A Nonenzymatic Amperometric Method for Fructosyl‐Valine Sensing Using Ferroceneboronic Acid

Fructosyl valine (Fru‐Val) is a glycosylated component of hemoglobin (HbA_1c) that can serve as a diagnostic target for type 2 diabetes. While average blood glucose levels fluctuate significantly, the more stable levels of HbA_1c can serve as a better long‐term diagnostic marker. Here a diagnostic system, incorporating an amperometric method, for detecting Fru‐Val (at +0.1 V vs. Ag/AgCl), using ferrocene boronic acid (FcBA) is presented. FcBA can complex diols, and has easily detectable redox properties. The boronic acid group in FcBA mediates complexation, while the Fe(II)/Fe(III) couple serves as a transducer. The diagnostic system, based on a miniaturized bare glassy carbon paste electrode (GCPE), has a fast response time.     

Electroanalytical Study of Prussian Blue Modified Glassy Carbon Paste Electrodes

Two types of glassy carbon (GC) powder (i.e., Sigradur K and Sigradur G) have been mixed with mineral oil to obtain glassy carbon paste electrodes (GCPE's). The electrochemical behavior of such electrodes at different percentages of glassy carbon has been evaluated with respect to the electrochemistry of ferricyanide as revealed with cyclic voltammetry and the best paste composition was chosen. GC was then modified with Prussian Blue (PB), mixed at different percentages with unmodified GC and with a fixed amount of mineral oil in order to obtain PB modified glassy carbon paste electrodes (PB‐GCPE's). PB‐GCPE's with different percentages of GC modified with PB (PB‐GC) were compared and the dependence on the amount of PB on their performances was evaluated by studying the parameters of cyclic voltammetry (i.e., current peak, ΔE_p, anodic and cathodic current ratio, charge density) and the amperometric response to H₂O₂. Data interpretation based on the GC surface area is presented. GCPE's with a selected amount of PB‐GC were then tested as H₂O₂ probes and all the analytical parameters together with the dependence on pH were evaluated. Some preliminary experiments with these electrodes assembled as glucose, lysine and lactate biosensors are also reported.     

Determination of Epinephrine at Different Types of Carbon Paste Electrodes

The voltammetric behavior of epinephrine was investigated by differential pulse voltammetry (DPV) at a carbon paste electrodes (CPE) made of different carbon powders – CR-2, glassy carbon (GC) microparticles, and single-wall carbon nanotubes (SWNT). In Briton-Robinson (BR) buffer solution pH 6, the linear dependence was found for the determination of epinephrine by the given method in the concentration ranges of 1·10^?6–1·10^?4 (CR-2), 1·10^?6–1·10^?4 (GC microparticles) and 4·10^?6–1·10^?4 (SWNT) mol·dm^?3. Limits of detection were 8·10^?7, 8·10^?7, and 2·10^?6 mol·dm^?3, respectively. The best results were obtained employing CPE containing carbon paste with 50% (m/m) of SWNT, a linear dynamic range being 4·10^?7–1·10^?4 mol·dm^?3 and a limit of detection 2·10^?7 mol·dm^?3. The attempt to increase the sensitivity by adsorptive accumulation of epinephrine was not successful.     

Comparison of Boron‐Doped Diamond and Glassy Carbon Electrodes for Determination of Procaine Hydrochloride

The electrochemical oxidation of procaine hydrochloride (PC?HCL, 2‐diethylaminoethyl 4‐aminobenzoate hydrochloride) was investigated at as‐deposited boron‐doped diamond (ad‐BDD) electrode, anodically oxidized BDD (ao‐BDD) electrode and glassy carbon (GC) electrode using cyclic voltammetry (CV). Well‐defined cyclic voltammograms were obtained for PC?HCL oxidation with high signal‐to‐background (S/B) ratio, low tendency for adsorption, good reproducibility and long‐term stability at ad‐BDD electrode, demonstrating its superior electrochemical behavior and significant advantages in contrast to ao‐BDD and GC electrode. At 100 μM PC?HCL, the voltammetric S/B ratio was nearly one order of magnitude higher at an ad‐BDD electrode than that at a GC electrode. In a separate set of experiments for oxidation of 100 μM PC?HCL, 96%, 92% and 84% of the initial oxidation peak current was retained at the ad‐BDD, ao‐BDD and GC electrode, respectively, by stirring the solution after the tenth cycle. The current response was linearly proportional to the square root of the scan rate within the range 10–1000 mV s^?1 in 10 μM PC?HCL solutions, indicating that the oxidation process was diffusion‐controlled with negligible adsorption at an ad‐BDD surface. The good linearity was observed for a concentration range from 5 to 200 μM with a linear equation of y=0.03517x+0.65346 (r=0.999), and the detection limit was 0.5 μM for oxidation of PC?HCL at the ad‐BDD electrode. The ad‐BDD electrode could maintain 100% of its original activity after intermittent use for 3 months.     

Novel Studies about the Electrooxidation of a Deoxynivalenol (DON) Mycotoxin Reduction Product Adsorbed on Glassy Carbon and Carbon Paste Electrodes

A novel and fast square‐wave adsorptive anodic stripping voltammetric procedure on glassy carbon and carbon paste electrodes is described for the indirect trace quantitation of deoxynivalenol (DON) mycotoxin that frequently contaminates soya and foodstuff. The in situ homogeneous reduction of the toxin by product/s of dissolved oxygen electroreduction in pH 8 buffer solution makes the quantitation of DON possible through a simple electroanalytical technique. Moreover, its potential use for the analysis of real samples was demonstrated using a soya flour sample spiked with DON without previous separating procedures. The DON detection limits were 3.6 and about 6 ppb from standard solutions and soya flour matrix, respectively.     

用碳糊修饰电极测定氨基酸的伏安法研究

用10％氧化铝的修饰碳糊电极研究了测定组氨酸的伏安法。 在0.05 mol/L 丁二酸－硼砂（pH=3.5)底液中在－0.6 V出现一还原峰, 结合2.5次微分技术测定组氨酸, 在3.20 ～130 μmol/L 浓度范围内有良好的线性关系, 相对标准偏差为3.4％, 检出限为0.4 μmol/L。 检测灵敏度比文献报道有较大的提高。 文中还讨论了电极过程。     

Behavior of Glassy Carbon Paste Electrode in Flowing Methanolic Solutions

Carbon paste electrodes are often used for electrochemical determinations, but their application in media with high content of organic solvents, particularly in HPLC, is limited by their low stability. The work presented here examines the effect of a moving methanol‐containing solution on a glassy carbon paste electrode by studying its electrochemical behavior in relation to the period of contact and methanol content in the solution. In combination with microscopic observation of the paste surface it can be concluded that the electrode is affected by the methanolic solution and the surface roughness increases, resulting in the stable state compatible with measurements in highly methanolic solutions.     

Characterization of DNA Layers Adsorbed on Glassy Carbon Electrodes

A DNA layer adsorbed at glassy carbon electrodes (GCE) was characterized by ellipsometry, atomic force microscopy (AFM) and scanning electron microscopy (SEM). The presence of the adsorbed DNA layer on polished glassy carbon electrodes was assessed indirectly by ellipsometric measurements. Ellipsometry was also useful to evaluate the influence of the oxide layer formed on glassy carbon electrodes, either spontaneously or after electrochemical pretreatments, on the DNA adsorption and further electrooxidation process. SEM and AFM images of the electrode surface covered by a thick layer of DNA reveal a nonuniform distribution, leaving channels and islands of the biological material.     

四氰基醌二甲烷修饰碳糊电极电催化氧化测定抗坏血酸

本用四氰基醌二甲烷作价体，制成ＴＣＮＱ－碳糊电极，研究了该电极的性能。电极对水溶液中的抗坏血酸在较宽的ｐＨ和浓度范围内均有良好的电催化氧化作用，电极的稳定性良好，在ＡＨ２浓度５．０×１０＾－５－５．０×１０－２ｍｏｌ／Ｌ范围内，催化峰电流与ＡＨ２浓度呈线性关系，响应时间小于３０ｓ．     

Determination of Carbendazim by Adsorptive Stripping Differential Pulse Voltammetry Employing Glassy Carbon Paste Electrode Modified with Graphene and Amberlite XAD 2 Resin

Graphene nanosheets (GNS) and amberlite XAD‐2 (XAD2) modified glassy carbon paste electrode (GNS‐XAD2‐GCPE) were fabricated for voltammetric determination of Carbendazim (MBC). GNS was synthesized by Hummer’s method and characterized by SEM, EDAX, and XRD techniques. After optimizing the analytical conditions in 0.4 M citrate buffer (pH 4.0), the peak current was found to be linear in the range of 8.36×10^?9 to 4.13×10^?6 M (r=0.9986) with detection limit of 3.14×10^?9 M (S/N=3) by AdSDPV. The method was validated for the determination of MBC in soil, fruit, blood serum, urine, waste and ground water samples with satisfactory recoveries.     

测酚用的酪氨酸酶媒体玻碳电极的研制

通过聚乙烯亚胺(PEI)包埋和外覆Nafion膜 ,将酪氨酸酶固定在以天青—双氰胺 -甲醛聚合物修饰的玻碳电极表面。工作电位 -100mV(vs.SCE),电极对多种酚有响应 ,对苯酚测定的线性范围为0.20～96μmol/L,响应时间t95 小于50s ,用于测标样和炼焦废水样 ,精密度、准确度好。     

用碳糊修饰电极测定氨基酸的伏安法研究：Ⅱ.组氨酸在氧化铝修饰碳糊 …

用１０％氧化铝的修饰碳糊电极研究了测定组氨酸的伏安法。在０．０５ｍｏｌ／Ｌ丁二酸－硼砂（ｐＨ＝３．５）底液中在－０．６Ｖ出现一还原峰,结合２．５次微分技术测定组氨酸,在３．２０～１３０μｍｏｌ／Ｌ浓度范围内有良好的线性关系,相对标准偏差为３．４％,检出限为０．４μｍｏｌ／Ｌ。检测灵敏度比文献报道有较大的提高。文中还讨论了电极过程。     

Comparison of Boron-Doped Diamond and Glassy Carbon Electrodes for Determination of Terbinafine in Pharmaceuticals Using Differential Pulse and Square Wave Voltammetry

This paper examines the electrochemical oxidation of terbinafine with the boron doped diamond and glassy carbon electrodes. The studies were performed by cyclic voltammetry (CV), differential pulse voltammetry (DPV), and square-wave voltammetry (SWV). The supporting electrolytes, solution pH, the range of potentials, and the scan rates were optimized. Terbinafine was irreversibly oxidized in all electrolytes, yielding well-defined peaks in the positive potential range. The peak potential shifted towards less positive values as the solution pH increased. Voltammetric determination of terbinafine was performed under the optimized conditions. Using the boron doped diamond electrode, a linear relationship between current and concentration was obtained between 5.44 × 10^?7 and 5.18 and 10^?6 mol/L with SWV and between 7.75 · 10^?7 and 8.55 · 10^?6 mol/L by DPV. At the glassy carbon electrode, a linear relationship between 7.75 · 10^?7 and 8.55 · 10^?6 mol/L was obtained by SWV and between 7.75 · 10^?7 and 1.05 · 10^?5 mol/L by DPV. The sensitivity, precision, and selectivity of the procedures were evaluated. In order to check the practical application of the developed methods, the concentration of terbinafine was determined in pharmaceutical preparations.     

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.     

Electrochemical Behavior and Determination of L‐Tyrosine at Single‐walled Carbon Nanotubes Modified Glassy Carbon Electrode

Based on single‐walled carbon nanotubes (SWCNTs) modified glassy carbon electrode (GCE/SWCNTs), a novel method was presented for the determination of L ‐tyrosine. The GCE/SWCNTs exhibited remarkable catalytic and enhanced effects on the oxidation of L ‐tyrosine. In 0.10 mol/L citric acid‐sodium citrate buffer solution, the oxidation potential of L ‐tyrosine shifted negatively from +1.23 V at bare GCE to +0.76 V at GCE/SWCNTs. Under the optimized experimental conditions, the linear range of the modified electrode to the concentration of L ‐tyrosine was 5.0×10^?6–2.0×10^?5 mol/L (R₁=0.9952) and 2.7×10^?5–2.6×10^?4 mol/L (R₂=0.9998) with a detection limit of 9.3×10^?8 mol/L. The kinetic parameters such as α (charge transfer coefficient) and D (diffusion coefficient) were evaluated to be 0.66, 9.82×10^?5 cm² s^?1, respectively. And the electrochemical mechanism of L ‐tyrosine was also discussed.     

Electrochemical Investigations of the Anticancer Drug Idarubicin Using Multiwalled Carbon Nanotubes Modified Glassy Carbon and Pyrolytic Graphite Electrodes

The effect of surface modifications on the electrochemical behavior of the anticancer drug idarubicin was studied at multiwalled carbon nanotubes modified glassy carbon and edge plane pyrolytic graphite electrodes. The surface morphology of the modified electrodes was characterized by scanning electron microscopy. The modified electrodes were constructed for the determination of idarubicin using adsorptive stripping differential pulse voltammetry. The experimental parameters such as supporting electrolyte, pH, accumulation time and potential, amount of carbon nanotubes for the sensitive assay of idarubicin were studied as details. Under the optimized conditions, idarubicin gave a linear response in the range 9.36×10^?8–1.87×10^?6 M for modified glassy carbon and 9.36×10^?8–9.36×10^?7 M for modified edge plane pyrolytic graphite electrodes. The detection limits were found as 1.87×10^?8 M and 3.75×10^?8 M based on modified glassy carbon and edge plane pyrolytic graphite electrodes, respectively. Interfering species such as ascorbic acid, dopamine, and aspirin showed no interference with the selective determination of idarubicin. The analyzing method was fully validated and successfully applied for the determination of idarubicin in its pharmaceutical dosage form. The possible oxidation mechanism of idarubicin was also discussed. The results revealed that the modified electrodes showed an obvious electrocatalytic activity toward the oxidation of idarubicin by a remarkable enhancement in the current response compared with bare electrodes.     

Cyclodextrin Modified Carbon Paste Based Electrodes as Sensors for the Determination of Carcinogenic Polycyclic Aromatic Amines

Voltammetric properties and possibility of the determination of carcinogenic aminoderivatives of polycyclic aromatic hydrocarbons, namely 1‐ and 2‐aminonaphthalene and 2‐aminobiphenyl, have been investigated. Carbon paste electrodes (CPE) modified with monomeric α‐, β‐ or γ‐cyclodextrin and carbon‐based screen‐printed electrodes (SPE) surface‐modified with a thin film of β‐cyclodextrin (β‐CDP) or carboxymethylated β‐cyclodextrin (β‐CDPA) condensation polymer were used for that purpose as simple electrochemical biosensors. Analytical procedure for the DPV determination of tested amines using these biosensors was proposed. Linear calibration plots within the concentration range of 2×10^?8 – 2×10^?7 mol dm^?3 and 2×10^?7–1×10^?6 mol dm^?3 with limits of quantification of the order of 10^?9 mol dm^?3 were obtained for the modified CPE and modified SPE.     

土豆汁修饰碳糊电极测定色氨酸的研究

本提出了用于测定色氨酸的土豆汁修饰碳糊电极，该电极选择性好，能有效地消除酪氨酸的干扰，在ｐＨ＝７．４的ＮａＨ２ＰＯ４－ＮａＯＨ生理缓冲液中，电极响应与色氨酸在９．８×１０＾－６～９．８×１０＾－５ｍｏｌ／Ｌ的浓度范围内呈线性关系，最低检出限是１．５×１０＾－６ｍｏｌ／Ｌ．并详细讨论了电极抗干扰能力与测定条件的关系。用该电极测定了实际样品氨基酸注射液中色氨酸的含量，结果与标准值吻合。     

Study of the Electrostatic Interaction of Lysine Monolayer on Glassy Carbon Electrodes Using the Electrochemical Method

A covalent modified glassy carbon electrode (GCE) with Lysine (Lys) has been fabricated via an electrochemical oxidation procedure. The electrostatic interaction of the monolayer has been investigated by cyclic voltammetry (CV) with Fe(CN)₆^3? redox probe in different concentrations of protons and different charged cations, respectively. The electrochemical method can be a new feasible method for the study of electrostatic interaction of the monolayer.     

Utilization of Carbon Paste Electrodes for the Voltammetric Determination of Chlortoluron

Conventional (CPE) and miniaturized (m‐CPE) carbon paste electrodes consisting of a carbon paste filled capillary were used for differential pulse voltammetric determination of chlortoluron in samples of river water and soil, in the latter case after the extraction by methanol. Britton‐Robinson buffer pH 3 with low content of methanol was found to be optimal for the determination. The achieved determination limits were 2.8 µmol L^?1 and 0.34 µmol L^?1 in river water, and 3.1 and 4.3 µg g^?1 in soil, using CPE and m‐CPE, respectively.