First Order Derivative Voltammetry on the in situ Surfactant Modified Electrode for Naringin Quantification

Carboxylated multi‐walled carbon nanotubes based glassy carbon electrodes (MWNT‐COOH/GCE) modified in situ with surfactants (sodium dodecyl sulfate (SDS), cetylpyridinium bromide (CPB) and Triton X100) have been tested for the naringin determination. The effect of surfactant nature and concentration on the voltammetric characteristics of naringin has been evaluated. Anionic 100 μM SDS shows the highest 2.7‐fold increase of the oxidation currents in comparison to MWNT‐COOH/GCE. The irreversible electrooxidation of naringin is surface‐controlled process with the one electron and one proton transfer. Under conditions of first order derivative linear sweep voltammetry in Britton‐Robinson buffer (BRB) pH 8.0, the analytical ranges of 0.75–25 and 25–100 μM with the LOD and LOQ of 0.14 and 0.46 μM, respectively, have been obtained. The electrode response is selective in the presence of ascorbic, gallic and p‐coumaric acids as well as quercetin, catechin and rutin. The method has been applied for the naringin quantification in grapefruit juices.     

Voltammetric Determination of Folic Acid Using Adsorption of Methylene Blue onto Electrodeposited of Reduced Graphene Oxide Film Modified Glassy Carbon Electrode

This work presents a sensitive voltammetric method for determination of folic acid by adsorbing methylene blue onto electrodeposited reduced graphene oxide film modified glassy carbon electrode (MB/ERGO/GCE) in 100 mM KCl‐10 mM sodium phosphate buffer solution (pH 7.40). The surface morphology of the MB/ERGO/GCE modified electrode was characterized using scanning electron microscopy, displays that both MB and ERGO distributed homogeneously on the surface of GCE. The MB/ERGO/GCE modified electrode shows more favorable electron transfer kinetics for potassium ferricyanide and potassium ferrocyanide probe molecules, which are important electroactive compounds, compared with bare GCE, MB/GCE, and ERGO/GCE. The electrochemical behaviors of folic acid at MB/ERGO/GCE were investigated by cyclic voltammetry, suggesting that the modified electrode exhibited excellent electrocatalytic activity towards folic acid compared with other electrodes. Under physiological condition, the MB/ERGO/GCE modified electrode showed a linear voltammetric response from 4.0 μM to 167 μM for folic acid, and with the detection limit of 0.5 μM (S/N=3). The stability, reproducibility and anti‐interference ability of the modified electrode were examined. The developed method has been successfully applied to determination of FA in tablets with a satisfactory recovery from 96 % to 100 %. The work demonstrated that the electroactive MB adsorbing onto graphene modified electrode showed an enhanced electron transfer property and a high resolution capacity to FA.     

Polyquercetin/MWNT‐modified Electrode for the Determination of Natural Phenolic Antioxidants

Novel highly sensitive voltammetric method for the gallic acid, catechin and epigallocatechin gallate (EGCG) quantification has been developed using glassy carbon electrode modified with multi‐walled carbon nanotubes and polyquercetin (polyquercetin/MWNT/GCE). The effect of electropolymerization parameters (number of cycles, monomer concentration and polarization window) on the electrode characteristics has been evaluated. The electrode surface has been characterized with SEM, CV and EIS. The linear dynamic ranges of 0.50–10 and 10–750 μM for gallic acid, 0.10–10 and 10.0–250 μM for catechin and 0.050–10 and 10–100 μM for EGCG have been obtained in differential pulse mode with the detection limits of 0.10, 0.024 and 0.014 μM, respectively. The approach has been successfully applied for the tea antioxidant capacity evaluation (AOC). The positive correlations with antioxidant activity towards DPPH^• and total phenolics (r =0.7845 and 0.7658 at r _crit=0.4227, n =22) have been obtained.     

Electrochemical Behavior and Voltammetric Determination of Curcumin at Electrochemically Reduced Graphene Oxide Modified Glassy Carbon Electrode

This work presents a sensitive voltammetric method for determination of curcumin by using a electrochemically reduced graphene oxide (ERGO) modified glass carbon electrode (GCE) in 100 mM KCl‐10 mM sodium phosphate buffer solution (pH 7.40). The electrochemical behaviors of curcumin at ERGO/GCE were investigated by cyclic voltammetry, suggesting that the ERGO/GCE exhibits excellent electrocatalytic activity towards curcumin, compared with bare GCE and GO/GCE electrodes. The electrochemical reaction mechanisms of curcumin, demethoxycurcumin and bisdemethoxycurcumin at the ERGO/GCE were also investigated and discussed systematically. Under physiological condition, the modified electrode showed linear voltammetric response from 0.2 μM to 60.0 μM for curcumin, with the detection limit of 0.1 μm. This work demonstrates that the graphene‐modified electrode is a promising strategy for electrochemical determination of biological important phenolic compounds.     

Construction of an electrochemical sensor based on the electrodeposition of Au-Pt nanoparticles mixtures on multi-walled carbon nanotubes film for voltammetric determination of cefotaxime

Mixtures of gold-platinum nanoparticles (Au-PtNPs) are fabricated consecutively on a multi-walled carbon nanotubes (MWNT) coated glassy carbon electrode (GCE) by the electrodeposition method. The surface morphology and nature of the hybrid film (Au-PtNPs/MWCNT) deposited on glassy carbon electrodes is characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) techniques. The modified electrode is used as a new and sensitive electrochemical sensor for the voltammetric determination of cefotaxime (CFX). The electrochemical behavior of CFX is investigated on the surface of the modified electrode using linear sweep voltammetry (LSV). The results of voltammetric studies exhibited a considerable improvement in the oxidation peak current of CFX compared to glassy carbon electrodes individually coated with MWCNT or Au-PtNPs. Under the optimized conditions, the modified electrode showed a wide linear dynamic range of 0.004-10.0 μM with a detection limit of 1.0 nM for the voltammetric determination of CFX. The modified electrode was successfully applied for the accurate determination of trace amounts of CFX in pharmaceutical and clinical preparations.     

Fabrication of Chitosan‐Multiwall Carbon Nanotube Nanocomposite Containing Ferri/Ferrocyanide: Application for Simultaneous Detection of D‐Penicillamine and Tryptophan

We report a simple and effective strategy for fabrication of the nanocomposite containing chitosan (CS) and multiwall carbon nanotube (MWNT) coated on a glassy carbon electrode (GCE). The characterization of the modified electrode (CS‐MWNT/GC) was carried out using scanning electron microscopy (SEM) and UV–vis absorption spectroscopy. The electrochemical behavior of CS‐MWNT/GC electrode was investigated and compared with the electrochemical behavior of chitosan modified GC (CS/GC), multiwalled carbon nanotube modified GC (MWNT/GC) and unmodified GC using cyclic voltammetry (CV) and electron impedance spectroscopy (EIS). The chitosan films are electrochemically inactive; similar background charging currents are observed at bare GC. The chitosan films are permeable to anionic Fe(CN)₆^3?/4? (FC) redox couple. Electrochemical parameters, including apparent diffusion coefficient for the Fe(CN)₆^3?/4? redox probe at FC/CS‐MWNT/GC electrode is comparable to values reported for cast chitosan films. This modified electrode also showed electrocatalytic effect for the simultaneous determination of D‐penicillamine (D‐PA) and tryptophan (Trp). The detection limit of 0.9 μM and 4.0 μM for D‐PA and Trp, respectively, makes this nanocomposite very suitable for determination of them with good sensitivity.     

Simultaneous electrochemical determination of norepinephrine,ascorbic acid and uric acid using a graphene modified glassy carbon electrode

This paper describes the simultaneous determination of ascorbic acid (AA), norepinephrine (NE) and uric acid (UA) using a graphene modified glassy carbon electrode (GME) in pH 4.0 phosphate buffer solution. The electrochemical behaviors of AA, NE and UA at a bare glassy carbon electrode (GCE) and the GME were studied by cyclic voltammetry. Bare GCE failed to resolve the voltammetric signals of AA, NE and UA in a mixture, whereas the GME not only resolved their voltammetric signals, but also exhibited excellent electrocatalytic activity towards their electrochemical oxidation. The oxidation peak currents of AA, NE and UA were linearly proportional to their concentrations over the range of 1.0.0–1000.0, 0.6–45.0 and 1.0–100.0 μM, respectively, and their detection limits were 1.2, 0.10 and 0.60 μM, respectively, The modified electrode is of excellent sensitivity and selectivity, and has been satisfactorily used for the simultaneous determination of AA, NE and UA in their ternary mixture.     

Electrochemical Behavior of 8‐Azaguanine at DNA Langmuir–Blodgett Modified Glassy Carbon Electrode and Its Analytical Application

A highly sensitive electrochemical biosensor for the detection of trace amounts of 8‐azaguanine has been designed. Double stranded (ds)DNA molecules are immobilized onto a glassy carbon electrode surface with Langmuir–Blodgett technique. The adsorptive voltammetric behaviors of 8‐azaguanine at DNA‐modified electrode were explored by means of cyclic voltammetry and square wave voltammetry. Compared with bare glassy carbon electrode (GCE), the Langmuir–Blodgett film modified electrode can greatly improve the measuring sensitivity of 8‐azaguanine. Under the optimum experimental conditions, the Langmuir–Blodgett film modified electrode in pH 3.0 Britton–Robinson buffer solutions shows a linear voltammetric response in the range of 5.0×10^?8 to 1.0×10^?5 mol L^?1 with detection limit 9.0×10^?9 mol L^?1. The method proposed was applied successfully for the determination of 8‐azaguanine in diluted human urine with wonderful satisfactory.     

Electrochemical Determination of Methotrexate at a Disposable Screen-Printed Electrode and Its Application Studies

Methotrexate is widely used for treatment of various neoplastic diseases. The present work details the voltammetric analysis of Methotrexate at a multi-walled carbon nanotube (MWNT) modified screen-printed electrode (SPE). The fabrication and evaluation of MWNT-derived screen-printed electrochemical sensors based on a MWNT ink are reported. The fabricated MWNT strips combine the attractive advantages of CNT materials and disposable screen printed electrodes. The anodic voltammetric behavior of methotrexate was studied using cyclic and square-wave voltammetric techniques in tris-HCl (pH = 7.5) solution. The oxidation of methotrexate was an irreversible adsorptive-driven process. The experimental conditions such as carbon ink, MWNT, pH, the concentration, and nature of buffer were investigated to optimize the determination of methotrexate. Under optimum conditions, the square-wave voltammetric peak currents were in a linear relationship to methotrexate concentrations in the range of 5.0 × 10^?7M–1.0 × 10^?4 M with a detection limit of 1.0 × 10^?7 M. The MWNT/SPE showed good stability, selectivity, and was successfully used to quantify methotrexate in pharmaceutical formulations.     

Enhanced Oxidation of Simvastatin at a Multi‐Walled Carbon Nanotubes‐Dihexadecyl Hydrogen Phosphate Composite Modified Glassy Carbon Electrode and the Application in Determining Simvastatin in Pharmaceutical Dosage Forms

A sensitive electrochemical method for the determination of simvastatin (SV) was established, based on the enhanced oxidation of SV at a multi‐walled carbon nanotubes‐dihexadecyl hydrogen phosphate composite modified glassy carbon electrode (MWNTs‐DHP/GCE). The voltammetric studies showed that MWNTs instead of DHP or GCE could effectively catalyze the oxidation of SV. The dependence of oxidation current on SV concentration was explored under optimal conditions, which exhibited a good linear relationship in the range of 1.0×10^?7–7.5×10^?6 M. The detection limit of SV was also examined and a low value of 5.0×10^?8 M was obtained for 5 min accumulation (σ=3). This electrode was applied to the detection of SV in drug forms and the results were in accordance with those obtained by UV spectroscopy.     

Voltammetric Determination of Neotame by Using Chitosan/Nickelnanoparticles/Multi Walled Carbon Nanotubes Biocomposite as a Modifier

A selective and simple biosensor was prepared by immobilizing chitosan/nickelnanoparticles/multi-walled carbon nanotubes biocomposite on the glassy carbon electrode surface for voltammetric quantification of neotame. The properties and morphology of the modified electrode surfaces were characterized by scanning electron microscope (SEM), energy dispersive X-ray analysis (EDX). Electro oxidation of neotame on this modified surface was examined through cyclic voltammetry (CV) and square wave voltammetry (SWV) techniques. The biocomposite modified surface (Chi/NiNPs/MWCNTs/GCE) proposed in this study showed good electrocatalytic activity for neotame with an improved voltammetric peak current at 1.004 V, unlike the bare glassy carbon electrode (GCE) surface and several other modified surfaces. Under optimum conditions, Chi/NiNPs/MWCNTs/GCE gave linear SWV responses at the range of 2 μM ∼50 μM for neotame with 0.84 μM determination limit. This voltammetric sensor was successfully employed for the quantification of neotame on food samples and showed long-term stability, advanced voltammetric behavior, and good repeatability. Selective, accurate, and precise determination of neotame highlight the importance of this electrode in monitoring the control of food additives and ensures attract a great deal of attention.     

Sensitive Voltammetric Determination of Baicalein at Thermally Reduced Graphene Oxide Modified Glassy Carbon Electrode

This work presents a sensitive voltammetric method for determination of the flavonoid baicalein by using a thermally reduced graphene oxide (TRGO) modified glassy carbon electrode (GCE) in 100 mM KCl‐10 mM sodium phosphate buffer solution (pH 7.40). The surface morphology and structure of TRGO investigated by atomic force microscopy, FT‐IR spectroscopy and Raman spectroscopy reveal that the TRGO prepared maintained as single or bilayer sheets and with significant edge‐plane‐like defect sites. The TRGO/GCE modified electrode shows more favorable electron transfer kinetics for potassium ferricyanide and potassium ferrocyanide probe molecules, which are important electroactive compounds, compared with bare GCE and GO/GCE electrodes. The electrochemical behaviors of baicalein at the TRGO/GCE were investigated by cyclic voltammetry, suggesting that the TRGO/GCE exhibits excellent electrocatalytic activity to baicalein. Under physiological conditions, the modified electrode showed linear voltammetric response from 10 nM to 10 µM for baicalein, with a detection limit of 6.0 nM. This work demonstrates that the graphene‐modified electrode is a promising tool for electrochemical determination of flavonoid drugs.     

A Sensitive Electrochemical Sensor for Voltammetric Determination of Ganciclovir Based on Au‐ZnS Nanocomposite

An electrode modified with ZnS and gold nanoparticles (Au‐ZnS NPs) is introduced for highly sensitive voltammetric determination of ganciclovir (GCV). Surface structure and topography of the modified electrode was studied by SEM, EDX and XRD techniques. Electrochemical oxidation of GCV was investigated by cyclic (CV) and square wave voltammetry (SWV) in Briton‐Robinson buffer solution (pH 1.5). The results showed that electrochemical oxidation of GCV at the Au‐ZnS modified glassy carbon electrode (GCE) is irreversible and exhibited diffusion controlled electrode process over the pH range from 1.0 to 6.0. The oxidation potential peak and pH relationship showed that electrons and protons were transferred simultaneously over the electrochemical oxidation process. Using the proposed sensor, the linear calibration curves were obtained in the ranges of 0.04–1.50 μM and 1.5–70.0 μM with detection limit of 0.01 μM GCV by SWV technique. The modified electrode was successfully applied as a sensitive, reproducible and repeatable sensor for determination of the trace amount of GCV in human serum, urine and cymevene vials. Reasonable results were obtained from comparing the measurements of the real samples by the new sensor to high performance liquid chromatography (HPLC) as a standard method.     

A Selective Simultaneous Determination of Levodopa and Serotonin Using a Glassy Carbon Electrode Modified with Multiwalled Carbon Nanotube/Chitosan Composite

A glassy carbon electrode (GCE) modified with carbon nanotube/chitosan (MWCNTs‐CHT/GCE) was used for the sensitive voltammetric determination of levodopa (Lev) and serotonin (Ser). The measurements were carried out using cyclic voltammetry (CV), differential pulse voltammetry (DPV) and chronoamperometry (CA). Under the optimum conditions the electrode provides a linear response versus Lev and Ser concentrations in the range of 2.0–220.0 µM and 0.5–130.0 µM, respectively, using DPV. The modified electrode was satisfactorily used for determination of Lev and Ser in human serum and urine with satisfactory results.     

Electropolymerized Eugenol‐MWNT‐Based Electrode for Voltammetric Evaluation of Wine Antioxidant Capacity

Eugenol electropolymerization conditions on multiwalled carbon nanotube based glassy carbon electrode (MWNT/GCE) have been found. The polyeugenol/MWNT/GCE shows reversible redox steps of o‐quinone fragment in acidic media. Natural phenolic antioxidants are oxidized on polyeugenol/MWNT/GCE at 0.52 V excluding resveratrol (0.62 V). Differential pulse voltammetry on polyeugenol/MWNT/GCE was applied for the evaluation of wine antioxidant capacity (AOC). The AOC was expressed in catechin equivalents per 1 L of wine. The linear dynamic range is 1.00–250 µM with LOD and LOQ of 0.21 and 0.71 µM of catechin, respectively. Positive correlations for AOC with antioxidant activity (r=0.9840) and total phenolics content (r=0.9944) were observed.     

Rapid and Sensitive Determination of Dinotefuran Residue Based on Electrochemical Enhancement of β‐cyclodextrin‐Graphene Composite

A rapid method for sensitive voltammetric determination of dinotefuran residue was reported. The proposed method was based on the electrocatalytic reduction of dinotefuran on β‐cyclodextrin‐graphene composite modified glassy carbon electrode (β‐CD‐rGO/GCE), giving rise to a higher reduction signal to dinotefuran relative to the bare (GCE) and graphene modified electrode (rGO/GCE). Moreover, a further signal enhancement was observed when the modified electrode incubated in solution at low temperature (0 °C) for a short time. The reduction mechanism and binding affinity were also discussed. The external standard calibration curve was obtained from linear sweep voltammetry in the range of 0.5 to 16.0 μM with a detection limit of 0.10 μM. In addition to optimization of pretreatment, this electrochemical method has been applied to the dinotefuran residue determination in millet samples with the detection limit of 0.01 mg kg^?1 and compared with an high performance liquid chromatography method. The proposed electrode and analysis methods were proven to be sensitive, accurate and rapid under the used conditions.     

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

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

Determination of Uric Acid and Norepinephrine by Chitosan‐Multiwall Carbon Nanotube Modified Electrode

A novel chemically modified electrode based on the chitosan‐multiwall carbon nanotube (MWNT) coated glassy carbon electrode (GCE) is described, which exhibited an attractive ability to determine uric acid (UA) and norepinephrine (NE) simultaneously. The responses of UA and NE merged into a large peak at a bare GCE, but yielded two well‐defined oxidation peaks at the chitosan‐MWNT modified GCE (MC/GCE). The experimental parameters were optimized, and a direct electrochemical method for the simultaneous determine for UA and NE is proposed. The MC/GCE showed good sensitivity, selectivity and stability.     

Voltammetric Determination of Xanthine with a Single‐Walled Carbon Nanotube‐Ionic Liquid Paste Modified Glassy Carbon Electrode

Single‐walled carbon nanotube (SWNT) and room temperature ionic liquid (i.e., 1‐butyl‐3‐methylimidazolium hexaflourophosphate, BMIMPF₆) were used to fabricate paste modified glassy electrode (GCE). It was found that the electrode showed sensitive voltammetric response to xanthine (Xt). The detection limit was 2.0×10^?9 M and the linear range was 5.0×10^?9 to 5.0×10^?6 M. The electrode also displayed good selectivity and repeatability. In the presence of uric acid (UA) and hypoxanthine (Hx) the response of Xt kept almost unchanged. Thus this electrode could find application in the determination of Xt in some real samples. The analytical performance of the BMIMPF₆‐SWNT/GCE was demonstrated for the determination of Xt in human serum and urine samples.     

单壁碳纳米管和室温离子液体胶修饰电极

短单壁碳纳米管(S-SWNTs)与疏水性室温离子液体(RTIL)1-丁基-3-甲基咪唑六氟磷酸盐(BMIMPF6)以质量比1:1研成胶, 修饰在玻碳电极(GCE)上制备S-SWNT&;RTIL/GCE. 以铁氰化钾、抗坏血酸(AA)和亚甲基蓝(MB)为电化学探针, 用伏安法表征. 结果表明, 该修饰电极具有优异的电催化性能和富集效应. 以B-R缓冲溶液为支持电解液, 单链鲱鱼精脱氧核糖核酸(ssDNA)在S-SWNT&;RTIL/GCE上具有灵敏的伏安响应, 于0.532和0.808 V处分别出现鸟嘌呤碱基和腺嘌呤碱基的氧化峰. 鸟嘌呤碱基和腺嘌呤碱基在S-SWNT&;RTIL/GCE上的电极反应标准速率常数k’s分别为1.84×10^-2和3.69×10^-2 s-1. 在最佳条件下, 应用微分脉冲伏安法检测, 鸟嘌呤碱基的氧化峰电流与ssDNA 的浓度在40 μg·L-1-5.0 mg·L-1 范围内呈现良好的线性关系, 检测限为5 μg·L-1 (S/N=3, 信噪比).