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.     

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).     

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.     

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.     

Simultaneous Voltammetric Detection of Salsolinol and Uric Acid in the Presence of High Concentration of Ascorbic Acid with Gold Nanoparticles/Functionalized Multiwalled Carbon Nanotubes Composite Film Modified Electrode

This work demonstrates gold nanoparticles (AuNPs)/functionalized multiwalled carbon nanotubes (f‐MWCNT) composite film modified gold electrode via covalent‐bonding interaction self‐assembly technique for simultaneous determination of salsolinol (Sal) and uric Acid (UA) in the presence of high concentration of ascorbic acid (AA). In pH 7.0 PBS, the composite film modified electrode exhibits excellent voltammetric response for Sal and UA, while AA shows no voltammetric response. The oxidation peak current is linearly increased with concentrations of Sal from 0.24–11.76 μmol L^?1 and of UA from 3.36–96.36 μmol L^?1, respectively. The detection limits of Sal and UA is 3.2×10^?8 mol L^?1 and 1.7×10^?7 mol L^?1 , respectively.     

Voltammetric Detection of Ethinylestradiol in Water and Synthetic Urine Samples using a Ni(II) Phthalocyanine/Iron Oxide Nanocomposite Electrode

A novel nickel phthalocyanine/iron oxide nanoparticle (NiTsPc/ION) nanocomposite electrode is proposed for the voltammetric detection of ethinyl estradiol. The method shows a wide linear range (0.07–30 μmol L⁻¹, R² >0.99), sensitivity of 0.308 μA cm⁻²/μmol L⁻¹ and limit of detection of 7.8 nmol L⁻¹ (3.3 Sb/b). Recoveries are above 95 % for quantification in tap and treatment plant water samples and synthetic urine. A single electrode can be used in seven consecutive runs (RSD=2.85 %) and responses of different electrodes vary only 7–9 %. The excellent sensing performance of the proposed sensor is ascribed to its porous morphology and efficient charge-transfer between ION and NiTsPc.     

A Novel Strategy for Quantifying Clopidogrel Using Square‐wave Voltammetry and a Boron‐doped Diamond Film

The voltammetric behavior of clopidogrel bisulfate (CLO), an antiplatelet agent, was investigated for the first time in the literature on a cathodically pretreated boron‐doped diamond electrode (CP‐BDDE) using cyclic (CV) and square‐wave voltammetry (SWV). It was observed an anodic peak for CLO, suitable for analytical purposes, at about 1.15 V (vs. Ag/AgCl (3.0 mol L^?1 KCl)) by CV in Britton‐Robinson buffer solution (pH 5.0). On the physical‐chemical characterization of the interface phenomena, it was proved that electrode reaction of the analyte was controlled by a diffusion process. At optimized square‐wave parameters (pulse amplitude of 60 mV, frequency of 30 Hz and scan increment of 3 mV), the obtained analytical curve was linear for the CLO concentration range from 0.60 to 60.0 μmol L^?1, with a detection limit of 0.60 μmol L^?1. The simple, rapid and greener analytical method, based on CP‐BDDE electrochemical sensor, was successfully applied in real samples (pharmaceuticals and urine).     

Resolution of a Mononitrophenol Isomers Mixture by Differential Alternative Pulses Voltammetry

The high resolution second order voltammetric technique, Differential Alternative Pulse Voltammetry (DAPV), was applied for the simultaneous quantification of the mononitrophenol (NP) isomers. Complete resolution of the three isomers was achieved at concentration ratios as high as 1 : 5, employing the corresponding anodic and cathodic peaks appeared on the DAPV curve. The working glassy carbon electrode was modified by a nanocomposite of graphite nanopowder and Au nanoparticles to increase the sensitivity. The linear concentration range was found to be extended up to 125 μmol L^?1 for both the m‐NP and p‐NP isomers, while the o‐NP isomer presented calibration plot of two linear sections: up to 100 μmol L^?1 and up to 225 μmol L^?1. The LOD was found to be as low as 1.5 μmol L^?1, 2.5 μmol L^?1, and 0.5 μmol L^?1 for o‐NP, m‐NP, and p‐NP, respectively. The accuracy of the proposed method was evaluated by quantification of spiked tap waters samples. No interference was observed from a range of phenolic compounds such as phenol, 4‐aminophenol, 4‐chlorophenol, 2,4‐dinitrophenol, and resorcinol.     

Differential Pulse Voltammetric Determination of Selenocystine and Selenomethionine Using SAM nanoSe0/Vc/SeCys‐Film Modified Au Electrode

The SAM nanoSe⁰/Vc/SeCys‐film modified Au electrode has been prepared to determine selenocystine and selenomethionine. The AFM and SEM showed the special three‐dimensional (3D) network structure of the sol‐gel films. The affinity between nanoparticles and biomolecules created special chemical characters analyzed by the XRD and fluorescence. The modified electrode was characterized by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The modified films partly had resistance in the charge transduction of Fe(CN) , but the less electron‐transfer resistance. Differential pulse voltammetric (DPV) determination of selenoamino acids using SAM nanoSe⁰/Vc/SeCys‐film modified Au electrode was presented. In PBS (pH 7.0)+0.1 mol L^?1 NaClO₄ solution, selenoamino acids yielded a sensitive reduction peak at about +400±50 mV. The peak current had a linear relationship with the concentration of selenoamino acids in the range of 5.0×10^?8–1.0×10^?5 mol L^?1, and a 3σ detection limit of selenoamino acids was 1.2×10^?8 mol L^?1. The relative standard deviation of DPV signals of 0.50×10^?6 mol L^?1 selenoamino acids was 3.8% (n=8) using the same electrode and was 4.4% (n=5) when using three modified electrodes prepared at different times. The content of selenoamino acids in the organo‐selenium powder were determined by DPV. The results showed 71.5 μg g^?1 of SeCys and 65.1 μg g^?1 of SeMet in the organo‐selenium powder.     

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.     

Electroanalysis of the Anthelmintic Drug Bithionol at Edge Plane Pyrolytic Graphite Electrode

An electrochemical study of the anthelmintic drug bithionol using edge plane pyrolytic graphite electrode (EPPGE) is presented for the first time by applying different electrochemical techniques, such as cyclic voltammetry (CV), square‐wave voltammetry (SWV), square‐wave adsorptive stripping voltammetry (SWAdSV), and alternating current (AC) impedance spectroscopy. Mechanistic aspects of the electrode reaction were studied implying a quasireversible electrode reaction from an adsorbed state of the reactant, coupled with a follow‐up chemical reaction to a final electroinactive product. The overall mechanism appears totally irreversible under conditions of CV at moderate scan rate, while being quasireversible under conditions of the fast SWV. Furthermore, an optimisation of the analytical procedure for quantitative determination of bithionol was conducted by applying SWV in an adsorptive stripping mode. The calibration curve was constructed in the concentration range of 0.1–1.0 μmol L^?1 (R²=0.9984) with a sensitivity of 3.6 μA L μmol^?1 and LOD of 26.7 nmol L^?1. The simple and sensitive SWAdSV procedure was proved to be suitable for the analysis of spiked urine samples.     

Development of an Amperometric Biosensor for β‐N‐Oxalyl‐L‐α,β‐Diaminopropionic Acid (β‐ODAP)

An amperometric method for the determination of the neurotoxic amino acid β‐N‐oxalyl‐L ‐α,β‐diaminopropionic acid (β‐ODAP) using a screen printed carbon electrode (SPCE) is reported. The electrode material was bulk‐modified with manganese dioxide and used as a detector in flow injection analysis (FIA). The enzyme glutamate oxidase (GlOx) was immobilized in a Nafion‐film on the electrode surface. The performance of the biosensor was optimized using glutamate as an analyte. Optimum parameters were found as: operational potential 440 mV (vs. Ag/AgCl), flow rate 0.2 mL min^?1, and carrier composition 0.1 mol L^?1 phosphate buffer (pH 7.75). The same conditions were used for the determination of β‐ODAP. The signal was linear within the concentration range 53–855 μmol L^?1 glutamate and 195–1950 μmol L^?1 β‐ODAP. Detection limits (as 3σ value) for both analytes were 9.12 and 111.0 μmol L^?1, respectively, with corresponding relative standard deviations of 3.3 and 4.5%. The biosensor retained more than 73% of its activity after 40 days of on‐line use.     

Study on Electrochemiluminesce of Ru(bpy3)2+ Immobilized in a Titania Sol‐Gel Membrane

The immobilization of tris(2,2′‐bipyridyl)ruthenium(II), Ru(bpy)₃²⁺, at a glassy carbon electrode was achieved by entrapping the Ru(bpy)₃²⁺ in a vapor deposited titania sol‐gel membrane. The electrogenerated chemiluminescence (ECL) of the immobilized Ru(bpy)₃²⁺ was studied. The Ru(bpy)₃²⁺ modified electrode showed a fast ECL response to both oxalate and proline. The ECL intensity was linearly related to concentrations of oxalate and proline over the ranges from 20 to 700 μmol L^?1 and 20 to 600 μmol L^?1, respectively. The detection limits for oxalate and proline at 3σ were 5.0 μmol L^?1 and 4.0 μmol L^?1, respectively. This electrode possessed good precision and stability for oxalate and proline determinations. The electrogenerated chemiluminescence mechanism of proline system was discussed. This work provided a new way for the immobilization of Ru(bpy)₃²⁺ and the application of titania sol‐gel membrane in electrogenerated chemiluminescence.     

Determination of three Tumor Biomarkers (Homovanillic Acid,Vanillylmandelic Acid,and 5‐Hydroxyindole‐3‐Acetic Acid) Using Flow Injection Analysis with Amperometric Detection

Flow injection analysis with amperometric detection (FIA‐AD) at screen‐printed carbon electrodes (SPCEs) in optimum medium of Britton‐Robinson buffer (0.04 mol ? L^?1, pH 2.0) was used for the determination of three tumor biomarkers (homovanillic acid (HVA), vanillylmandelic acid (VMA), and 5‐hydroxyindole‐3‐acetic acid (5‐HIAA)). Dependences of the peak current on the concentration of biomarkers were linear in the whole tested concentration range from 0.05 to 100 μmol ? L^?1, with limits of detection (LODs) of 0.065 μmol ? L^?1 for HVA, 0.053 μmol ? L^?1 for VMA, and 0.033 μmol ? L^?1 for 5‐HIAA (calculated from peak heights), and 0.024 μmol ? L^?1 for HVA, 0.020 μmol ? L^?1 for VMA, and 0.012 μmol ? L^?1 for 5‐HIAA (calculated from peak areas), respectively.     

Simultaneous Determination of Rosmarinic Acid and Protocatechuic Acid at Poly(o‐Phenylenediamine)/Pt Nanoparticles Modified Glassy Carbon Electrode

A system of Pt nanoparticles and poly(ortho‐phenylenediamine) film electrochemically deposited onto a glassy carbon electrode (GCE/PoPD/Pt) was fabricated. Scanning electron microscopy, Fourier‐transform infrared spectroscopy, and atomic force microscopy techniques were used to identify the surface characteristics of the composite electrode. The conductive polymers and Pt nanoparticles together resulted in a synergistic effect, and the new formed surface was highly active against polyphenolic structures. Rosmarinic acid (RA) and protocatechuic acid (PCA) are phenolic compounds found in plants, and they are used in many applications, particularly as pharmaceuticals. The GCE/PoPD/Pt was used for the simultaneous determination of RA and PCA in a pH 2.0 H₂SO₄ solution for the first time. The RA and PCA concentrations were determined using differential pulse voltammetry (DPV) and chronoamperometry. By the amperometry measurement, for RA and PCA, a linear relation was observed in the concentration ranges of 1–55 μmol L^?1 and 1–60 μmol L^?1, with detection limits of 0.5 μmol L^?1 and 0.6 μmol L^?1, respectively. In the simultaneous determination with DPV, the detection limits for both RA and PCA were calculated as 0.7 μmol L^?1. The GCE/PoPD/Pt was successfully used for the simultaneous determination of RA and PCA in a real sample, and its accuracy was verified by high‐performance liquid chromatography studies.     

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.     

Modified Carbon Paste Electrode for Kinetic Investigation and Simultaneous Determination of Ascorbic and Uric Acids

The present work explores, for the first time, the electrocatalytic oxidation of ascorbic acid (AscH₂) and its determination in the presence of uric acid (UA) on the in situ activated 4‐nitrophthalonitrile modified carbon paste electrode. The kinetic constant κ for the catalytic reaction for the electrocatalytic oxidation of ascorbic acid, evaluated by cyclic voltammetry, chronoamperometry and RDE voltammetry provided values around 10⁶ L mol^?1 s^?1. The sensor provided a linear response range for AscH₂ and UA from 5.0 up to 120.0 μmol L^?1 with detection limits of 1.6 μmol L^?1and 1.3 μmol L^?1, respectively. The sensor was applied for the simultaneous determination of AscH₂ and UA in urine samples and the average recoveries for these samples were 99.8 (±3.1)% and 99.9 (±2.1)%, respectively .     

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.     

Voltammetric Behavior of Testosterone on Bismuth Film Electrode: Highly Sensitive Determination in Pharmaceuticals and Human Urine by Square‐Wave Adsorptive Stripping Voltammetry

In this paper, an electrochemical application of bismuth‐film electrode (BiFE) fabricated via ex‐situ electrodeposition onto a glassy carbon electrode for testosterone determination was investigated in aqueous and aqueous/surfactant solutions. In cyclic voltammetry, the compound showed one irreversible and adsorption‐controlled reduction peak. The BiFE revealed good linear response in the examined concentration range of 1 to 45 nmol L^?1 testosterone in Britton? Robinson buffer, pH 5.0 containing 3 mmol L^?1 cetyltrimethylammonium bromide. The limit of detection was 0.3 nmol L^?1 (0.09 ng mL^?1). Finally, the BiFE was satisfactorily applied for quantitation of testosterone in both pharmaceutical (oil‐based ampoule) and biological (human urine) 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.