A New Amperometric Carbon Paste Enzyme Electrode for Ethanol Determination

Abstract

In this study, a new amperometric carbon paste enzyme electrode for determination of ethanol was developed. The carbon paste was prepared by mixing alcohol dehydrogenase, its coenzyme nicotinamide adenine dinucleotide (oxidized form, NAD⁺), poly(vinylferrocene) (PVF) that was used as a mediator, graphite powder and paraffin oil, then the paste was placed into cavity of a glass electrode body. Determination of ethanol was performed by oxidation of nicotinamide adenine dinucleotide (reduced form, NADH) generated enzymatically at +0.7 V. The effects of enzyme, coenzyme and PVF amounts; pH; buffer concentration and temperature were investigated. The linear working range of the enzyme electrode was 4.0×10^?4–4.5×10^?3 M, determination limit was 3.9×10^?4 M and response time was 50 s. The optimum pH, buffer concentration, temperature, and amounts of enzyme, NAD⁺ and PVF for enzyme electrode were found to be 8.5, 0.10 M, 37°C, 2.0, 6.0, and 12.0 mg, respectively. The storage stability of enzyme electrode at +4°C was 7 days. Enzyme electrode was used for determination of ethanol in two different wine samples and results were in good agreement with those obtained by gas chromatography.     

碱性介质中异丙醇在铂电极表面的吸附和电化学氧化

运用电化学循环伏安、原位FTIR反射光谱和石英晶体微天平(EQCM)等方法研究了碱性介质中异丙醇在Pt电极表面吸附和氧化行为. 结果表明：碱性介质中异丙醇电氧化过程不存在自毒化现象. 虽然电化学原位FTIR反射光谱未能检测到CO等毒性物种, 但EQCM结果证明异丙醇或其解离产物吸附于铂电极上. 在实验条件下, 碱性介质中异丙醇在铂电极上氧化的最终产物只有丙酮, 预示着碱性介质中异丙醇通过脱氢步骤氧化成丙酮. EQCM研究还从电极表面质量定量变化的角度提供了异丙醇吸附和电氧化反应机理的新数据.     

Methylthiouracil‐modified Carbon Paste Electrode as a New Voltammetric Sensor Based on a 1,4‐Michael Addition Reaction for Detection of Dopamine

A sensitive dopamine sensor was constructed based on the modified carbon paste electrode with methylthiouracil as a nucleophile in the 1,4‐Michael addition reaction. An ECE mechanism was suggested for dopamine oxidation at the modified electrode. Design of experiments was used in the optimization of variables. Under the optimum conditions, calibration graph was linear in the range of 0.20–15.0 µM with a detection limit of 73 nM. The relative standard deviations (n=5) for 0.50 µM of dopamine was 3.83 %. The selectivity of the sensor was also studied. The developed sensor was applied for analysis of pharmaceutical and biological samples.     

TiO2‐modified Carbon Paste Electrode as a Sensor for the Assay of Weak Organic Acids/Bases and Complex Matrix Samples

The construction, general performance characteristics and analytical application of a titanium dioxide–modified carbon paste electrode sensitive to hydrogen ions, based on incorporation of titanium dioxide in a carbon paste matrix, is described. The proposed electrochemical sensor exhibits a linear response in the pH range from 2 to 10, at 25 °C, with a sub‐Nernstian slope. The value of a slope is in a direct correlation with the electrode composition – the optimum content of a titanium dioxide in carbon paste is 30 %. Titanium dioxide‐modified carbon paste electrode shows fast response time and reproducibility, confirmed by different compounds determination in both, individual and complex material, namely, in synthetic and real samples. Besides, the electrode shows high selectivity in the presence of the alkali and the alkaline earth ions as Na⁺, K⁺, Ca²⁺ or Mg²⁺. The standard deviation of the investigated acids (acetic, oxalic, 5‐sulfosalicylic, p‐toluensulfonic acid, and amino acid‐glycine) and bases (N,N′‐diphenylguanidine and collidine) is less than 1.3 %. The obtained data are compared with those obtained by using a conventional glass pH‐electrode under the same experimental conditions and indicate a high correlation between them.     

Enhanced Electrocatalytic Activity of Methanol and Ethanol Oxidation in Alkaline Medium at Bimetallic Nanoparticles Electrochemically Decorated Fullerene-C60 Nanocomposite Electrocatalyst: An Efficient Anode Material for Alcohol Fuel Cell Applications

Direct alcohol fuel cells (DAFCs) have been recently playing a pivotal role in electrochemical energy sources and portable electronics. Research in DAFCs has proceeded to engage major attention due to their high catalytic activity, long-term stability, portability, and low cost. Herein, we present a facile surfactant-free route to anchor bimetallic Pd−W nanoparticles supported fullerene-C₆₀ catalyst (Pd-W@Fullerene-C₆₀) for high-performance electrooxidation of alcohols (methanol & ethanol) for DAFCs applications. Structural, elemental composition, and morphological analysis of the proposed catalyst were carried out using UV-Vis spectroscopy, X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and energy-dispersive x-ray spectroscopy (EDX). Electrochemical properties such as electrochemical activity, electrochemical active surface area (ECSA), and long-term stability of the Pd-W@Fullerene-C₆₀ catalyst for ethanol and methanol oxidation in the alkaline medium were explored by using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and chronoamperometry (CA). Results revealed that the proposed catalyst showed enlarged ECSA, tremendous electrocatalytic activity, high poison tolerance limit, good reproducibility, and enhanced long-term stability as compared to the monometallic catalyst and commercially available catalyst (Pt/C) towards ethanol and methanol oxidation reaction. This enhanced potentiality of the Pd-W@Fullerene-C₆₀ catalyst is due to the synergistic effect of W−Pd nanoparticles and excellent electron kinetic from fullerene support material. These findings strongly suggest the Pd-W@Fullerene-C₆₀ catalyst as potential anode material for the alcohol oxidation reaction.     

Electrochemical Oxidation and Determination of Theophylline at a Carbon Paste Electrode Using Cetyltrimethyl Ammonium Bromide as Enhancing Agent

Abstract

The oxidation of theophylline was studied at a carbon paste electrode in the presence of cetyltrimethyl ammonium bromide by cyclic and differential pulse voltammetry. The results indicated that the electrochemical responses of theophylline are apparently improved by cetyltrimethyl ammonium bromide, due to the enhanced accumulation of theophylline at carbon paste electrode surface. Under optimal conditions the peak current was proportional to theophylline concentration in the range of 8.0 × 10^?7 to 2.0 × 10^?4 M with a detection limit of 1.85 × 10^?7 M by differential pulse voltammetry. The proposed method was applied to the determination of theophylline in tablet and urine samples.     

Preparation,Characterization and Electrochemical Application of ZnS/ZnAl2S4 Nanocomposite for Voltammetric Determination of Methionine and Tryptophan Using Modified Carbon Paste Electrode

ZnS/ZnAl₂S₄ nanocomposite and 2‐chlorobenzoyl ferrocene, were synthesized and used to construct a modified carbon paste electrode. The electrooxidation of methionine at the surface of the modified electrode was studied. Under the optimized conditions, the square wave voltammetric (SWV) peak current of methionine increased linearly with methionine concentration in the range of 5.0×10^?8 to 8.0×10^?4 M and detection limit of 10.0 nM was obtained for methionine. The prepared modified electrode exhibits a very good resolution between the voltammetric peaks of methionine and tryptophan which makes it suitable for the detection of methionine in the presence of tryptophan in real samples.     

方波伏安法测定新型修饰多壁碳纳米管糊电极对肼的电催化氧化(英文)

The application of p-aminophenol as a suitable mediator, as a sensitive and selective voltammetric sensor for the determination of hydrazine using square wave voltammetric method were described. The modified multiwall carbon nanotubes paste electrode exhibited a good electrocatalytic activity for the oxidation of hydrazine at pH = 7.0. The catalytic oxidation peak currents showed a linear dependence of the peaks current to the hydrazine concentrations in the range of 0.5–175 μmol/L with a correlation coefficient of 0.9975. The detection limit (S/N = 3) was estimated to be 0.3 μmol/L of hydrazine. The relative standard deviations for 0.7 and 5.0 μmol/L hydrazine were 1.7 and 1.1%, respectively. The modified electrode showed good sensitivity and selectivity. The diffusion coefficient (D = 9.5 × 10–4 cm2/s) and the kinetic parameters such as the electron transfer coefficient (α = 0.7) of hydrazine at the surface of the modified electrode were determined using electrochemical approaches. The electrode was successfully applied for the determination of hydrazine in real samples with satisfactory results.     

Application of Carbon Paste Electrode Modified with Carbon Nanofibres/Polyaniline/Platinum Nanoparticles as an Electrochemical Sensor for the Determination of Bezafibrate

The present study deals with the development of an electrochemical sensor for quantitative determination of Bezafibrate (BZF) based on carbon nanofibers/polyaniline/platinum nanoparticles modified carbon paste electrode (CNF/PANI/Pt/CPE). BZF is a fibric acid derivative and is used largely in the treatment of lipid disorders. The nanocomposite was synthesized by in situ polymerization of aniline using ammonium persulphate and platinum nanoparticles were uniformly decorated on the CNF/PANI surface by reducing hexachloroplatinic acid using sodium borohydride. The electrochemical response of BZF at CNF/PANI/Pt/CPE was studied using cyclic voltammetry (CV), differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS). The above study resulted into significant improvement of the electrochemical signal towards the oxidation of BZF, revealing that the oxidation process is highly favorable at the surface of modified electrode. The anodic peak current I_p (μA) is found to be linearly dependent on BZF concentration in the range of 0.025 μM to 100 μM with a detection limit of 2.46 nM. The practical analytical utilities of the sensor were investigated by performing the experiments on synthetic pharmaceutical formulations, human blood serum and urine samples which offered good recovery, suggesting the high efficacy and authenticity of CNF/PANI/Pt/CPE sensor for BZF determination.     

Graphene Paste Electrode: Analytical Applications for the Quantification of Dopamine,Phenolic Compounds and Ethanol

This work reports the analytical applications of a graphene paste electrode (GrPE) for the quantification of dopamine, ethanol and phenolic compounds. Dopamine was detected by differential pulse voltammetry‐adsorptive stripping with medium exchange at submicromolar levels even in the presence of high excess of ascorbic acid and serotonin. The electrocatalytic activity of graphene towards the oxidation of NADH and the reduction of quinones allowed the sensitive amperometric determination of ethanol and phenols using GrPE modified with alcohol dehydrogenase/NAD⁺ or polyphenol oxidase, respectively, with successful applications in real samples like alcoholic beverages and tea.     

基于表面活性剂单分子层修饰碳糊电极的一氧化氮电化学传感器及其应用

报道了一种表面活性剂单分子层修饰碳糊电极,并用于NO的高灵敏电化学检测。研究表明,表面活性剂通过烷基链在电极表面形成的疏水性单分子层微环境对NO的电化学响应具有较好的促进作用。其中,阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)对NO的电化学氧化表现出最强的催化活性和增敏作用。在Nafion膜覆盖的CTAB修饰碳糊电极上,NO的安培响应与其浓度在3.6×10-8～1.8×10-5mol/L范围内呈良好的线性关系,检出限为1.8×10-8mol/L。该电极作为低成本、高灵敏的NO电化学传感器,被成功应用于大鼠肺组织细胞中NO释放的实时监测。     

Simultaneous Determination of Dopamine and Uric Acid by Electrocatalytic Oxidation on a Carbon Paste Electrode Using Pyrogallol Red as a Mediator

A sensitive and selective electrochemical method for the simultaneous determination of dopamine (DA) and uric acid (UA) was developed using a pyrogallol red modified carbon paste electrode. Under the optimized conditions, the peak current was linearly dependent on 1.0–700.0 μmol L^?1 DA and 50.0–1000.0 μmol L^?1 UA. The detection limits for DA and UA were 0.78 μmol L^?1 and 35 μmol L^?1, respectively. Finally, this method was also examined for the determination of DA and uric acid in real samples such as drugs and urine.     

A New Sensor for Simultaneous Determination of Tyrosine and Dopamine Using Iron(III) Doped Zeolite Modified Carbon Paste Electrode

A new chemically modified electrode is constructed based on iron(III) doped zeolite modified carbon paste electrode (Fe³⁺Y/ZMCPE). The new sensor could be used for the simultaneous determination of the biologically important compounds dopamine (DA) and tyrosine (Tyr). The measurements are carried out using differential pulse voltammetric (DPV) method. The prepared modified electrode shows voltammetric responses of high sensitivity, selectivity and stability for DA and Tyr under optimal conditions, which makes it a suitable sensor for simultaneous trace detection of DA and Tyr in solution. Application of the DPV method demonstrates that in the Briton Robinson buffer solutions (pH=5) containing 50 µmol/L Tyr, there is a linear relationship between the oxidation peaks and the concentrations of DA over the range of 0.1–200 µmol/L, with a detection limit of 0.05 µmol/L (S/N=3). For Tyr a linear correlation between oxidation peak current and concentration of Tyr over the range of 0.5–200 µmol/L (containing 50 µmol/L DA), with a detection limit of 0.08 µmol/L is obtained. The analytical performances of this sensor are evaluated for the detection of DA and Tyr in human serum and a medicine.     

Carbon Paste Electrode Modified with Functionalized Nanoporous Silica Gel as a New Sensor for Determination of Silver Ion

A new dipyridyl‐functionalized silica gel (DPSG) was synthesized. The potentiometric response of silver ion was investigated at a carbon paste electrode chemically modified with functionalized nanoporous silica gel. The electrodes with a DPSG proportions of 10.1% (w/w), showed very stable potential. Calibration plots with Nernstian slopes for Ag⁺ were observed, 58.7 (±0.9) mV decade^?1, over a wide linear range of concentration (5.0×10^?7 to 1.0×10^?1 M). The electrode has a detection limit of 1.0×10^?7 M. The selectivity coefficients measured by the match potential method in acetate buffer, pH 5.5, were investigated. The electrode has fast response time, high performance, high sensitivity in wide cation activity ranges, and good long term stability (more than 6 months). The method was satisfactory and used to determine the concentration of silver ion in waste waters contaminated by this metal.     

An Electrochemical Sensor for Determination of Ultratrace Cd,Cu and Hg in Water Samples by Modified Carbon Paste Electrode Base on a New Schiff Base Ligand

This paper describes the preparation and electrochemical application of a new chemically modified electrode for simple and highly sensitive simultaneous determination of copper, mercury and cadmium using cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Firstly, a new bis‐Schiff base ligand, 2,2′‐((pyridine‐2,6‐diylbis (azanylylidene)) bis (methanylylidene))bis(4‐bromophenol) (ligand L ) has been synthesized by reaction of the 2,6‐diamino pyridine with 5‐bromo salicylaldehyde or salicylaldehyde at ethanol under refluxing. The structure of the synthesized compound resulted from the IR, ¹HNMR, MS, UV spectroscopy and elemental analysis data. Afterwards, a novel, simple and effective chemically modified carbon paste electrode with ligand L was prepared. The electrochemical properties and applications of the modified electrode, including the pH, percentage of modifier, the electron transfer, optimized conditions, linear response and detection limit were investigated. High sensitivity and reproducibility, together with the ease of preparation and regeneration of the electrode surface by simple polishing, make the electrode very suitable for the voltammetric determination of copper, mercury and cadmium in several Merck samples and water samples.     

Application of Novel Zn‐Ferrite Modified Glassy Carbon Paste Electrode as a Sensor for Determination of Cd(II) in Waste Water

This paper describes the preparation of a new sensor based on Zn‐ferrite modified glassy carbon paste electrode and its electrochemical application for the determination of trace Cd(II) ions in waste waters using differential pulse anodic stripping voltammetry (DPASV). Different Zn/Ni ferrite nanoparticles were synthesized and characterized using scanning electron microscopy (SEM) and X‐ray powder diffraction (XRPD). The prepared ferrite nanoparticles were used for the preparation of Zn‐ferrite‐modified glassy carbon paste electrode (ZnMGCPE) for determination of Cd(II) at nanomolar levels in waste water at pH 5. The different parameters such as conditions of preparation, Zn²⁺/Ni²⁺/Fe²⁺ ratio and electrochemical parameters, percentage of modifier, accumulation time, pH and accumulation potential were investigated. Besides, interference measurements were also evaluated under optimized parameters. The best voltammetric response was observed for ZnFe₂O₄ modifier, when the percentage of modifier was 3 %, accumulation time 9 min, pH of supporting electrolyte 5 and accumulation potential ?1.05 V. Thus prepared electrode displays excellent response to Cd(II) with a detection limit of 0.38 ppb, and selective detection toward Cd(II) was achieved.     

Fabrication and Application of a Sensitive and Highly Stable Copper Hexacyanoferrate Modified Carbon Ionic Liquid Paste Electrode for Hydrogen Peroxide and Glucose Detection

A three‐factor mixture design and response surface methodology were employed to find the optimal weight ratio of graphite powder, n‐dodecylpyridinium hexafluorophosphate and paraffin for the fabrication of a copper hexacyanoferrate modified carbon ionic liquid paste electrode (CuHCFe‐CILPE). The fabricated sensor showed electrocatalytic activity towards oxidation and reduction of hydrogen peroxide. It also was observed that the electrocatalytic activity for hydrogen peroxide oxidation was much higher than the electrocatalytic activity for hydrogen peroxide reduction. Glucose oxidase was then successfully immobilized on the surface of the proposed sensor to examine the possibility of using CuHCFe‐CILPE for the biosensor fabrication.     

A Disposable Sensor Chip Using a Paste Electrode with Surface-Imprinted Graphite Particles for Rapid and Reagentless Monitoring of Theophylline

This work focuses on a carbon-based imprinted polymer composite, employed as a molecular recognition and sensing interface in fabricating a disposable electrochemical sensor. The carbon-paste electrode was made of a molecularly imprinted polymer comprising a copolymer of methacrylic acid as the functional monomer and blended crosslinking monomers of N,N′-methylenebisacrylamide, and ethylene glycol dimethacrylate, with theophylline as the template. The analytical properties of the proposed theophylline sensor were investigated, and the findings revealed an increase in differential pulse voltammetric current compared to the non-imprinted electrode. Under optimized conditions, the sensor has shown high sensitivity, high selectivity, lower detection limit (2.5 µg/mL), and satisfactory long-term stability. Further, the sensor was tested in whole bovine blood and validated without any matrix effect and cross-reactivity. Additionally, chronoamperometry of the sensor chip supported a rapid determination of THO with a short response time of 3 s. This carbon-paste electrode is highly specific for theophylline and may be applied as a drug sensor for clinical use.     

Determination of Ascorbic Acid in the Presence of Uric Acid and Folic Acid by a Nanostructured Electrochemical Sensor Based on a TiO2 Nanoparticle Carbon Paste Electrode

A carbon paste electrode (CPE), modified with novel hydroquinone/TiO₂ nanoparticles, was designed and used for simultaneous determination of ascorbic acid (AA), uric acid (UA) and folic acid (FA). The magnitude of the peak current for modified TiO₂-nanoparticle CPE (MTNCPE) increased sharply in the presence of ascorbic acid and was proportional to its concentration. A dynamic range of 1.0–1400.0 μM, with the detection limit of 6.4 × 10^?7 M for AA, was obtained using the DPV technique (pH = 7.0). The prepared electrode was successfully applied for the determination of AA, UA, and FA in real samples.     

Zeolite-Modified Carbon-Paste Electrode as a Selective Voltammetric Sensor for Detection of Tryptophan in Pharmaceutical Preparations

Abstract

Several synthetic zeolites such as mazzite, mordenite, zeolite L, zeolite beta, and MCM-41 were tested as electrode modifiers in voltammetric determination of tryptophan. It was found that addition of zeolite beta to the carbon paste would generate the peak current of Trp because of its catalytic effect. The anodic peak currents were proportional to Trp concentrations in the range of 5.0 × 10^?7 to 5.0 × 10^?3 M. The detection limit was 1.0 × 10^?7 M. The influence of several species, especially other amino acids, were tested. The proposed method was applied successfully to the determination of tryptophan in pharmaceutical formulations.