Amperometric nonenzymatic determination of glucose based on a glassy carbon electrode modified with nickel(II) oxides and graphene

We have developed a stable and sensitive nonenzymatic glucose sensor by modifying a glassy carbon electrode (GCE) with a composite incorporating nickel(II) oxides and reduced graphene. The oxides were generated by directly electrodepositing nickel on the GCE with a graphene modifier using a multi-potential pulse process, and then oxidizing nickel to nickel(II) oxides by potential cycling. In comparison to the conventional nickel(II) oxides-modified GCE, this new nickel(II) oxides-graphene modified GCE (NiO-GR/GCE) has an about 1.5 times larger current response toward the nonenzymatic oxidation of glucose in alkaline media. The response to glucose is linear in the 20 μM to 4.5 mM concentration range. The limit of detection is 5 μM (at a S/N of 3), and the response time is very short (<3 s). Other beneficial features include selectivity, reproducibility and stability. A comparison was performed on the determination of glucose in commercial red wines by high-performance liquid chromatography (HPLC) and revealed the promising aspects of this sensor with respect to the determination of glucose in real samples.

Amperometric determination of L-cysteine using a glassy carbon electrode modified with palladium nanoparticles grown on reduced graphene oxide in a Nafion matrix

An amperometric sensor for L-Cys is described which consists of a glassy carbon electrode (GCE) that was modified with reduced graphene oxide placed in a Nafion film and decorated with palladium nanoparticles (PdNPs). The film was synthesized by a hydrothermal method. The PdNPs have an average diameter of about 10 nm and a spherical shape. The modified GCE gives a linear electro-oxidative response to L-Cys (typically at +0.6 V vs. SCE) within the 0.5 to 10 μM concentration range. Other figures of merit include a response time of less than 2 s, a 0.15 μM lower detection limit (at signal to noise ratio of 3), and an analytical sensitivity of 1.30 μA·μM^?1·cm^?2. The sensor displays selectivity over ascorbic acid, uric acid, dopamine, hydrogen peroxide, urea, and glucose. The modified GCE was applied to the determination of L-Cys in human urine samples and gave excellent recoveries.

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Graphical abstract Spherical palladium nanoparticles (PdNPs) on reduced graphene oxide-Nafion (rGO-Nf) films were synthesized using a hydrothermal method. This nanohybrid was used for modifying a glassy carbon electrode to develop a sensor electrode for detecting L-cysteine that has fast response (less than 2 s), low detection limit (0.15 μM), and good sensitivity (0.092 μA μM^-1 cm^-2).

     

Amperometric nonenzymatic determination of glucose via a glassy carbon electrode modified with nickel hydroxide and N-doped reduced graphene oxide

The authors describe a nonenzymatic glucose sensor that was obtained by electrochemical deposition and oxidization of metallic nickel on the surface of nitrogen-doped reduced graphene oxide (N-RGO) placed on a glassy carbon electrode (GCE). An analysis of the morphology and chemical structure indicated the composite to possess a well-defined vermicular Ni(OH)₂ nanorods combined with N-RGO. The electrochemical performance of the modified GCE with respect to the detection of glucose in 0.1 M NaOH was investigated by cyclic voltammetry and amperometry. The wrinkle and protuberance of N-RGO for loading of nanostructured Ni(OH)₂ are found to increase electrical conductivity, surface area, electrocatalytical activity and stability. The modified GCE displays a high electrocatalytic activity towards the oxidation of glucose in 0.1 M NaOH solution. The lower detection limit is 0.12 μM at an applied potential of +0.45 V (vs Ag/AgCl) (S/N=3), and the sensitivity is 3214 μA mM^?1 cm^?2. The modified GCE possesses long-term stability, good reproducibility and high selectivity over fructose, sucrose and lactose.

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Graphical abstract The composite of vermicular Ni(OH)₂ nanorods combined with N-doped reduced graphene oxide is a viable catalyst for non-enzymatic electrochemical sensing of glucose.

     

Voltammetric determination of N-acetylcysteine using a carbon paste electrode modified with copper(II) hexacyanoferrate(III)

The preparation and electrochemical characterization of a carbon paste electrode modified with copper(II) hexacyanoferrate(III) (CuHCF) as well as its behavior as electrocatalyst toward the oxidation of N-acetylcysteine were investigated. The electrochemical behavior of the modified electrode and the electrooxidation of N-acetylcysteine were explored using sweep linear voltammetry. The best voltammetric response was observed for a paste composition of 20% (w/w) copper(II) hexacyanoferrate(III) complex, acetate buffer solution at pH of 6.0 as the electrolyte and scan rate of 10 mV s^− 1. A linear voltammetric response for N-acetylcysteine was obtained in the concentration range from 1.2 × 10^− 4 to 8.3 × 10^− 4 mol L^− 1, with a detection limit of 6.3 × 10^− 5 mol L^− 1. The proposed electrode is useful for the quality control and routine analysis of N-acetylcysteine in pharmaceutical formulations.     

Voltammetric determination of cadmium(II) using a chemically modified electrode

An 1-(pyridylazo)-2-naphthol modified glassy carbon electrode has been investigated as sensor for the measurement of trace levels of Cd2+. Cd2+ is deposited on the surface of a PAN modified glassy carbon electrode at -1.10 V (vs. SCE) via forming Cd2+-PAN and subsequent reduction at the electrode. In the following step, Cd-PAN is oxidized, and voltammograms are recorded by scanning the potential in a positive direction. Calibration plots were found to be linear in the range 2 x 10(-8) mol/L to 8 x 10(-7) mol/L. The detection limit was 5 x 10(-10) mol/L, and the coefficient of variation, determined on one single electrode at a concentration of 5 x 10(-7) mol/L, was calculated to be 3.2% (n = 5). Using this new kind of modified electrode, trace levels of Cd(II) in water samples were determined; the average recovery was calculated to be 98.78%.     

Voltammetric determination of cadmium(II) using a chemically modified electrode

An 1-(pyridylazo)-2-naphthol modified glassy carbon electrode has been investigated as sensor for the measurement of trace levels of Cd²⁺. Cd²⁺ is deposited on the surface of a PAN modified glassy carbon electrode at –1.10 V (vs. SCE) via forming Cd²⁺–PAN and subsequent reduction at the electrode. In the following step, Cd-PAN is oxidized, and voltammograms are recorded by scanning the potential in a positive direction. Calibration plots were found to be linear in the range 2 × 10^–8 mol/L to 8 × 10^–7 mol/L. The detection limit was 5 × 10^–10 mol/L, and the coefficient of variation, determined on one single electrode at a concentration of 5 × 10^–7 mol/L, was calculated to be 3.2% (n = 5). Using this new kind of modified electrode, trace levels of Cd(II) in water samples were determined; the average recovery was calculated to be 98.78%. Received: 17 August 2000 / Revised: 19 December 2000 / Accepted: 27 December 2000     

Amperometric sandwich immunoassay for the carcinoembryonic antigen using a glassy carbon electrode modified with iridium nanoparticles,polydopamine and reduced graphene oxide

The authors describe a sandwich-type electrochemical immunoassay for sensitive determination of the carcinoembryonic antigen (CEA). It is based on the use of iridium nanoparticles (Ir NPs) acting as electrochemical signal amplifier on the surface of a glassy carbon electrode. At first, polydopamine-reduced graphene oxide (PDA-rGO) was employed to immobilize primary antibody (Ab₁) against CEA. Secondly, Ir-NPs were used as a support for the immobilization of secondary antibody (Ab₂) to afford signal labels. The large surface area of PDA-rGO and the excellent electro-oxidative H₂O₂-sensing properties of Ir NPs result in a sensitive assay for CEA. Operated best at a working voltage of ?0.6 V (vs. SCE), the assay has a linear range that extends from 0.5 pg?mL^?1 to 5 ng·mL^?1, and the lower detection limit is 0.23 pg?mL^?1. The immunosensor displays satisfactory reproducibility and stability, thus demonstrating a reliable immunoassay strategy for tumor biomarkers. It was applied to the determination of CEA in spiked serum samples.

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Graphical abstract Schematic of an amperometric sandwich immunoassay for the carcinoembryonic antigen using a glassy carbon electrode modified with polydopamine, reduced graphene oxide and iridium nanoparticles

     

Amperometric enzymatic determination of bisphenol A using an ITO electrode modified with reduced graphene oxide and Mn3O4 nanoparticles in a chitosan matrix

Microchimica Acta - The authors describe a nanostructured hybrid platform for amperometic determination of the plasticizer bisphenol A (BPA). It consists of two dimensional sheets of reduced...     

Photoelectrochemical determination of hydrogen peroxide using a gold electrode modified with fluorescent gold nanoclusters and graphene oxide

Nanocomposites consisting of gold nanoclusters and graphene oxide (AuNC/GO) were prepared and investigated with respect to the design of new sensors for hydrogen peroxide (H₂O₂). The AuNC/GO hybrid nanomaterials were deposited on a gold electrode by the layer-by-layer assembly method, where they showed enhanced photoelectrical and sensing properties. The presence of graphene oxide improves the photoinduced electron separation efficiency of the AuNCs, as well as the catalytic effect of AuNCs on the electroreduction of H₂O₂. Compared to an electrode modified with AuNCs only, the new electrodes display a more than ten-fold enhanced photocurrent at a working voltage of -500 mV (vs. Ag/AgCl), higher sensitivity for H₂O₂ (25.76 nA?mM^?1), lower LOD (2 μM) and extended linear range (from 30 μM to 5 mM). The sensors were applied to the determination of H₂O₂ extracted from living human umbilical vein endothelial cells stimulated by angiotensin II.

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Graphical abstract Graphene oxide (GO) not only improves the photoinduced charge separation efficiency of fluorescent gold nanoclusters (AuNCs) based photoelectrochemical sensors, but also enhances the catalytic property of AuNCs on the detection of hydrogen peroxide (H₂O₂).

     

Amperometric determination of nitric oxide at a carbon nanotube modified electrode with redox polymer coating

A novel chemically modified electrode based on an osmium complex-containing redox polymer film coated on single-walled carbon nanotube (SWNT) modified glassy carbon electrode (GCE) has been described for the determination of nitric oxide. The results showed that the oxidation current increased significantly at the SWNT/redox polymer coated GCE, as compared to that observed on a bare GCE- and SWNT-modified GCE. Amperometric measurement was carried out at the potential of +0.80?V (vs. Ag|AgCl) and the current response to NO was found to be directly proportional to its concentration in the range from 2.0?×??0^?? to 4.0?×??0^?? M, and the detection limit was estimated to be 5.0?×??0^?? M.     

Amperometric detection of nitric oxide using a glassy carbon electrode modified with gold nanoparticles incorporated into a nanohybrid composed of reduced graphene oxide and Nafion

Microchimica Acta - The authors show that the electrocatalytic performance toward the detection of nitric oxide (NO) can be enhanced by making use of gold nanoparticles (AuNP) in a matrix...     

High-sensitivity determination of Pb(II) and Cd(II) on a glassy carbon electrode modified with polypyrrole/sepiolite nanofibers

Polypyrrole-sepiolite (PPy/SPL) nanofibers were prepared by in situ chemical oxidation polymerization in the presence of sepiolite. A PPy/SPL composite modified glassy carbon electrode (PPy/SPL/GCE) was prepared and characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and electrochemical methods. Differential pulse anodic stripping voltammetry for the simultaneous determination of trace Pb(II) and Cd(II) was carried out at the PPy/SPL/GCE. Operational parameters such as the deposition potential and time, the amount of modified suspension, and the pH values were optimized for the purpose of determination of trace metal ions in 0.10 M acetate buffer solution. Under the optimal conditions, the stripping peak currents showed good linear relationships with Pb(II) and Cd(II) at concentration ranges of 5.0 × 10^–9?1.2 × 10^–6 M and 5.0 × 10^–9?1.2 × 10^–7 M, and the detection limits were 1.2 and 1.5 nM, respectively. The proposed method is applicable to the simultaneous determination of trace Pb(II) and Cd(II) in real water samples with the relative standard deviations of less than 4.4% and the recovery rates of 97.9?102.2%.     

A gold electrode modified with amino-modified reduced graphene oxide,ion specific DNA and DNAzyme for dual electrochemical determination of Pb(II) and Hg(II)

Multilayered reduced graphene oxide (rGO) was functionalized with amino groups by treatment with nitrogen plasma. Raman spectroscopy showed plasma treatment not to substantially alter the chemical structure of rGO and that a wide range of functional nitrogen groups is evenly incorporated into the carbon lattice. The amino-modified rGO was used to design an electrochemical biosensor in which a DNAzyme, substrate DNA and Pb(II) and Hg(II) binding DNA were immobilized on the amino-rGO placed on a gold electrode. The high concentration of amino groups and the rough surface of the rGO favor DNA immobilization. Heavy metal ions are bound to the surface via specific interaction between DNA and the two ions which are detected by electrochemical impedance spectroscopy at a potential of 0.2 V (vs. Ag/AgCl). The detection limits for Pb(II) and Hg(II) are as low as 7.8 and 5.4 pM, respectively, and the analytical ranges extend from 0.01 to 100 nM. The sensor is highly specific and stable and therefore represents a highly promising tool for use in environmental monitoring.

A nanofilm of reduced graphene oxide was first modified with amino groups by treatment with nitrogen plasma. A special DNA was then anchored to the surface to obtain a biosensor for simultaneous detection of Pb(II) and Hg(II). The sensor has detection limits as low as 7.8 and 5.4 pM and is highly selective.

     

Voltammetric determination of nitric oxide using a glassy carbon electrode modified with a nanohybrid consisting of myoglobin,gold nanorods,and reduced graphene oxide

Microchimica Acta - Myoglobin-modified gold nanorods incorporating reduced graphene oxide (rGO) were fabricated and deposited on a glassy carbon electrode (GCE) to obtain a sensor for nitric oxide...     

Electrochemical determination of dopamine and uric acid using a glassy carbon electrode modified with a composite consisting of a Co(II)-based metalorganic framework (ZIF-67) and graphene oxide

A composite was prepared from a Co(II)-based zeolitic imidazolate framework (ZIF-67) and graphene oxide (GO) by an in situ growth method. The material was electrodeposited on a glassy carbon electrode (GCE). The modified GCE was used for the simultaneous voltammetric determination of dopamine (DA) and uric acid (UA), typically at working potentials of 0.11 and 0.25 V (vs. SCE). The morphology and structure of the nanocomposite were characterized by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy and X-ray diffraction. The modified electrode exhibits excellent electroanalytical performance for DA and UA owing to the synergistic effect of the high electrical conductivity of GO and the porosity of ZIF-67. By applying differential pulse voltammetry, a linear response is found for DA in the 0.2 to 80 μM concentration range, and for UA between 0.8 and 200 μM, with detection limits of 50 and 100 nM (at S/N =?3), respectively. Further studies were performed on the effect of potential interferents, and on electrode stability and reproducibility. The modified GCE was applied to the simultaneous detection of DA and UA in spiked human urine and gave satisfying recoveries.

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Graphical abstract Schematic of the preparation procedure of GO-ZIF67 and electrochemical reaction mechanisms of UA and DA at the GO-ZIF67-modified glassy carbon electrode (GCE). GO: graphene oxide; ZIF-67: Co(II)-based zeolitic imidazolate framework.

     

Voltammetric determination of isoprenaline in pharmaceutical preparations using a copper(II) hexacyanoferrate(III) modified carbon paste electrode

The electroanalytical determination of isoprenaline in pharmaceutical preparations of a homemade carbon paste electrode modified with copper(II) hexacyanoferrate(III) (CuHCF) was studied by cyclic voltammetry. Several parameters were studied for the optimization of the sensor such as electrode composition, electrolytic solution, pH effect, potential scan rate and interferences in potential. The optimum conditions were found in an electrode composition (in mass) of 15% CuHCF, 60% graphite and 25% mineral oil in 0.5 mol l⁻¹ acetate buffer solution at pH 6.0. The analytical curve for isoprenaline was linear in the concentration range from 1.96×10⁻⁴ to 1.07×10⁻³ mol l⁻¹ with a detection limit of 8.0×10⁻⁵ mol l⁻¹. The relative standard deviation was 1.2% for 1.96×10⁻⁴ mol l⁻¹ isoprenaline solution (n=5). The procedure was successfully applied to the determination of isoprenaline in pharmaceutical preparations; the CuHCF modified carbon paste electrode gave comparable results to those results obtained using a UV spectrophotometric method.