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.     

Selective Electrochemical Determination of Dopamine with Molecularly Imprinted Poly(Carbazole‐co‐Aniline) Electrode Decorated with Gold Nanoparticles

Dopamine (DA) is a significant neurotransmitter in the central nervous system, coexisting with uric acid (UA) and ascorbic acid (AA). UA and AA are easily oxidizable compounds having potentials close to that of DA for electrochemical analysis, resulting in overlapping voltammetric response. In this work, a novel molecularly imprinted (MI) electrochemical sensor was proposed for selective determination of DA (in the presence of up to 80‐fold excess of UA and AA), relying on gold nanoparticles (Au_nano)‐decorated glassy carbon (GC) electrode coated with poly(carbazole (Cz)‐co‐aniline (ANI)) copolymer film incorporating DA as template (DA imprinted‐GC/P(Cz‐co‐ANI)‐Au_nano electrode, DA‐MIP‐Au_nano electrode). The DA recognizing sensor electrode showed great electroactivity for analyte oxidation in 0.2 mol L^?1 pH 7 phosphate buffer. Square wave voltammetry (SWV) was performed within 10^?4–10^?5 mol L^?1 of DA, of which the oxidation peak potential was observed at 0.16 V. The limit of detection (LOD) and limit of quantification (LOQ) were 2.0×10^?6 and 6.7×10^?6 mol L^?1, respectively. Binary and ternary synthetic mixtures of DA‐UA, DA‐AA and DA‐UA‐AA yielded excellent recoveries for DA. Additionally, DA was quantitatively recovered from a real sample of bovine serum spiked with DA, and determined in concentrated dopamine injection solution. The developed SWV method was statistically validated against a literature potentiodynamic method using a caffeic acid modified‐GC electrode.     

Differential Pulse Voltammetric Determination of 2‐Methyl‐4,6‐Dinitrophenol using Bismuth Bulk Electrode

This work reports the application of bismuth bulk electrode (BiBE) for the determination of 2‐methyl‐4,6‐dinitrophenol (MDNP) by differential pulse voltammetry (DPV) in Britton‐Robinson buffer of pH 12.0 as an optimal medium. BiBE was prepared by transferring molten bismuth into a glass tube under constant stream of nitrogen. The linear concentration dependences were measured from 1 to 10 μmol ? L^?1 and from 10 to 100 μmol ? L^?1 by using optimum accumulation potential of ?0.7 V and optimum accumulation time 30 s. Under these conditions limit of determination and limit of quantification was 0.45 and 1.5 μmol ? L^?1, respectively. The developed method was successfully applied for the analysis of tap water as a model sample.     

MWCNTs/Ionic Liquid/Graphene Quantum Dots Nanocomposite Coated with Nickel‐Cobalt Bimetallic Catalyst as a Highly Selective Non‐enzymatic Sensor for Determination of Glucose

In this work, a glassy carbon electrode (GCE) was modified with multiwall carbon nanotubes/ionic liquid/graphene quantum dots (MWCNTs/IL/GQDs) nanocomposite. Then, the nanocomposite was decorated with nickel‐cobalt nanoparticles (Ni?Co NPs), and it was used as a non‐enzymatic glucose sensor. Field emission scanning electron microscopy, X‐ray diffraction spectroscopy, and energy dispersive spectroscopy were employed to prove the electrodeposition of the Ni?Co NPs on the surface of MWCNTs/IL/GQDs/GCE. Also, cyclic voltammetric and amperometric methods were utilized for the investigation of the electrochemical behaviour of the Ni?Co NPs/MWCNTs/IL/GQDs/GCE for glucose oxidation. The novel amperometric sensor displayed two linear ranges from 1.0 to 190.0 μmol L^?1 and 190.0 to 4910 μmol L^?1 with a low detection limit of 0.3 μmol L^?1 as well as fast response time (2 s) and high stability. Also, the sensor showed good selectivity for glucose determination in the presence of ascorbic acid, citric acid, dopamine, uric acid, fructose, and sucrose, as potential interference species. Finally, the performance of the proposed sensor was investigated for the glucose determination in real samples. Ni?Co NPs/MWCNTs/IL/GQDs/GCE showed good sensitivity and excellent selectivity.     

Differential Pulse Voltammetric Determination of Selenocystine Using Selenium‐gold Film Modified Electrode

Differential pulse voltammetric determination of selenocystine (SeC) using selenium‐gold film modified glassy carbon electrode ((Se‐Au)/GC) is presented. In 0.10 mol?L^?1 KNO₃ (pH 3.20) solution, SeC yields a sensitive reduction peak at ?740 mV on (Se‐Au)/GC electrode. The peak current has a linear relationship with the concentration of SeC in the range of 5.0×10^?8–7.0×10^?4 mol?L^?1, and a 3σ detection limit of SeC is 3.0×10^?8 mol?L^?1. The relative standard deviation of the reduction current at SeC concentration of 10^?6 mol?L^?1 is 3.88% (n=8) using the same electrode, and 4.19% when using three modified electrodes prepared at different times. The content of SeC in the selenium‐enriched yeast and selenium‐enriched tea is determined. The total selenium in ordinary or selenium‐enriched tea is determined by DAN fluorescence method. The results indicate that in selenium‐enriched yeast about 20% of total selenium is present as SeC and in selenium‐enriched tea SeC is the major form of selenoamino acids. The total selenium content in selenium‐enriched tea soup is 0.09 μgSe/g accounting by 7% compared with that in selenium‐enriched tea. Hence, only a little amount of selenium is utilized by drinking tea, and most selenium still stay in tealeaf. Uncertainty are 22.4% and 16.1% for determination of SeC in selenium‐enriched yeast and selenium‐enriched tea by differential pulse voltammetry (DPV) on (Se‐Au)/GC electrode, respectively.     

Electrochemical Determination of the Herbicide Bentazone Using a Carbon Nanotube β‐Cyclodextrin Modified Electrode

An electrochemical sensor has been developed for the determination of the herbicide bentazone, based on a GC electrode modified by a combination of multiwalled carbon nanotubes (MWCNT) with β‐cyclodextrin (β‐CD) incorporated in a polyaniline film. The results indicate that the β‐CD/MWCNT modified GC electrode exhibits efficient electrocatalytic oxidation of bentazone with high sensitivity and stability. A cyclic voltammetric method to determine bentazone in phosphate buffer solution at pH 6.0, was developed, without any previous extraction, clean‐up, or derivatization steps, in the range of 10–80 µmol L^?1, with a detection limit of 1.6 µmol L^?1 in water. The results were compared with those obtained by an established HPLC technique. No statistically significant differences being found between both methods.     

Fe3O4@SiO2‐PANI‐Au Nanocomposite Prepared for Electrochemical Determination of Quercetin in Food Samples and Biological Fluids

A new electrochemical sensor based on Fe₃O₄@SiO₂‐PANI‐Au nanocomposite was fabricated for modification of glassy carbon electrode (Fe₃O₄@SiO₂‐PANI‐Au GCE). The Fe₃O₄@SiO₂‐PANI‐Au nanocomposite was characterized by TEM, FESEM‐EDS‐Mapping, XRD, and TGA methods. The Fe₃O₄@SiO₂‐PANI‐Au GC electrode exhibited an acceptable sensitivity, fast electrochemical response, and good selectivity for determination of quercetin. Under optimal conditions, the linear range for quercetin concentrations using this sensor was 1.0×10^?8 to 1.5×10^?5 mol L^?1, and the limit of detection was 3.8×10^?9 mol L^?1. The results illustrated that the offered sensor could be a possible alternative for the measurement of quercetin in food samples and biological fluids.     

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.     

Immobilization of Enzymes on the Nano‐Au Film Modified Glassy Carbon Electrode for the Determination of Hydrogen Peroxide and Glucose

A new enzyme‐based amperometric biosensor for hydrogen peroxide was developed relying on the efficient immobilization of horseradish peroxidase (HRP) to a nano‐scaled particulate gold (nano‐Au) film modified glassy carbon electrode (GC). The nano‐Au film was obtained by a chitosan film which was first formed on the surface of GC. The high affinity of chitosan for nano‐Au associated with its amino groups resulted in the formation of nano‐Au film on the surface of GC. The film formed served as an intermediator to retain high efficient and stable immobilization of the enzyme. H₂O₂ was detected using hydroquinone as an electron mediator to transfer electrons between the electrode and HRP. The HRP immobilized on nano‐Au film maintained excellent electrocatalytical activity to the reduction of H₂O₂. The experimental parameters such as the operating potential of the working electrode, mediator concentration and pH of background electrolyte were optimized for best analytical performance of amperometry. The linear range of detection for H₂O₂ is from 6.1×10^?6 to 1.8×10^?3 mol L^?1 with a detection limit of 6.1 μmol L^?1 based on signal/noise=3. The proposed HRP enzyme sensor has the features of high sensitivity (0.25 Almol^?1cm^?2), fast response time (t_90%≤10 s) and a long‐term stability (>1 month). As an extension, glucose oxidase (GOD) was chemically bound to HRP‐modified electrode. A GOD/HRP bienzyme‐modified electrode formed in this way can be applied to the determination of glucose with satisfactory performance.     

Electrode Based on Nickel‐containing SBA‐15 for the Determination of Copper in Ethanol Biofuel

A sensor based in a graphite–polyurethane composite electrode modified with the mesoporous nanostructured silica with hexagonal array of pores called Santa Barbara Amorphous type material (SBA‐15) containing nickel was built. The presence of Ni, incorporated during the synthesis of SBA‐15, resulted in an increase in sensitivity when compared to the other electrodes based on the unmodified SBA‐15. A procedure was proposed for the determination of Cu²⁺ in ethanol biofuel by square wave stripping voltammetry with linear response in concentration levels of 1.0×10^?8 and 1.0×10^?7 mol L^?1, resulting in a limit of detection of 1.83×10^?10 mol L^?1 and precision (RSD) of 2.09 %.     

ABTS‐Multiwalled Carbon Nanotubes Nanocomposite/Bi Film Electrode for Sensitive Determination of Cd and Pb by Differential Pulse Stripping Voltammetry

A 2,2′‐azinobis (3‐ethylbenzothiazoline‐6‐sulfonate) diammonium salt (ABTS)‐multiwalled carbon nanotubes (MWCNTs) nanocomposite/Bi film modified glassy carbon (GC) electrode was constructed for the differential pulse stripping voltammetric determination of trace Pb²⁺ and Cd²⁺. This electrode was more sensitive than ABTS‐free Bi/GC and Bi/MWCNTs/GC electrodes. Linear responses were obtained in the range from 0.5 to 35 μg L^?1 for Cd²⁺ and 0.2 to 50 μg L^?1 Pb(II), with detection limits of 0.2 μg L^?1 for Cd²⁺ and 0.1 μg L^?1 for Pb²⁺, respectively. This sensor was applied to the simultaneous detection of Cd²⁺ and Pb²⁺ in water samples with satisfactory recovery.     

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.     

Electrochemical Sensor Based on Multi‐walled Carbon Nanotubes and Cobalt Phthalocyanine Composite for Pyridoxine Determination

In this work, an electrochemical sensor based on pyrolytic graphite electrode (PGE), cobalt phthalocyanine (CoPc) and multiwalled carbon nanotube (MWCNT) composite designed as PGE‐MWCNT/CoPc was developed and validated for pyridoxine (vitamin B6) determination employing Differential Pulse Voltammetry (DPV). The electrochemical behaviour of pyridoxine at the PGE‐MWCNT/CoPc has been evaluated and the charge transfer coefficient, α, and the charge transfer rate constant, κ, were calculated as 0.30 and 11.67±0.43 s^?1, respectively, which indicates that, although this system is irreversible, it is viable kinetically to be used as a sensor. The optimized experimental conditions were pH 5.5 in 0.30 mol L^?1 phosphate buffer. The linear range found was 10 to 400 μmol L^?1 of pyridoxine, with r=0.9987. The limits of detection and quantification were 0.50 and 1.67 μmol L^?1, respectively, showing the good sensitivity of the method. The method was successfully applied for the pyridoxine determination in real samples of pharmaceutical formulation with RSD% lower than 5 % indicating that it can be used for routine quality control pharmaceutical formulations containing pyridoxine. Furthermore, it has the advantages of a fast response, a low detection limit and low cost.     

Determination of Rutin in Green Tea Infusions Using Square‐Wave Voltammetry with a Rigid Carbon‐Polyurethane Composite Electrode

This paper presents a comparative study on the electrochemical behavior of the flavonoid rutin on a rigid carbon‐polyurethane composite electrode and on a glassy carbon electrode. The electrochemical oxidation reaction of rutin was found to be quasireversible and affected by adsorption on the electrode surface. A square‐wave voltammetric method was developed for determination of rutin in green tea infusion samples using the RCPE electrode and data treatment by a deconvolution procedure. The detection limit achieved in buffered solutions was 7.1×10^?9 mol L^?1 using the RCPE and 1.7×10^?8 mol L^?1 using the GC electrode the average reproducibility for five determinations being 3.5%.     

Molecularly Imprinted Electrochemical Sensor Based on Modified Reduced Graphene Oxide‐gold Nanoparticles‐polyaniline Nanocomposites Matrix for Dapsone Determination

This work was designed to develop an electrochemical sensor based on molecular imprinted polyaniline membranes onto reduced graphene oxide (RGO) and gold nanoparticles (AuNPs) modified glassy carbon (GC) electrode for dapsone (DDS) determination. The prepared RGO/AuNPs/PANI‐MIPs nanocomposite was characterized by Ultra‐Violet‐Visible (UV‐Vis), Fourier transform infrared spectroscopy (FT‐IR) and scanning electronic microscopy (SEM) images. The feature of the imprinted electrode was evaluated by cyclic voltammetry (CV), differential pulse voltammetry (DPV) and impedance spectroscopy (IS). Throughout this study several analytical parameters, such as incubation time, pH value, concentration of monomer/template molecules and electro‐polymerization cycles were investigated. Under the optimized conditions, the experimental results showed best analytical performances for DDS detection with a sensitivity of 0.188 Ω/mol L^?1, a linear range from 1.0×10^?7 M to 1.0×10^?3 M and a detection limit of 6.8×10^?7 M. The bioanalytical sensor was applied to the determination of dapsone in real samples with high selectivity and recovery.     

Voltammetric Sensor for Sodium Nitroprusside Determination in Biological Fluids Using Films of Poly‐L‐Lysine

Sodium nitroprusside (NP), a commercial vasodilator, can be pre‐concentrated on vitreous carbon electrode modified by films of 97.5%: 2.5% poly‐L ‐lysine (PLL): glutaraldehyde (GA). This coating gives acceptable anion exchange properties whilst giving the required improvement of adhesion to the glassy carbon electrode surface. Linear response range and detection limit on nitroprusside in B‐R buffer pH 4.0, were 1×10^?6 to 2×10^?5 mol L^?1 and 1×10^?7 mol L^?1, respectively. The repeatability of the proposed sensor, evaluated in term of relative standard deviation, was measured as 4.1% for 10 experiments. The voltammetric sensor was directly applied to determination of nitroprusside in human plasma and urine samples and the average recovery for these samples was around 95–97% without any pre treatment.     

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.     

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.     

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.     

A Novel Sensor Based on Manganese azo‐Macrocycle/Carbon Nanotubes to Perform the Oxidation and Reduction Processes of Two Diphenol Isomers

The present work describes the development of a selective and sensitive voltammetric sensor for simultaneous determination of catechol (CC) and hydroquinone (HQ), based on a glassy carbon (GC) electrode modified with manganese phthalocyanine azo‐macrocycle (MnPc) adsorbed on multiwalled carbon nanotubes (MWCNT). Scanning electron microscopy and scanning electrochemical microscopy were used to characterize the composite material (MnPc/MWCNT) on the glassy carbon electrode surface. The modified electrode showed excellent electrochemical activity towards the simultaneous oxidation and reduction of CC and HQ. On the MnPc/MWCNT/GC electrode, both CC and HQ can generate a pair of quasi‐reversible and well‐defined redox peaks. Under optimized experimental and operational conditions, the cathodic peak currents were linear over the range 1–600 µmol L^?1 for both CC and HQ, with limits of detection of 0.095 and 0.041 µmol L^?1, respectively. The anodic peak currents were also linear over the range 1–600 µmol L^?1 for both CC and HQ, with limits of detection of 0.096 and 0.048 µmol L^?1, respectively. The proposed method was effectively applied for the simultaneous detection of hydroquinone and catechol in water samples and the results were in agreement with those obtained by a comparative method described in the literature.