for the determination of Clo. The corresponding current at approx. +1.1 V increased linearly with Clo concentration within two linear dynamic ranges of 0.75–4.00 μmol L^?1 (R²=0.9934) and 4.00–15.00 μmol L^?1 (R²=0.9942) with a sensitivity for the first calibration range of 0.76 μA L μmol^?1, a limit of detection of 0.19 μmol L^?1, and a limit of quantification of 0.64 μmol L^?1. The developed method was subsequently applied for quantitative analysis of Clo in milk samples with results proving high repeatability and recovery.     

Flow Injection Analysis of Maleic Hydrazide Using an Electrochemical Sensor Based on Palladium‐Dispersed Carbon Paste Electrode

A new analytical methodology for the electrochemical detection of the herbicide maleic hydrazide (3,6‐dihydroxypyridazine) by flow injection analysis is presented. This method is supported by the novel application of a palladium‐dispersed carbon paste electrode as an amperometric sensor for this herbicide. Maleic hydrazide shows anodic electrochemical activity on carbon‐based electrodes (glassy carbon or carbon paste electrodes) in all the pH range. This electrochemical activity is enhanced using metal‐dispersed carbon paste electrodes, especially at Pd‐dispersed CPE which displays good oxidation signals at 690 mV (0.050 M phosphate buffer pH 7.0), 140 mV lower than at unmodified electrodes. Under the optimized conditions, the electroanalytical performance of Pd‐dispersed CPE in flow injection analysis was excellent, with good reproducibility (RSD 3.3%) and a wide linear range (1.9×10^?7 to 1.0×10^?4 mol L^?1). A detection limit of 1.4×10^?8 mol L^?1 (0.14 ng maleic hydrazide) was obtained for a sample loop of 100 μL at a fixed potential of 700 mV in 0.050 M phosphate buffer solution at pH 7.0 and a flow rate of 2.0 mL min^?1. The proposed method was applied for the maleic hydrazide detection in natural drinking water samples.     

Electrogenerated Chemiluminescence of Tris(2,2′‐bipyridyl)ruthenium(II) Immobilized in Humic Acid‐Silica‐Poly(vinyl alcohol) Composite Films

In this paper, we report the first attempt to use humic acid (HA) as modifiers to prepare the organic‐inorganic hybrid modified glassy carbon electrodes based on HA‐silica‐PVA (poly(vinyl alcohol)) sol‐gel composite. Electroactive species of tris(2,2′‐bipyridyl)ruthenium(II) (Ru(bpy) ) can easily incorporate into the HA‐silica‐PVA films to form Ru(bpy) modified electrodes. The amount of Ru(bpy) incorporated in the composite films strongly depends on the amount of HA in the hybrid sol. Electrochemical and electrogenerated chemiluminescence (ECL) of Ru(bpy) immobilized in HA‐silica composite films coated on a glassy carbon electrode have been studied with tripropylamine (TPA) as the coreactant. The analytical performance of this modified electrode was evaluated in a flow injection analysis (FIA) system with a homemade flow cell. The as‐prepared electrode showed good stability and high sensitivity. The detection limits (S/N=3) were 0.050 μmol L^?1 for TPA and 0.20 μmol L^?1 for oxalate, and the linear ranges were from 0.10 μmol L^?1 to 1.0 mmol L^?1 for TPA and from 1.0 μmol L^?1 to 1.0 mmol L^?1 for oxalate, respectively. The resulting electrodes were stable over two months.     

Electrochemical Determination of Dicofol at Nickel Nanowire Modified Poly(p‐aminophenol) Film Electrode

An electrochemical sensor was fabricated by construction of nickel nanowires on the surface of poly(p‐aminophenol) (PPAP) modified glassy carbon electrode. The electrochemical response of dicofol, a known pesticide and used for agricultural activities such as cyclic voltammetry and differential pulse voltammetry, were investigated and the results were compared with those obtained unmodified electrodes. Following the optimization of NaOH concentration, polymerization cycle number, Ni nanowire amount, the linear range for the dicofol was studied and found as 0.83–30.7 μmol L^?1 (R²=0.9981) at Ni/PPAP/GCE with a 0.08 μmol L^?1 detection limit according to S/N=3. Finally, the proposed Ni/PPAP/GCE sensor was successfully applied for the dicofol analysis in soil samples. The characterization of the developed surface was carried out by scanning electron microscopy and X‐Ray photoelectron spectroscopy.     

Poly(Taurine‐Glutathione)/Carbon Nanotube Modified Glassy Carbon Electrode as a New Levofloxacin Sensor

A new highly sensitive and selective electrochemical levofloxacin sensor based on co‐polymer‐carbon nanotube composite electrode was developed. Taurine and Glutathione were electrochemically co‐polymerized on multiwalled carbon nanotubes modified glassy carbon electrode (Poly(TAU‐GSH)/CNT/GCE) and used as a levofloxacin sensor in pH 6 phosphate buffer solution. The new composite electrode surfaces were characterized by scanning electron microscopy, atomic force microscopy and electrochemical impedance spectroscopy. Under the optimized conditions, two linear segments were obtained for increasing LEV concentrations between 20 nmol L^?1‐1 μmol L^?1 and 1.5 μmol L^?1‐55 μmol L^?1 LEV with a detection limit of 9 nmol L^?1 using amperometry. Poly(TAU‐GSH)/CNT/GCE exhibited high sensitivity, selectivity with good stability. The new sensor was employed for real samples of LEV tablets and urine. Promising results were obtained with good accuracy which were also in accordance with LC‐MS/MS analysis.     

Ultralow Cost Electrochemical Sensor Made of Potato Starch and Carbon Black Nanoballs to Detect Tetracycline in Waters and Milk

Detection of traces from pharmaceutical drugs such as antibiotics in drinking water and foodstuff is essential for guaranteeing human health in some environments, and this has to be done with low cost technologies to be widely deployed in public services and industry. In this paper, we describe an ultralow cost (<US$ 0.005 per unit of sensing layer) electrochemical sensor to detect the antibiotic tetracycline, which is made of a homogeneous thin film of potato starch (PS) and carbon black (CB) deposited on glassy carbon electrodes (GCE). Detection of tetracycline was also performed in real samples consisting of tap water, river water, milk and in solutions prepared with commercial tablets of this medicine in the range between 5.0 and 120 μmol L⁻¹, with a detection and quantification limit of 1.15 and 4.47 μmol L⁻¹, respectively. The high sensitivity was attributed to the enhanced conductivity and larger surface area induced by incorporating the carbon black into potato starch. The CB‐PS/GCE electrodes were reproducible and stable, thus serving as a generic platform for detection of other antibiotics and hormones whose redox potentials are similar to those of tetracycline.     

Electrochemical Sensor Based on Casein and Carbon Black for Bisphenol A Detection

Bisphenol A (BPA) is an environmental endocrine disrupting chemical, which can lead to various adverse health effects. Aiming to develop effective tools for the detection of BPA, this work reports a low cost and stable film based on casein (CAS) and Carbon Black (CB). The proposed material (CAS‐CB) showed structures of CAS surrounded by CB agglomerates observed by Scanning Electron Microscopy while Fourier Transform Infrared Spectroscopy analysis illustrated characteristic bands of casein. Cyclic Voltammetry (CV) and linear sweep voltammetry (LSV) were used to investigate the electrochemical behavior of BPA using the CAS‐CB. Under optimal conditions, LSV detection presented a limit of detection of 0.25 μmol L^?1 in a linear range from 0.49 to 24 μmol L^?1. Additionally, the working electrode (GC) modified by the proposed film (CAS‐CB) was applied for BPA sensing in environmental and milk samples. The results showed recoveries between 95.4 to 114 % attesting the efficiency of this new material, which has simplicity in the preparation, high conductivity, and adsorption capability.     

A Sensitive Sensor Based on CuTSPc and Reduced Graphene Oxide for Simultaneous Determination of the BHA and TBHQ Antioxidants in Biodiesel Samples

A novel and sensitive electrochemical sensor was developed for the simultaneous determination of the butylated hydroxyanisole (BHA) and tert‐butylhydroquinone (TBHQ) antioxidants in biodiesel samples employing the differential pulse voltammetry (DPV). In this sense, a glassy carbon electrode (GCE) modified with copper (II) tetrasulfonated phthatocyanine immobilized on reduced graphene oxide (CuTSPc/rGO) allowed the detection of BHA and TBHQ at potentials lower than those observed at unmodified electrodes. The sensor was characterized by cyclic voltammetry (CV) and linear scan voltammetry (LSV). After optimization of the experimental parameters, the analytical curves for simultaneous determination of BHA and TBHQ by DPV technique demonstrated an excellent linear response from 0.1 to 500 µmol L^?1 with detection limit of 0.045 µmol L^?1 for TBHQ and 0.036 µmol L^?1 for BHA. Finally, the proposed method was successfully applied in the simultaneous determination of BHA and TBHQ in six biodiesel samples, and the results obtained were found to be similar to those obtained using the HPLC method with agreement at 95 % confidence level.     

Graphene Quantum Dots Modified Screen‐printed Electrodes as Electroanalytical Sensing Platform for Diethylstilbestrol

In present work a simple methodology for electroanalytical sensing of diethylstilbestrol (DES) using graphene quantum dots (GQD) surface modified screen‐printed electrodes (SPE) is reported. GQD was synthesized by simple bottom‐up method based on citric acid pyrolysis at 200 °C and electrodeposited directly at electrode surface under cyclic voltammetric conditions. The obtained GQD presented an average diameter of 7 nm and was characterized by techniques such as transmission and scanning electron microscopy, and electrochemical impedance spectroscopy. The proposed sensor exhibits a linear response from 0.05 to 7.5 μmol L^?1, with limit of detection and quantification of 8.8 nmol L^?1 and 29.0 nmol L^?1, respectively. The repeatability study presented RSD=3.6 % for 6 consecutive measurements using the same electrode surface and the reproducibility study showed RSD=6.6 % for measurements with 6 different electrode surfaces. The proposed sensor was successfully applied for DES determination in synthetic urine and tap water spiked samples and good recoveries were obtained without any sample pre‐treatment, showing its promising analytical performance.     

An Electrochemical Sensor Based on Reduced Graphene Oxide,Gold Nanoparticles and Molecular Imprinted Over‐oxidized Polypyrrole for Amoxicillin Determination

An electrochemical sensor for amoxicillin (AMX) detection based on reduced graphene oxide (RGO), molecular imprinted overoxidized polypyrrole (MIOPPy) modified with gold nanoparticles (AuNPs) is described in this work. The electrochemical behavior of the imprinted and non‐imprinted polymer (NIP) was carried out by cyclic voltammetry (CV) and impedance spectroscopy (IS). The structure and morphology of the prepared MIP sensor were characterized by scanning electron microscopy (SEM), UV‐Visible, Fourier transform infrared spectroscopy (FTIR) and its experimental parameters such as monomer and template concentration, pH buffer solution, incubation time of AMX and AuNPs, scan rate as well as electropolymerization scan cycles were optimized to improve the performance of the sensor. The peak current obtained at the MIP electrode was proportional to the AMX concentration in the range from 10^?8 to 10^?3 mol L^?1 with a detection limit and sensitivity of 1.22 10^?6 mol L^?1 (Signal to noise ratio=3) and 2.52×10^?6 μAmol^?1 L, respectively. It was also found that this sensor exhibited reproducibility and excellent selectivity against molecules with similar chemical structures. Besides, the analytical application of the AMX sensor confirms the feasibility of AMX detection in milk and human serum.     

Electroanalytical Determination of Carbaryl in Natural Waters on Boron Doped Diamond Electrode

The anodic voltammetric behavior of carbaryl on a boron‐doped diamond electrode in aqueous solution is reported. The results, obtained by square‐wave voltammetry at 0.1 mol L^?1 Na₂SO₄ and pH 6.0, allow the development of a method to determine carbaryl, without any previous step of extraction, clean‐up, preconcentration or derivatization, in the range 2.5–30.0×10^?6 mol L^?1, with a detection limit of 8.2±0.2 μg L^?1 in pure water. The analytical sensitivity of this electrochemical method diminished slightly, from 3.07 mA mmol^?1 L to 2.90 mA mmol^?1L, when the electrolyte was prepared with water samples collected from two polluted points in an urban creek. In these conditions, the recovery efficiencies obtained were around 104%. The effect of other pesticides (fenthion and 4‐nitrophenol) was evaluated and found to exert a negligible influence on carbaryl determination. The square‐wave voltammetric data obtained for carbaryl were typical of an irreversible electrode process with mass transport control. The combination of square‐wave voltammetry and diamond electrodes is an interesting and desirable alternative for analytical determinations.     

Batch‐injection versus Flow‐injection Analysis Using Screen‐printed Electrodes: Determination of Ciprofloxacin in Pharmaceutical Formulations

This article highlights the potential use of multi‐walled carbon‐nanotube modified screen‐printed electrodes (SPEs) for the amperometric sensing of ciprofloxacin and compares the association of batch‐injection analysis (BIA) and flow‐injection analysis (FIA) with amperometric detection. Both analytical systems provided precise (RSD<5 %) and sensitive determination of ciprofloxacin (LOD<0.1 μmol L^?1) within wide linear range (up to 200 μmol L^?1). Accuracy of both methods was attested by recovery values (93–107 %) and comparison with capillary electrophoresis. The BIA system is completely portable (especially due to association with SPEs) and provided faster analyses (130 h^?1) and more sensitive detection than the FIA system due to the higher flow rates of injection.     

A Novel Electrochemical Sensor Based on Silsesquioxane/Nickel (II) Phthalocyanine for the Determination of Sulfanilamide in Clinical and Drug Samples

This paper describes the immobilization of nickel (II) phthalocyanine‐tetrasulfonic acid tetrasodium salt (NiTsPc) in 3‐n‐propyl(3‐methylpyridinium) silsesquioxane chloride (Si3Pic⁺Cl^?). This hybrid material was synthetized and characterized by ²⁹Si NMR CP‐MAS, FTIR and DRS. The modified material, designated as Si3Pic⁺Cl^?/NiTsPc, was used to build carbon paste electrodes to determine sulfanilamide (SFL) by differential pulse voltammetry. The modified electrode showed a higher current response when compared to the bare carbon paste electrode. The evaluation of SFL was possible in the presence of salicylic acid, commonly used in solid ointment compositions in a high concentration. Theoretical calculations using density functional theory were done aiming to shed light at dimerization process at SFL. The oxidation peak increased with increasing concentrations of SFL in the range of 35–301 μmol L^?1. The LOD and LOQ values obtained were 12 and 35 μmol L^?1 of SFL, respectively. The novel electrochemical sensor was successfully applied for the determination of SFL in pet drug samples, urine and serum through the standard addition method. Validation was performed through a comparison with values obtained by the molecular absorption spectrometry method and there were no significant differences in the results, as confirmed by the statistical paired t‐test. This demonstrates the promise of a new approach for analytical application in clinical and drug samples of sulfonamide compounds.     

A Simple Approach to Simultaneous Electroanalytical Quantification of Acetaminophen and Tramadol Using a Boron‐doped Diamond Electrode in the Existence of Sodium Dodecyl Sulfate

The present work describes the individual, selective and simultaneous quantification of acetaminophen (ACP) and tramadol hydrochloride (TRA) using a modification‐free boron‐doped diamond (BDD) electrode. Cyclic voltammetric measurements revealed that the profile of the binary mixtures of ACP and TRA were manifested by two irreversible oxidation peaks at about +1.04 V (for ACP) and +1.61 V (for TRA) in Britton‐Robinson (BR) buffer pH 3.0. TRA oxidation peak was significantly improved in the presence of anionic surfactant, sodium dodecyl sulfate (SDS), while ACP signal did not change. By employing square‐wave stripping mode in BR buffer pH 3.0 containing 8×10^?4 mol L^?1 SDS after 30 s accumulation under open‐circuit voltage, the BDD electrode could be used for quantification of ACP and TRA simultaneously in the ranges 1.0–70 μg mL^?1 (6.6×10^?6–4.6×10^?4 mol L^?1) and 1.0–70 μg mL^?1 (3.3×10^?6–2.3×10^?4 mol L^?1), with detection limits of 0.11 μg mL^?1 (7.3×10^?7 mol L^?1) and 0.13 μg mL^?1 (4.3×10^?7 mol L^?1), respectively. The practical applicability of the proposed approach was tested for the individual and simultaneous quantification of ACP and/or TRA in the pharmaceutical dosage forms.     

Validated Voltammetric Method for the Simultaneous Determination of Anti‐diabetic Drugs,Linagliptin and Empagliflozin in Bulk,Pharmaceutical Dosage Forms and Biological Fluids

A cobalt oxide nanoparticles (Co₃O₄NPs) and multi walled carbon nanotubes (MWCNTs) modified carbon paste electrodes were used to study the electrochemical behavior of linagliptin and empagliflozin in Britton Robinson buffer solution of pH 8.0 using cyclic and square wave voltammetry. The above mentioned modified electrodes showed highly sensitive sensing and gave an excellent anodic response for both drugs. The peak current varied linearly over the concentration ranges: 3.98×10^?5–1.53×10^?3 mol L^?1 (18.82–723.00 μg/mL) and 7.94×10^?6–1.07×10^?4 mol L^?1 (3.65–48.25 μg/mL) with determination coefficients of 0.9999 and 0.9998 for linagliptin and empagliflozin, respectively. The recoveries and relative standard deviations were found in the following ranges: 98.80 %–102.00 % and 0.23 %–1.90 % for linagliptin and 98.30 %–101.80 % and 0.11 %–1.86 % for empagliflozin. The detection and quantification limits were 1.13×10^?5 and 3.76×10^?5 mol L^?1 (5.34and17.77 μg/mL) for linagliptin, 1.71×10^?6and 5.68×10^?6 mol L^?1 (0.77 and 2.56 μg/mL) for empagliflozin. The proposed sensors have been successfully applied for the determination of the drugs in bulk, pharmaceutical formulations and biological fluids.     

Direct Electrochemical Determination of Glyphosate at Copper Phthalocyanine/Multiwalled Carbon Nanotube Film Electrodes

A copper phthalocyanine/multiwalled carbon nanotube film‐modified glassy carbon electrode has been used for the determination of the herbicide glyphosate (Gly) at ?50 mV vs. SCE by electrochemical oxidation using differential pulse voltammetry (DPV). Cyclic voltammetry and electrochemical impedance spectroscopy showed that Gly is adsorbed on the metallic centre of the copper phthalocyanine molecule, with formation of Gly‐copper ion complexes. An analytical method was developed using DPV in pH 7.4 phosphate buffer solution, without any pretreatment steps: Gly was determined in the concentration range of 0.83–9.90 μmol L^?1, with detection limit 12.2 nmol L^?1 (2.02 μg L^?1).     

Electrochemical Sensing Platform Based on Nano‐Perovskite/Glycine/Carbon Composite for Amlodipine and Ascorbic Acid Drugs

People suffered from essential hypertension have increased oxidative stress. Thus, adding vitamin C to their medical therapy resulted in decreasing the oxidative stress and increasing the antioxidant status. This may prevent further vascular damage due to the oxidative stress, leading to a better diagnosis in critical hypertension patients. A novel sensor was fabricated based on NdFeO₃ nano‐perovskite/glycine/carbon nanotubes modified carbon paste electrode in presence of sodium dodecyl sulfate; GLNFCNTCP‐SDS for electrochemical sensing and simultaneous determination of antihypertensive and antioxidant drugs, Amlodipine (AML) and ascorbic acid. The developed nanocomposite showed interactive characteristics of all the modifiers as high conductivity, enhanced surface area, surface fouling resistance and stability. This leads to accelerated electron transfer rate and increased current response of electro‐oxidation of AML by 8.3 folds compared to unmodified electrode. The method validity was investigated successfully by the quantitative analysis of AML in human urine samples and Norvasc tablets with acceptable recovery results. The featured merits of the proposed composite in the analysis of AML in human urine samples were; wide concentration range of 0.003 μmol L^?1 to 200 μmol L^?1, sensitivity of 113.2 μA/μmol L^?1, detection limit of 0.704 nmol L^?1, and quantification limit of 2.35 nmol L^?1.