Study on Diffusion Mechanisms and Determination of Dihydroxybenzene Isomers at the Pre‐anodized Inlaying Ultrathin Carbon Paste Electrode

In this paper, nichrome was adopted as a substrate, to fabricate the pre‐anodized inlaying ultrathin carbon paste electrode (PAIUCPE). The electrochemical behaviors and diffusion mechanisms of three dihydroxybenzene isomers at the electrode were carefully investigated. The effect of pH on oxidation peak current was also detailedly explained. The results were shown that oxidation peak current not only related to the reaction of electroactive materials at the working electrode, but also depended on the reaction variable of reduction at the auxiliary electrode. The oxidation peaks of hydroquinone (HQ), catechol (CC) and resorcinol (RC) located at 0.181 V, 0.288 V and 0.736 V. For CC, RC and HQ, the oxidation peak currents were linear to the concentrations at the range of 5.0 × 10^?6～5.0 × 10^?4 mol/L, 3.0 × 10^?6～5.0 × 10^?4 mol/L and 4.0 × 10^?6～4.0 × 10^?4 mol/L with the detection limits of 2.0 × 10^?7 mol/L, 1.2 × 10^?7 mol/L and 1.2 × 10^?7 mol/L, respectively. The proposed method was successfully applied in the simultaneous determination of dihydroxybenzene isomers in artificial sewage samples with satisfactory results.     

Electrochemiluminescent Detection Method for Glyphosate in Soybean on Carbon Fiber-ionic Liquid Paste Electrode

A carbon fiber paste electrode using ionic liquid as the binder (CFILE) was fabricated. The electrochemical characteristics of the electrode was examined in ferro‐/ferricyanide solution and showed better conductivity and reversibility when compared with graphite paste‐ionic liquid electrode (GPILE) and a little better than that on the carbon nanotube paste‐ionic liquid electrode (CNTILE). Glyphosate (GLY), a pesticide, exhibited excellent catalysis to the oxidation of Ru(bpy)²⁺₃ on CFILE and brought an obvious enhancement to the electrochemiluminescence (ECL) intensity of Ru(bpy)²⁺₃. Based on the catalytic ability of GLY, a simple ECL method for GLY detection had been established. Under optimum conditions, the enhanced ECL intensities were found to had linearly respond to the GLY concentration between 3.0×10^?7 and 3.0×10^?5 mol/L, and the detection limit (S/N=3) was 2.0×10^?7 mol/L. The electrode also showed excellent sensitivity in detecting GLY‐spiked soybean samples. The linear range for GLY in soybean samples was 1.0×10^?6–4.0×10^?5 mol/L and the detection limit was 5.0×10^?7 mol/L, equal to 8.45 µg GLY in per gram of soybean. The detection limit in soybean sample was lower than the USA, EU regulation and so on. If the method is coupled with the separation technology, it can be applied to detect the GLY in the contaminated samples.     

Determination of nicotine and its metabolite cotinine in urine and cigarette samples by capillary electrophoresis coupled with electrochemiluminescence

In this paper, CE coupled with electrochemiluminesence (ECL) detection using a 76‐μm Pt disk as working electrode was developed for nicotine (NIC) determination. The major metabolite of NIC is cotinine (COT), which has a similar tertiary amine structure to NIC. However, there is a carbonyl group attached in the structure of COT, which leads to the great decrease in ECL response. In order to improve the ECL response of COT, NaBH₄ was used for carbonyl reduction. After reduction, NIC and COT were separated and detected by CE‐ECL. ECL response plotted with NIC concentration was linear between 5.0×10^?7 and 5.0×10^?5 mol/L (81–8100 μg/L), with LOD of 5.0×10^?8 mol/L (8.1 μg/L). The developed CE‐ECL method was applied for NIC determination in urine and cigarette samples.     

The electrochemical oxidation of pentachlorophenol and its sensitive determination at chitosan modified carbon paste electrode

We report on a novel electrochemical method to detect trace pentachlorophenol (PCP) by using a chitosan (CS) modified carbon paste electrode (CS/CPE). Compared with that at a bare carbon paste electrode (CPE), the current response was greatly improved at the CS/CPE due to the enhancement effect of CS. Under optimal working conditions, the oxidation peak current of PCP was proportional to its concentration in the range of 1.0 × 10^?7 to 5.0 × 10^?6 and 5.0 × 10^?6 to 1.0 × 10^?4 mol/L, with an extremely low detection limit of 4.0 × 10^?8 mol/L. Our method was successfully used to detect the PCP concentration in vegetable samples.     

A sensitive electrochemical sensor for detection of rutin based on a gold nanocage‐modified electrode

In this article, an electrochemical sensor based on a gold nanocage (AuNC)‐modified carbon ionic liquid electrode (CILE) was fabricated and applied to the sensitive rutin determination. The presence of AuNCs on the electrode surface greatly improved the electrochemical performance of the working electrode due to its specific microstructure and high metal conductivity. Electrochemical behavior of rutin on AuNCs/CILE was studied using cyclic voltammetry and differential pulse voltammetry with the related electrochemical parameters calculated. Under the optimal experimental conditions, the oxidation peak current of rutin and its concentration had good linear relationship in the range from 4.0 × 10^?9 to 7.0 × 10^?4 mol/L with a low detection limit of 1.33 × 10^?9 mol/L (3σ). This fabricated AuNCs/CILE was applied to direct detection of the rutin concentration in drug samples with satisfactory results, showing the real application of AuNCs in the field of chemically modified electrodes.     

Preparation of a Novel COOH Ion Implantation Sensor and Its Application

A novel ion implantation sensor (DNA/COOH/ITO) based on DNA immobilization in COOH/ITO probe was manufactured for the first time. The surface morphologies of the electrodes were characterized by X‐ray photoelectron spectroscopy (XPS), field‐emission‐scanning electron microscopy (FSEM) and electrochemical methods. In a 0.5 mol/L PBS solution, a sensitive oxidation peak of DNA on the COOH/ITO electrode was obtained by voltammetry. The electrochemical behavior of DNA was studied. And the oxidative peak potential of DNA was +0.400 V (vs. Ag/AgCl). Its peak current was proportional to the concentration of DNA over the range of 1.0×10^?8?1.0×10^?6 mol/L with a detection limit of 5.0×10^?9 mol/L (about 0.5 ng/mL). This sensor was applied to the direct detection of DNA samples.     

Effect of Pulse Width of Square Potential to Remove Silver Interference in the Determination of Mercury(II)

A graphite electrode modified with silver (Ag‐CPE) has been applied to detect mercury(II) using differential pulse voltammetry (DPV). Under optimized conditions, the calibration curve is linear in the range from 5.0×10^?8 mol L^?1 to 1.0×10^?4 mol L^?1 of mercury(II). The detection limit was found to be 3.38×10^?8 mol L^?1 with a relative standard deviation (RSD) of 2.25 % (n=8). The proposed method was successfully applied for the detection of mercury(II) in leachate samples. The Ag‐CP composites were characterized using X‐ray diffraction (XRD), BET adsorption analysis and scanning electron microscopy (SEM).     

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.     

Voltammetric Determination of L‐Dopa Using a Carbon Nanotubes‐Nafion Modified Glassy Carbon Electrode

Abstract

A method for determination of L‐dopa by the adsorption stripping voltammetry (ASV) using a multiwalled carbon nanotubes (MWNTs)–Nafion modified glassy carbon electrode (GMGCE) was proposed. This chemically modified electrode (CME) shows a better stability. A sensitive oxidation peak was observed and the anodic peak potential is ca. 0.374V (vs. SCE). The influences of various experimental parameters on the current peak were completely studied. Under the optimized condition, the method has been applied to the determination of L‐dopa in samples. There is a good linear relationship between the peak current (i_p) and L‐dopa concentration in the range of 3.5×10^?7～1.5×10^?5 mol/L, with the limit of detection 5.0×10^?8 mol/L.     

Application of Nafion／Cobalt Hexacyanoferrate Chemically Modified Electrodes for the Determination of Electroinactive Cations by Ion Chromatography

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Study on the Electrochemical Behavior of Dopamine and Uric Acid at a 2‐Amino‐5‐mercapto‐[1,3,4] Triazole Self‐Assembled Monolayers Electrode

Selected from a series of structurally related heteroaromatic thiols, a newly synthesized reagent 2‐amino‐5‐mercapto‐[1,3,4] triazole (MATZ) was used to fabricate self‐assembled monolayers (SAMs) on gold electrode for the first time. The MATZ/Au SAMs was characterized by electrochemical methods and scanning electronic microscopy (SEM). In 0.04 mol/L Britton–Robinson buffer solution (pH 5), the electrochemical behavior of dopamine showed a quasireversible process at the MATZ/Au SAMs with an electrode kinetic constant 0.1049 cm/s. However, the electrochemical reaction of uric acid at the SAMs electrode showed an irreversible oxidation process, the charge‐transfer kinetics of uric acid was promoted by the SAMs. By Osteryoung square‐wave voltammetry (OSWV), the simultaneous determination of dopamine and uric acid can be accomplished with an oxidation peak separation of 0.24 V, the peak current of dopamine and uric acid were linearly to its concentration in the range of 2.5×10^?6–5.0×10^?4 mol/L for dopamine and 1×10^?6–1×10^?4 mol/L for uric acid with a detection limit of 8.0×10^?7 mol/L for dopamine and 7.0×10^?7 mol/L for uric acid. The MATZ/Au SAMs electrode was used to detect the content of uric acid in real urine and serum sample with satisfactory results.     

Electrochemical Detection of Methimazole by Capillary Electrophoresis at a Carbon Fiber Microdisk Electrode

We developed a sensitive, simple and low cost method to determine methimazole based on capillary electrophoresis with electrochemical detection (CE‐EC) at a carbon fiber microdisk electrode (CFE). We investigated the effects of detection potential, the concentration and pH value of the phosphate buffer, and injection time as well as separation voltage on the detection of methimazole. Under the optimized conditions: the detection potential at 1.30 V, 10 mmol/L phosphate buffer (pH 7.0), injection time 30 s at a height of 20 centimeter and separation voltage at 15 kV, the linear range was obtained from 1.0×10^?7 to 2.0×10^?4 mol/L, covering 3 orders of magnitude with a correlation coefficient of 0.9995. The LOD (S/N=3) obtained was 5.0×10^?8 mol/L. The RSD of migration time and peak current for 2.0×10^?4 mol/L methimazole was 1.04% and 1.54% (n=10), respectively. The method was also used to analyze methimazole tablets and human urine sample.     

Catalysis‐Electrochemical Detection of Horseradish Peroxidase at Zeptomole Level in Capillary Zone Electrophoresis

Capillary zone electrophoresis with catalysis‐electrochemical detection has been developed and applied to determining horseradish peroxidase (HRP) at zeptomole levels. In this method, an on‐line enzyme catalysis reactor with a reaction capillary was designed. Isoenzymes of HRP were separated by capillary zone electrophoresis, and then they catalyzed the enzyme substrate 3,3′,5,5′‐tetramethylbenzide (TMB(Red)) and H₂O₂ in the reaction capillary. The reaction product, TMB(Ox), could be determined using amperometric detection on a carbon fiber microdisk bundle electrode at the outlet of the reaction capillary. Because of enzyme amplification, a significant amount of TMB(Ox) could be produced for detection. Therefore, the limit of detection (LOD) of HRP is very low. The optimum conditions of the method are 1.5×10^?2 mol/L borate (pH 7.4) for the run buffer, 2×10^?3 mol/L for the concentration of H₂O₂, 2×10^?4 mol/L TMB(Red)+2.0×10^?2 mol/L citrate‐phosphate (pH 5.0) for the substrate solution, 40 cm for the liquid pressure height, 20 kV for the separation voltage, 100 mV for the detection potential. HRP could be measured with a detection limit of 4.8×10^?12 mol/L or 47.5 zmol (S/N=3). The linear range is from 2.40×10^?11 to 2.40×10^?8 mol/L. Using this method, commercial HRP was measured at zeptomole within ten minutes.     

Electrochemiluminescence Biosensor for Glucose Based on Graphene/Nafion/GOD Film Modified Glassy Carbon Electrode

Glucose oxidase(GOD) was encapsulated in the Graphene/Nafion film modified glassy carbon electrode(GCE) and used as an ECL sensor for glucose. The GOD retains its bioactivity after being immobilized into the composite film. The sensor gives a linear response for glucose in the range of 2.0×10^?6–1.0×10^?4 mol/L with a detection limit of 1.0×10^?6 mol/L. The sensor showed good stability, the RSD for continuous scanning for 5.0×10^?5 mol/L glucose was 4.21 % (n=5). After being stored in 0.05 mol/L pH 7.4 PBS in 4 °C for two weeks, the modified electrode maintains 80 % of its initial activity. The glucose sensor provides new opportunity for clinical diagnosis applications.     

One‐Step Synthesis of β‐Cyclodextrin Functionalized Graphene/Ag Nanocomposite and Its Application in Sensitive Determination of 4‐Nitrophenol

β‐Cyclodextrin functionalized graphene/Ag nanocomposite (β‐CD/GN/Ag) was prepared via a one‐step microwave treatment of a mixture of graphene oxide and AgNO₃. β‐CD/GN/Ag was employed as an enhanced element for the sensitive determination of 4‐nitrophenol. A wide linear response to 4‐nitrophenol in the concentration ranges of 1.0×10^?8–1.0×10^?7 mol/L, and 1.0×10^?7–1.5×10^?3 mol/L was achieved, with a low detection limit of 8.9×10^?10 mol/L (S/N=3). The mechanism and the heterogeneous electron transfer kinetics of the 4‐nitrophenol reduction were discussed according to the rotating disk electrode experiments. Furthermore, the sensing platform has been applied to the determination of 4‐nitrophenol in real samples.     

Direct Electrochemistry of Hemoglobin Entrapped in Composite Electrodeposited Chitosan‐Multiwall Carbon Nanotubes and Nanogold Particles Membrane and Its Electrocatalytic Application

Hemoglobin was entrapped in composite electrodeposited chitosan‐multiwall carbon nanotubes (MCNTs) film by assembling gold nanoparticles and hemoglobin step by step. In phosphate buffer solution (pH 7), a pair of well‐defined and quasireversible redox peaks appeared with formal potential at ?0.289 V and peak separation of 100 mV. The redox peaks respected for the direct electrochemistry of hemoglobin at the surface of chitosan‐MCNTs‐gold nanoparticles modified electrode. The parameters of experiments have also been optimized. The composite electrode showed excellent electrocatalysis to peroxide hydrogen and oxygen, the peak current was linearly proportional to H₂O₂ concentration in the range from 1×10^?6 mol/L to 4.7×10^?4 mol/L with a detection limit of 5.0×10^?7 mol/L, and this biosensor exhibited high stability, good reproducibility and better selectivity. The biosensor showed a Michaelis–Menten kinetic response as H₂O₂ concentration is larger than 5.0×10^?4 mol/L, the apparent Michaelis–Menten constant for hydrogen peroxide was calculated to be 1.61 μmol/L.     

Catalytic Adsorptive Stripping Voltammetry of Germanium(IV) in the Presence of Gallic Acid and Vanadium(IV)‐EDTA

A highly sensitive and selective catalytic adsorptive cathodic striping procedure for the determination of trace germanium is presented. The method is based on adsorptive accumulation of the Ge(IV)‐gallic acid (GA) complex onto a hanging mercury drop electrode, followed by reduction of the adsorbed species. The reduction current is enhanced catalytically by addition of vanadium(IV)‐EDTA. The optimal experimental conditions include the use of 0.03 mol/L HClO₄ (pH1.6), 6.0×10^?3 mol/L GA, 3.0×10^?3 mol/L V(IV), 4.0×10^?3 mol/L EDTA, an accumulation potential of ?0.10 V(vs. Ag/AgCl), an accumulation time of 120 s and a differential pulse potential scan mode. The peak current is proportional to the concentration of Ge(IV) over the range of 3.0×10^?11 to 1.0×10^?8 mol/L and the detection limit is 2×10^?11 mol/L for a 120 s adsorption time. The relative standard deviation at 5.0×10^?10 mol/L level is 3.1%. No serious interferences were found. The method was applied to the determination of germanium in ore, mineral water and vegetable samples with satisfactory results.     

A Novel Glucose Biosensor Based on Palladium Nanoparticles and Its Application in Detection of Glucose Level in Urine

IntroductionThelevelofglucoseinbloodorurineindicateshyper andhypoglycaemia ,bothofwhichcanresultfromavarietyofendocrinedisorders .1 4 Therapidandreliabledetermi nationofglucoselevelisaroutineprojectinclinicchem istry.Urinesamplesaresaferandmoreconvenientthanbloodones .Meanwhile ,theconcentrationofglucoseinserumiscloselyassociatedwiththatinurine .2 4 Eventhoughglucoseelectrodeshavebeensuccessfullyusedinseruminclinicalapplication ,thequestionstillremainedofhowtodetecttheglucoselevelinurine ,wh…     

Determination of Trace Copper by Adsorptive Voltammetry Using a Multiwalled Carbon Nanotube Modified Carbon Paste Electrode

A new method for the determination of trace copper was described. A multiwalled carbon nanotube modified carbon paste electrode was prepared and the adsorptive voltammetric behavior of copper‐alizarin red S (ARS) complex at the modified electrode was investigated. By use of the second‐order derivative linear sweep voltammetry, it was found that in 0.04 mol/L acetate buffer solution (pH 4.2) containing 4×10^?6 mol/L ARS, when accumulation potential is 0 mV, accumulation time is 60 s and scan rate is 100 mV/s, the complex can be adsorbed on the surface of the electrode, yielding one sensitive reduction peak at ?172 mV (vs. SCE). The peak current of the complex is proportional to the concentration of Cu(II) in the range of 2.0×10^?11–4.0×10^?7 mol L^?1 with a detection limit (S/N=3) of 8.0×10^?12 mol/L (4 min accumulation). The proposed method was successfully applied to the determination of copper in biological samples with satisfactory results, the recoveries were found to be 96%–102%.     

铜氮杂配合物修饰金电极对抗坏血酸的分析测定

本实验制备了一种新型的氮杂铜配合物修饰金电极,该电极可用于抗坏血酸的测定。采用循环伏安法和扫描电化学显微镜技术对电极进行了表征。该修饰电极可催化氧化抗坏血酸,相对于裸电极抗坏血酸在修饰电极上氧化电位移动了250mV,并且氧化电流在抗坏血酸的浓度为5.0×10−7 to 4.0×10−5 mol/L时呈线性关系,检测限为4.8×10-8 mol/L。用此方法测定抗坏血酸与文献报道的测定结果一致,这表明该电极可用作抗坏血酸测定的电化学传感器。