Selective and Sensitive Electrochemical Sensor for L‐Methionine at Physiological pH Using Functionalized Triazole Polymer Film Modified Electrode

This communication describes the determination of an essential amino acid, L ‐methionine (L ‐Met) in the presence of important interferents, ascorbic acid (AA) and uric acid (UA) at physiological pH using a glassy carbon electrode modified with an electropolymerized film of 3‐amino‐5‐mercapto‐1,2,4‐triazole (p‐AMTa). The bare glassy carbon electrode fails to show a voltammetric signal for L ‐Met in the presence of AA and UA at pH 7.2. However, the p‐AMTa electrode separates the voltammetric signals of AA, UA and L ‐Met with pronounced oxidation currents. The amperometric current of L ‐Met was increased linearly from 1.0×10^?7 to 1×10^?4 M and the detection limit was found to be 4.12×10^?10 M (S/N=3).     

Selective Electrochemical Epinephrine Sensor Using Self‐Assembled Monomolecular Film of 1,8,15,22‐Tetraaminophthalocyanatonickel(II) on Gold Electrode

This article describes the highly sensitive and selective determination of epinephrine (EP) using self‐assembled monomolecular film (SAMF) of 1,8,15,22‐tetraamino‐phthalocyanatonickel(II) (4α‐Ni^IITAPc) on Au electrode. The 4α‐Ni^IITAPc SAMF modified electrode was prepared by spontaneous adsorption of 4α‐Ni^IITAPc from dimethylformamide solution. The modified electrode oxidizes EP at less over potential with enhanced current response in contrast to the bare Au electrode. The standard heterogeneous rate constant (k°) for the oxidation of EP at 4α‐Ni^IITAPc SAMF modified electrode was found to be 1.94×10^?2 cm s^?1 which was much higher than that at the bare Au electrode. Further, it was found that 4α‐Ni^IITAPc SAMF modified electrode separates the voltammetric signals of ascorbic acid (AA) and EP with a peak separation of 250 mV. Using amperometric method the lowest detection limit of 50 nM of EP was achieved at SAMF modified electrode. Simultaneous amperometric determination of AA and EP was also achieved at the SAMF modified electrode. Common physiological interferents such as uric acid, glucose, urea and NaCl do not interfere within the potential window of EP oxidation. The present 4α‐Ni^IITAPc SAMF modified electrode was also successfully applied to determine the concentration of EP in commercially available injection.     

Amperometric Determination of Ascorbic Acid at an Electrodeposited Redox Polymer Film Modified Gold Electrode

A sensitive and selective electrochemical method for the determination of ascorbic acid was developed. It was shown that a hydrated osmium complex‐containing redox polymer film can be electrodeposited at the gold electrode and it exhibits excellent electrocatalytic activity towards the oxidation of ascorbic acid. In contrast to a bare gold electrode, the oxidation current of ascorbic acid increased greatly and the oxidation peak potential shifted negatively to about 0.01 V (vs. SCE) at the modified electrode. Amperometric measurements were performed at an applied potential of 0.01 V and a linear response was obtained in the range of 2–400 μM with a limit of detection (LOD) of 0.6 μM (S/N=3). The interference studies showed that the modified electrode exhibits excellent selectivity in the presence of large excess of uric acid and dopamine. The proposed procedure was successfully applied to the determination of ascorbic acid in human urine samples.     

Selective Detection of Uric Acid in the Presence of Ascorbic Acid and Dopamine Using Polymerized Luminol Film Modified Glassy Carbon Electrode

Electrochemically polymerized luminol film on a glassy carbon electrode (GCE) surface has been used as a sensor for selective detection of uric acid (UA) in the presence of ascorbic acid (AA) and dopamine (DA). Cyclic voltammetry was used to evaluate the electrochemical properties of the poly(luminol) film modified electrode. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) have been used for surface characterizations. The bare GCE failed to distinguish the oxidation peaks of AA, DA and UA in phosphate buffer solution (pH 7.0), while the poly(luminol) modified electrode could separate them efficiently. In differential pulse voltammetric (DPV) measurements, the modified GCE could separate AA and DA signals from UA, allowing the selective determination of UA. Using DPV, the linear range (3.0×10^?5 to 1.0×10^?3 M) and the detection limit (2.0×10^?6 M) were estimated for measurement of UA in physiological condition. The applicability of the prepared electrode was demonstrated by measuring UA in human urine samples.     

Selective Electroanalysis of Ascorbic Acid Using a Nickel Hexacyanoferrate and Poly(3,4‐ethylenedioxythiophene) Hybrid Film Modified Electrode

The mixed‐valent nickel hexacyanoferrate (NiHCF) and poly(3,4‐ethylenedioxythiophene) (PEDOT) hybrid film (NiHCF‐PEDOT) was prepared on a glassy carbon electrode (GCE) by multiple scan cyclic voltammetry. The films were characterized using atomic force microscopy, field emission scanning electron microscopy, energy dispersive spectroscopy, X‐ray diffraction, and electrochemical impedance spectroscopy (AC impedance). The advantages of these films were demonstrated for the detection of ascorbic acid (AA) using cyclic voltammetry and amperometric techniques. The electrocatalytic oxidation of AA at different electrode surfaces, such as the bare GCE, the NiHCF/GCE, and the NiHCF‐PEDOT/GCE modified electrodes, was determined in phosphate buffer solution (pH 7). The AA electrochemical sensor exhibited a linear response from 5×10⁻⁶ to 1.5×10⁻⁴ M (R²=0.9973) and from 1.55×10⁻⁴ to 3×10⁻⁴ M (R²=0.9983), detection limit=1×10⁻⁶ M, with a fast response time (3 s) for AA determination. In addition, the NiHCF‐PEDOT/GCE was advantageous in terms of its simple preparation, specificity, stability and reproducibility.     

Selective Simultaneous Determination of Paracetamol and Uric Acid Using a Glassy Carbon Electrode Modified with Multiwalled Carbon Nanotube/Chitosan Composite

A multiwalled carbon nanotube/chitosan modified glassy carbon electrode (MWCNTs‐CHT/GCE) has been used for simultaneous determination of paracetamol (PAR) and uric acid (UA). The measurements were carried out using differential pulse voltammetry (DPV), cyclic voltammetry (CV) and chronoamperometry (CA). DPV measurements showed a linear relationship between oxidation peak current and concentration of PAR and UA in phosphate buffer (pH 7) over the concentration range 2 µM to 250 µM, and 10 µM to 400 µM, respectively. The analytical performance of this sensor has been evaluated for detection of PAR and UA in human serum and human urine with satisfactory results.     

对乙酰氨基酚在分子印迹膜修饰玻碳电极上的电化学行为及测定

以对乙酰氨基酚（PCT）为模板分子,甲基丙烯酸为功能单体,采用光引发原位聚合法在玻碳电极（GCE）表面聚合成膜,以甲醇-甲酸将模板分子洗脱,制得对乙酰氨基酚分子印迹膜修饰电极（MIP-GCE）,建立了该电极直接测定PCT的分析方法。结果表明,该传感器具有较高的选择性和灵敏度,PCT浓度在5.0×10-5~1.0×10-3 mol?L-1范围内与其峰电流呈良好的线性关系,检出限为1.4×10-6 mol?L-1。应用该法测定药物中PCT的含量,在干扰物质共存情况下的回收率为96%~105%。     

Electrochemical Determination of Phenolic Acids at a Zn/Al Layered Double Hydroxide Film Modified Glassy Carbon Electrode

A stable sensor for the determination of gallic acid (GA) and caffeic acid (CA) was fabricated by electrodeposition of Zn‐Al‐NO₃ layered double hydroxide film on a glassy carbon electrode (LDHf/GCE). A sensitive electrochemical method was achieved for the determination of GA and CA in a phosphate buffer solution (pH 3). The differential pulse voltammetry response of the LDHf/GCE to GA has a linear concentration range from 4 µM to 600 µM with a correlation coefficient of 0.9985 and the calculated detection limit of 1.6 µM at a signal‐to‐noise ratio of 3. The differential pulse voltammetry response of the LDHf/GCE to CA has a linear concentration range from 7 µM to 180 µM with a correlation coefficient of 0.9969 and the calculated detection limit of 2.6 µM at a signal‐to‐noise ratio of 3. The constructed sensor was applied to the determination of GA in commercial green tea samples.     

Simultaneous Determination of Paracetamol,Ascorbic Acid and Codeine by Differential Pulse Voltammetry on the Aluminum Electrode Modified by Thin Layer of Palladium

In the present work an aluminum electrode was modified with thin layer of metallic palladium. The ability of the electrode for electrooxidation and subsequent differential pulse voltammetric determination of paracetamol (PCT), ascorbic acid (AA) and codeine (CO) was evaluated. The results obtained indicated that a linear range from 0.1–3 mM and a detection limit of 5 μM for both three compounds is accessible. The peak separation of AA, PCT and CO is more than 300 mV large enough, allowed simultaneous determination of these compounds. The proposed method was applied for determination of AA, PCT and CO in some real samples.     

Highly Selective and Sensitive Detection of Dopamine in the Presence of Excessive Ascorbic Acid Using Electrodes Modified with C60‐Functionalized Multiwalled Carbon Nanotube Films

Electrochemical detection of dopamine (DA) in the presence of a large excess of ascorbic acid (AA) was investigated with a novel all‐carbon nanocomposite film of C₆₀‐MWCNTs (C₆₀‐functionalized multi‐walled carbon nanotubes) using a bare MWCNTs film as control. Although both films can selectively detect DA from AA by separating their oxidation potentials, the C₆₀‐MWCNTs film shows special selectivity and good sensitivity for detecting DA. On one hand, the C₆₀‐MWCNTs composite film shows a higher activity for DA oxidation with enhanced peak current. On the other hand, the C₆₀‐MWCNTs composite film effectively suppresses the oxidation of AA. Remarkably, it is found that the oxidation current of DA is over 2 times higher than that of AA even when the concentration of AA is about 3 to 4 orders of magnitude higher than that of DA. This offers a tremendous advantage for the simple and clean detection of DA free of the interfering AA signal in a real assay. Cyclic voltammetry, differential pulse voltammetry, and electrochemical impedance spectrometry are used to characterize the C₆₀‐MWCNTs composite film. These novel properties are interpreted to arise from the facile electron transfer between C₆₀ and MWCNTs in the C₆₀‐MWCNTs nanocomposite film.     

Selective Electrochemical Determination of Uric Acid in the Presence of Ascorbic Acid Using a Carbon Paste Electrode Modified with β‐Cyclodextrin

Uric acid (UA) was determined in the presence of ascorbic acid (AA) by using a carbon paste electrode modified superficially by a β‐cyclodextrin film (CPE/β‐CD). The surface carbon paste electrode was prepared applying a 30 cycles potential program and using a 1 M HClO₄+0.01 M β‐CD electrolytic solution. The UA and AA solutions were used to evaluate the electrode selectivity and sensitivity by cyclic voltammetric and amperometric methods. In these experiments the detection limit for UA was (4.6±0.01)×10^?6 M and the RSD calculated from the amperometric curves was 10%. From the data obtained it was possible to quantify UA in the urine and saliva samples. Selective detection of UA was improved by formation of an inclusion complex between β‐CD and UA. The results show that the CPE/β‐CD is a good candidate due to its selectivity and sensitivity in the UA determination in complex samples like the biological fluids.     

Highly Sensitive and Selective Determination of Dopamine Based on Graphite Nanosheet‐Nafion Composite Film Modified Electrode

A graphite nanosheet (GNS)‐Nafion modified glassy carbon (GC) electrode was prepared and used for highly sensitive and selective determination of dopamine (DA). The GNS‐Nafion/GC electrode displayed excellent electrocatalytic activities towards DA and ascorbic acid (AA). The selective determination of DA was carried out successfully in the presence of AA by differential pulse voltammetry. High sensitivity (3.695 μA μM^?1) and low detection limit (0.02 μM, S/N=3) for the DA detection were obtained. These good properties can be attributed to a large amount of edge plane defects presented on GNSs and the charge‐exclusion and concentration features of Nafion.     

Detection of Uric Acid in the Presence of Dopamine and High Concentration of Ascorbic Acid Using PDDA Modified Graphite Electrode

The properties of graphite electrode (Gr) modified with poly(diallyl dimethyl ammonium chloride) (PDDA) for the detection of uric acid (UA) in the presence of dopamine (DA) and high concentration of ascorbic acid (AA) have been investigated by cyclic voltammetry, differential pulse voltammetry and chronoamperometry. The polymer modified graphite electrode was prepared by a very simple method just by immersing the graphite electrode in PDDA solution for 20 minutes. The PDDA/Gr modified electrode displayed excellent electrocatalytic activity towards the oxidation of UA, DA and AA compared to that at the bare graphite electrode. The electrochemical oxidation signals of UA, DA and AA are well resolved into three distinct peaks with peak potential separations of 220 mV, 168 mV and 387 mV between AA‐DA, DA‐UA and AA‐UA respectively in cyclic voltammetry studies and the corresponding peak potential separations are 230 mV, 130 mV and 354 mV respectively in differential pulse voltammetry. The lowest detection limits obtained for UA, DA and AA were 1×10^?7 M, 2×10^?7 M and 800×10^?9 M respectively. The PDDA/Gr electrode efficiently eliminated the interference of DA and a high concentration of AA in the determination of UA with good selectivity, sensitivity and reproducibility. The modified electrode was also successfully applied for simultaneous determination of UA, DA and AA in their ternary mixture.     

Selective Determination of Quercetin Using Carbon Nanotube‐Modified Electrodes

Electrochemical detection of quercetin has been carried out on glassy carbon electrodes modified with carbon nanotubes and Nafion (GC/Nafion‐CNT). GC/Nafion‐CNT electrodes did not show passivation effect that occurs on the unmodified electrodes and displayed better stability and reproducibility. Quercetin oxidation was most favorable in acidic conditions and current gradually decreased as the solution pH increased. No oxidation was observed when two ? OH groups in a catechol moiety were fully deprotonated. These electrodes enabled selective determination of quercetin in the presence of interfering species such as ascorbic acid, uric acid, glucose, and catechol in large excess. Quantification of quercetin in a yellow onion has been made and favorably compared with reported values. Good selectivity and high sensitivity obtained by Osteryoung sSquare‐wave voltammetry can open new possibilities of direct quercetin determination in vegetables with a minimal sample treatment.     

Selective Detection of Ascorbic Acid Using Octacyanomolybdate‐Doped‐Glutaraldehyde‐Cross‐Linked Poly‐L‐Lysine Film Modified Glassy Carbon Electrode

The present work describes oxidation of ascorbic acid (AA) at octacyanomolybdate‐doped‐glutaraldehyde‐cross‐linked poly‐L ‐lysine (PLL‐GA‐Mo(CN) film modified glassy carbon electrode in 0.1 M H₂SO₄. The modified electrode has been successfully prepared by means of electrostatically trapping Mo(CN) mediator in the cationic film of glutaraldehyde‐cross‐linked poly‐L ‐lysine. The dependence of peak current of modified electrode in pure supporting indicates that the charge transfer in the film was a mixed process at low scan rates (5 to 200 mV s^?1), and kinetically restrained at higher scan rates (200 to 1000 mV s^?1). Cyclic voltammetry and rotating disk electrode (RDE) techniques are used to investigate the electrocatalytic oxidation of ascorbic acid and compared with its oxidation at bare and undoped PLL‐GA film coated electrodes. The rate constant of catalytic reaction k obtained from RDE analysis was found to be 9.5×10⁵ cm³ mol^?1 s^?1. The analytical determination of ascorbic acid has been carried out using RDE technique over the physiological interest of ascorbic acid concentrations with a sensitivity of 75 μA mM^?1. Amperometric estimation of AA in stirred solution shows a sensitivity of 15 μA mM^?1 over the linear concentration range between 50 and 1200 μM. Interestingly, PLL‐GA‐Mo(CN) modified electrode facilitated the oxidation of ascorbic acid but not responded to other electroactive biomolecules such as dopamine, uric acid, NADH, glucose. This unique feature of PLL‐GA‐Mo(CN) modified electrode allowed for the development of a highly selective method for the determination of ascorbic acid in the presence of interferents.     

Differential Pulse Voltammetric Determination of Selenocystine and Selenomethionine Using SAM nanoSe0/Vc/SeCys‐Film Modified Au Electrode

The SAM nanoSe⁰/Vc/SeCys‐film modified Au electrode has been prepared to determine selenocystine and selenomethionine. The AFM and SEM showed the special three‐dimensional (3D) network structure of the sol‐gel films. The affinity between nanoparticles and biomolecules created special chemical characters analyzed by the XRD and fluorescence. The modified electrode was characterized by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The modified films partly had resistance in the charge transduction of Fe(CN) , but the less electron‐transfer resistance. Differential pulse voltammetric (DPV) determination of selenoamino acids using SAM nanoSe⁰/Vc/SeCys‐film modified Au electrode was presented. In PBS (pH 7.0)+0.1 mol L^?1 NaClO₄ solution, selenoamino acids yielded a sensitive reduction peak at about +400±50 mV. The peak current had a linear relationship with the concentration of selenoamino acids in the range of 5.0×10^?8–1.0×10^?5 mol L^?1, and a 3σ detection limit of selenoamino acids was 1.2×10^?8 mol L^?1. The relative standard deviation of DPV signals of 0.50×10^?6 mol L^?1 selenoamino acids was 3.8% (n=8) using the same electrode and was 4.4% (n=5) when using three modified electrodes prepared at different times. The content of selenoamino acids in the organo‐selenium powder were determined by DPV. The results showed 71.5 μg g^?1 of SeCys and 65.1 μg g^?1 of SeMet in the organo‐selenium powder.     

Electrocatalytic Sensor for the Determination of Chemical Oxygen Demand Using a Lead Dioxide Modified Electrode

An amperometric method that makes use of a nano‐PbO₂ modified electrode as an electrocatalytic sensor for the determination of chemical oxygen demand (COD) is described. The sensor signal was observed as a result of the detection of the oxidation current due to electrocatalytic oxidation of organic compounds in the sample solution. This sensor responded linearly to the COD_Cr of standard samples in the range of 5–3 000 ppm and the detection limit was 2.5 ppm. When using the sensor to determine real samples, it displays short analysis time, simplicity and no sample pretreatment. The sensor was stable for over 20 days in real wastewater samples and has successfully been applied to the determination of COD in real wastewater samples.     

A Selective and Sensitive Method for Simultaneous Determination of Traces of Paracetamol and p‐Aminophenol in Pharmaceuticals Using Carbon Ionic Liquid Electrode

A reliable and simple electrochemical method has been proposed for the simultaneous determination of paracetamol (PAR) and p‐aminophenol (PAP) in pharmaceutical formulations. The oxidation and reduction peak potentials in cyclic voltammetry (CV) for PAR on carbon ionic liquid electrode (CILE) were occurred at 370 and 225 mV vs. Ag/AgCl, respectively at pH 7.0, while those for PAP on CILE appeared at 128 mV and 68 mV, respectively at the scan rate of 0.05 V s^?1. In comparison to the conventional carbon paste electrode, the apparent reversibility and kinetics of the electrochemical reactions of PAR and PAP were significantly improved on CILE. In differential pulse voltammetric technique, the peak potentials for PAR and PAP appeared at 345 and 130 mV, respectively, with the peak separation of 215 mV, sufficient for their simultaneous determination in samples containing these two species. The proposed method was used for simultaneous determination of PAR and PAP in tablets. PAR and PAP can be determined in the ranges of 2.0×10^?6–2.2×10^?3 M and 3.0×10^?7–1.0×10^?3 M, with the detection limits of 5.0×10^?7 and 1.0×10^?7 M (calculated by 3σ), respectively. The relative standard deviations for the determination of PAR and PAP were less than 2%.     

Thiol‐Functionalized Silica Thin Film Modified Electrode in Determination of Mercury Ions in Natural Water

The use of a thin thiol‐functionalized silica film modified glassy carbon electrode in the determination of Hg(II) ions in a natural water sample is described. A typical measurement involves two successive steps: a glassy carbon electrode coated with a thin mesoporous silica film containing 10% of mercaptopropyl groups, according to the MPTMS/TEOS ratio in the starting sol‐gel, was first immersed into the accumulation medium for 15 min, then removed, and finally transferred into a detection solution containing KCl 1.0 mol L^?1 where detection was performed by anodic stripping voltammetry. In this medium the previously accumulated Hg²⁺ species complexed by the thiol groups in an open circuit preconcentration step is then directly reduced at ?0.6 V during 60 s prior to be quantified by a differential pulse anodic scan from ?0.6 to 0.3 V (vs. Ag/AgCl). A stripping peak appeared at about ?0.01 V, which is directly proportional to the quantity of the analyte previously accumulated into the film. The best results were obtained under the following conditions: 100 mV pulse amplitude and 10 mV s^?1 scan rate in 1.0 mol L^?1 KCl solution pH 2.0. Using such parameters a linear dynamic range from 1.00 to 10.0×10^?8 mol L^?1 Hg(II) was observed with a limit of detection of 4.3 nmol L^?1 for an accumulation time of 15 min. Hg(II) spiked in a natural water sample was determined between 97.0 and 101.4% mean recovery at 10^?8 mol L^?1 level. The results indicate that this electrode is sensitive and selective for the Hg(II)determination.