Electrochemical determination of nitrite using a gold nanoparticles-modified glassy carbon electrode prepared by the seed-mediated growth technique.

Seed-mediated growth of gold nanoparticles on glassy carbon (GC) surfaces was developed. The field emission scanning electron microscopy (FE-SEM) and electrochemical characterization confirmed the effective attachment of gold nanoparticles on GC surface with such a wet-chemical method. The as-prepared gold nanoparticles attached glassy carbon electrode (Au/GCE) presented excellent catalytic ability toward the oxidation of nitrite. Compared with bare GCE and planar gold electrode, the Au/GCE obviously decreased the overpotential of nitrite oxidation and improved the peak current. The catalytic current was found to be linearly proportional to the nitrite concentration in the range of 1 x 10(-5) - 5 x 10(-3) M, with a detection limit of 2.4 x 10(-6) M. The Au/GCE was successfully applied to the electrochemical determination of nitrite in a real wastewater sample, showing excellent stability and anti-interference ability.     

Development of a paper-based,inexpensive, and disposable electrochemical sensing platform for nitrite detection

Electrochemical techniques are attractive for nitrite detection owing to their intrinsic advantages. However, traditional electrochemical sensors often suffer from the effects of fouling due to the adsorption of oxidation products on the electrode surface. In this work, a paper-based, inexpensive, disposable electrochemical sensing platform was developed for nitrite analysis based on a simple and efficient vacuum filtration system. Taking advantage of the physicochemical properties of graphene nanosheets and gold nanoparticles, the mass transport regime of nitrite at the paper-based electrode was thin layer diffusion rather than planar diffusion. In comparison with the electrochemical responses of commercial gold electrodes and glassy carbon electrodes (GCE), a considerably larger current signal was seen at the paper-based sensing interface, which significantly improved its sensitivity for nitrite detection. In particular, the paper-based electrode was a disposable sensing device, so that it effectively avoided the fouling effect arising from the adsorption of oxidation products. Moreover, the paper-based sensing platform made it possible to determine nitrite in environmental and food samples in an accurate, convenient, inexpensive, and reproducible way, indicating that the proposed system is promising for practical applications in environmental monitoring and public health.     

A Sensitive Electrochemical Sensor for Voltammetric Determination of Ganciclovir Based on Au‐ZnS Nanocomposite

An electrode modified with ZnS and gold nanoparticles (Au‐ZnS NPs) is introduced for highly sensitive voltammetric determination of ganciclovir (GCV). Surface structure and topography of the modified electrode was studied by SEM, EDX and XRD techniques. Electrochemical oxidation of GCV was investigated by cyclic (CV) and square wave voltammetry (SWV) in Briton‐Robinson buffer solution (pH 1.5). The results showed that electrochemical oxidation of GCV at the Au‐ZnS modified glassy carbon electrode (GCE) is irreversible and exhibited diffusion controlled electrode process over the pH range from 1.0 to 6.0. The oxidation potential peak and pH relationship showed that electrons and protons were transferred simultaneously over the electrochemical oxidation process. Using the proposed sensor, the linear calibration curves were obtained in the ranges of 0.04–1.50 μM and 1.5–70.0 μM with detection limit of 0.01 μM GCV by SWV technique. The modified electrode was successfully applied as a sensitive, reproducible and repeatable sensor for determination of the trace amount of GCV in human serum, urine and cymevene vials. Reasonable results were obtained from comparing the measurements of the real samples by the new sensor to high performance liquid chromatography (HPLC) as a standard method.     

A MnOOH‐Polyaniline Nanocomposite Modified Gold Electrode for Electrochemical Sensing of Nitrite

A novel non‐enzymatic nitrite sensor was fabricated by immobilizing MnOOH‐PANI nanocomposites on a gold electrode (Au electrode). The morphology and composition of the nanocomposites were investigated by transmission electron microscopy (TEM ) and Fourier transform infrared spectrum (FTIR ). The electrochemical results showed that the sensor possessed excellent electrocatalytic ability for NO₂⁻ oxidation. The sensor displayed a linear range from 3.0 μmol•L⁻¹ to 76.0 mmol•L⁻¹ with a detection limit of 0.9 μmol•L⁻¹ (S/N = 3), a sensitivity of 132.2 μA •L•mol⁻¹•cm⁻² and a response time of 3 s. Furthermore, the sensor showed good reproducibility and long‐term stability. It is expected that the MnOOH‐PANI nanocomposites could be applied for more active sensors and used in practice for nitrite sensing.     

Electrochemical Codeposition of Platinum and Molybdenum Oxides: Formation of Composite Films with Distinct Electrocatalytic Activity for Hydrogen Peroxide Detection

The electrochemical properties of gold electrode surfaces modified by molybdenum oxide films intercalated with platinum microparticles have been described. The incorporation of Pt microparticles at the oxide film was characterized by PIXE (particle induced X‐ray emission) spectroscopy. The modified electrode showed electrochemical activity at around ?0.5 V in 50 mmol L^?1 Na₂SO₄ supporting electrolyte (pH 3), corresponding to the reduction of protons at platinum sites and further transfer of hydrogen atoms to form reduced molybdenum oxides (bronzes). At 0.1 V, the MoO₃ / Pt electrode showed a better performance for hydrogen peroxide oxidation than on platinized gold electrodes. The solution pH has a marked effect on the voltammetric profile and best responses for hydrogen peroxide were obtained at the 5.0 to 6.0 pH range. The activation of the electrode by polarization at negative potentials was also studied and a mechanism by which more platinum sites are available as a consequence of this process was proposed. Calibration plots for hydrogen peroxide were highly linear (r=0.9989) in the 0.2 to 1.6 mmol L^?1 concentration range, with a relative standard deviation (RSD)<1%.     

Electrocatalytical Oxidation of Nitrite and Its Determination Based on Au@Fe3O4 Nanoparticles

A promising electrochemical nitrite sensor was fabricated by immobilizing Au@Fe₃O₄ nanoparticles on the surface of L ‐cysteine modified glassy carbon electrode, which was characterized by scanning electron microscopy, X‐ray photoelectron spectroscopy, electrochemical impedance spectroscopy and cyclic voltammetry. The proposed sensor exhibited excellent electrocatalytic activity toward nitrite oxidation. The kinetic parameters of the electrode reaction process were calculated, (1–α)n_α was 0.38 and the heterogeneous electron transfer coefficient (k) was 0.13 cm s^?1. The detection conditions such as supporting electrolyte and pH value were optimized. Under the optimized conditions, the linear range for the determination of nitrite was 3.6×10^?6 to 1.0×10^?2 M with a detection limit of 8.2×10^?7 M (S/N=3). Moreover, the as‐prepared electrode displayed good stability, repeatability and selectivity for promising practical applications.     

Amperometric nitrite biosensor based on a gold electrode modified with cytochrome c on Nafion and Cu-Mg-Al layered double hydroxides

An amperometric biosensor for nitrite was prepared by immobilizing cytochrome c (Cyt c) on a gold electrode that was modified with Nafion and a Cu-Mg-Al layered double hydroxide (Cu-LDH). The Cu-LDH was characterized by Fourier transform infrared spectroscopy and powder X-ray diffraction. The UV-visible spectrum suggests that Cyt c retains its native conformation in the modified film. The direct electrochemical investigation indicated that the composite film represents a good platform for the immobilization of Cyt c as well as an excellent promoter for the electron transfer between Cyt c and the gold electrode. Moreover, the biosensor showed a remarkable bioelectrocatalytic activity for the oxidation of nitrite with a linear range from 0.75 to 123 μM. The detection limit is 2?×?10^?7 M (S/N?=?3). The biosensor was successfully applied to the determination of nitrite in food samples.     

Electrochemical Characterization of Self‐Assembled Monolayer of a Novel Manganese Tetrabenzylthio‐Substituted Phthalocyanine and Its Use in Nitrite Oxidation

Manganese phthalocyanine MnPc(SPh)₄ has been synthesized and used to form self assembled monolayers on gold electrodes. The well packed SAM monolayer was characterized by analyzing the blocking of a number of Faradic processes by cyclic voltammetry, evaluating the electrical characteristics of the modified electrode by electrochemical impedance and imaging the modified surface by electrochemical scanning microscopy. Finally, MnPc(SPh)₄‐SAM modified electrode displayed an electrocatalytic behavior toward the oxidation of nitrite.     

Electrochemical study and flow-injection amperometric detection of trace NO(2)(-) at CuPtCl(6) chemically modified electrode

A thin film of mixed-valent CuPtCl₆ is deposited on a glassy carbon electrode by continuous cyclic scanning in a solution containing 3×10⁻³ M CuCl₂+3×10⁻³ M K₂PtCl₆+1 M KCl in the potential range from 700 to −800 mV. The cyclic voltammetry is used to study the electrochemical behaviors of nitrite on CuPtCl₆/GC modified electrode and the electrode displays a good catalytic activity toward the oxidation of nitrite. The effects of the film thickness, pH, the electrode stability and precision have been evaluated. Experiments in flow-injection analysis are performed to characterize the electrode as an amperometric sensor for the detection of nitrite. The modified electrode shows a wide dynamic range, quite a low detection limit and short response time. The linear relationship between the flow-injection peak currents and the concentrations of nitrite is at a range of 1×10⁻⁷–2×10⁻³ M with a detection limit of 5×10⁻⁸ M.     

Lab‐on‐a‐Chip Sensor with Evaporated Bismuth Film Electrode for Anodic Stripping Voltammetry of Zinc

In this work, we report on the development of a lab‐on‐a‐chip electrochemical sensor that uses an evaporated bismuth electrode to detect zinc using square wave anodic stripping voltammetry. The microscale electrochemical cell consists of a bismuth working electrode, an integrated silver/silver chloride reference electrode, and a gold auxiliary electrode. The sensor exhibits a linear response in 0.1 M acetate buffer at pH 6 with zinc concentrations in the 1–30 μM range and a calculated detection limit of 60 nM. The sensor successfully detected zinc in a bovine serum extract and the results were corfirmed by independent AAS measurements. Our results demonstrate the advantageous qualities of this lab‐on‐a‐chip electrochemical sensor for clinical applications, which include small sample volume (µL scale), reduced cost, short response time and high accuracy at low concentrations of analyte.     

A novel nitrite sensor based on poly-1-naphthylamine doped by a ferrocenesulfonic-acid-modified electrode

A novel sensor for detecting nitrite based on poly-1-naphthylamine doped by a ferrocenesulfonic acid (PNAFc) modified electrode has been proposed. X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM) have confirmed that ferrocene-sulfonic acid (Fc) can be doped in poly-1-naphthylamine (PNA) and enhances its electrochemical activity. In a nitrite solution, the PNAFc electrode shows an excellent electrocatalytic activity for the oxidation of nitrite. Based on differential pulse voltammetry (DPV), the response was evaluated with respect to pH, scan rate, temperature, and other variables. The optimum analytical conditions for the determination of nitrite were established. Under optimum conditions, the linear range for nitrite determination was from 0.5 to 100 μM with a detection limit of 0.5 μM. The stability and anti-interference ability of the PNAFc electrode were also evaluated. The results indicate that this sensor is feasible for the determination of nitrite in real water samples. The text was submitted by the authors in English.     

Electrocatalytic Oxidation and Determination of Nitrite at Multi‐walled Carbon Nanotubes Modified Carbon Ceramic Electrode

In the present work, the electrochemical oxidation of nitrite on carbon ceramic electrode (CCE) modified with multi‐walled carbon nanotubes (MWCNTs) was investigated. The modified electrode exhibited catalytic activity toward the electrooxidation of nitrite. Experimental parameters such as solution pH, scan rate, concentration of nitrite and nanotubes amount were studied. It was shown nitrite can be determined by differential pulse voltammetry (DPV) and hydrodynamic amperometry (HA) using the modified electrode. Under the optimized conditions the calibration plots are linear in the concentration ranges of 15‐220 and 50‐3000 μM with limit of detections of 4.74 and 35.8 μM for DPV and HA, respectively. The modified electrode was successfully applied for analysis of nitrite in spinach sample. The results were favorbly compared to those obtained by UV‐Visible spectrophotometric method. The results of the analysis suggest that the proposed method has promise for the routine determination of nitrite in the examined products.     

Catalytic Detection of Iodide at Cationic Kaolinite Modified Gold Electrode in Presence of Thiosulfate

A gold electrode modified by a thin film of cationic kaolinite was used for the electrochemical detection of iodide in aqueous solution in the presence of thiosulfate. At gold electrode, iodide showed two electrochemical systems in the potential range explored (0.10 V to 0.85 V). The pH‐independent system was assigned to the redox couple I₂/I^? and the pH‐dependent one assigned to the redox couple HIO/ . For increased amount of thiosulfate the oxidation peak intensity of the first system increases sharply followed by the gradual decrease of the reduction peak, due to the chemical reaction between thiosulfate and oxidized iodide. The calibration curve in the presence of excess thiosulfate resulted in an increase of the sensitivity by a factor of 7. To improve this sensitivity, the bare gold electrode was coated by a thin film of an anionic exchanger kaolinite, obtained by grafting the ionic liquid (1‐(2‐hydroxyethyl)‐4‐(tert‐butyl) pyridinium chloride). Accumulation‐detection method yielded a spectacular increase of the oxidation peak current of iodide in the presence of thiosulfate ions. At optimized experimental conditions, a sensitivity of 2.45 μA.μM^?1 and a detection limit of 65 nM were obtained. The method was successfully applied for total iodine determination in povidone?iodine formulation.     

Nanocellulose/Carbon Nanoparticles Nanocomposite Film Modified Electrode for Durable and Sensitive Electrochemical Determination of Metoclopramide

A novel electrochemical sensor based on nanocellulose‐carbon nanoparticles (NC‐CNPs) nanocomposite film modified glassy carbon electrode (GCE) is developed for the analysis of metoclopramide (MCP). Atomic force microscopy, scanning electron microscopy and electrochemical impedance spectroscopy were used to characterize the roughness, surface morphology and performance of the deposited modifier film on GCE. SEM image demonstrated that modifier nanoparticles are uniformly deposited on GCE, with an average size of less than 50 nm. The electrochemical behavior of MCP and its oxidation product is studied using linear sweep and cyclic voltammetry over a wide pH range on NC‐CNPs modified glassy carbon electrode. The results revealed that the oxidation of MCP is an irreversible and pH‐dependent process that proceeds in an adsorption‐controlled mechanism and results in the formation of a main oxidation product, which adsorbs on the surface of NC‐CNPs/ GCE. The modified electrode showed a distinctive anodic response towards MCP with a considerable enhancement (49 fold) compared to the bare GCE. Under the optimized conditions, the modified electrode exhibited a wide linear dynamic range of 0.06–2.00 µM with a detection limit of 6 nM for the voltammetric determination of MCP. The prepared modified electrode showed several advantages such as simple preparation method, high stability, reproducibility, and repetitive usability. The modified electrode is successfully applied for the accurate determination of trace amounts of MCP in pharmaceutical and clinical preparations.     

Hydroxyl radicals electrochemically generated in situ on a boron-doped diamond electrode

The hydroxyl radicals electrochemically generated in situ on a boron-doped diamond (BDD) electrode have been investigated for the first time in different electrolyte media, over the whole pH range between 1 and 11. A more extensive characterisation of BDD electrochemical properties is very important to understand the reactivity of organic compounds towards electrochemical oxidation on the BDD electrode, which is related to their interaction with adsorbed hydroxyl radicals due to water oxidation on the electrode surface. An oxidation peak corresponding to the transfer of one electron and one proton was observed in pH <9 electrolytes, associated with the water discharge process and electrochemical generation of hydroxyl radicals, which can interact and enhance the electro-oxidation of organic compounds. In pH >9 electrolytes the electrochemical generation of hydroxyl radicals was not observed; ammonia buffer electrolyte gave a pH-independent peak corresponding to the ammonia oxidation reaction. Additionally, for most pH values studied, a few small peaks associated with the electrochemical interaction between non-diamond carbon species on the doped diamond electrode surface and the electrolyte were also seen, which suggests that the doped diamond is relatively unreactive, but not completely inert, and the electrogenerated hydroxyl radicals play a role as mediator in the oxidation of organics.     

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.     

原位电化学还原制备石墨烯修饰玻碳电极及其对亚硝酸根离子的电催化氧化性能

通过原位电化学还原直接制备石墨烯修饰玻碳电极,并用电化学阻抗谱（EIS）和扫描电子显微镜（SEM）对其进行了表征,研究了亚硝酸根离子（NO2-）在石墨烯修饰玻碳电极上的电化学行为.结果表明：石墨烯修饰玻碳电极对NO2-的氧化反应有良好的电催化活性,NO2-的浓度与峰电流呈良好的线性关系,且在pH 7.0的磷酸盐缓冲液（PBS）中其氧化峰电流最高.利用该方法测定了模拟废水中NO2的含量,结果令人满意.     

Electrochemical behavior of dopamine at a quercetin-SAM-modified gold electrode and analytical application

A stable quercetin–thioglycolic acid-modified gold electrode (Qu–TCA/Au) was prepared as a self-assembled monolayer (SAM) and its electrochemical behavior was investigated by electrochemical methods. In 0.05-M phosphate buffer solution (pH 7.0) quercetin exhibits quasi-reversible signals at the Qu–TCA/Au electrode. The stability of the quercetin-modified gold electrode is very good. The quercetin self-assembled monolayer is an effective mediator for the oxidation of dopamine, which was investigated by cyclic voltammetry and differential pulse voltammetry. Ascorbic acid does not interfere with determination of dopamine at an electrode modified with a mixture of quercetin–thioglycolic acid and quercetin–11-mercaptoundecanoic acid. This modification allows dopamine to be determined in the presence of ascorbic acid in the range from 3×10^–5 to 3×10^–4 M. The detection limit is 1×10^–6 M. Scanning electrochemical microscopy (SECM) was employed to study the electrochemical performances of the modified gold electrode indicating different feedback modes at differently modified surfaces.     

Electrochemical Oxidation of Rutin

An electrochemical investigation of rutin oxidation on a glassy carbon electrode was carried out using cyclic voltammetry, differential pulse voltammetry and square‐wave voltammetry over a wide pH interval. The electrochemical oxidation is a complex process, which proceeds in a cascade mechanism, related with the 4‐hydroxyl groups of the rutin molecule. The catechol 3′,4′‐dihydroxyl group is the first to be oxidized by a two‐electron – two‐proton reversible oxidation reaction, followed by an irreversible oxidation reaction due to the 5,7‐dihydroxyl group. Both mechanisms are pH dependent. An adsorption process is also observed and the oxidation products block the electrode surface.     

Electrochemical Detection of Nitric Oxide on a SWCNT/RTIL Composite Gel Microelectrode

Single walled carbon nanotubes (SWCNT) and room temperature ionic liquid (RTIL) were used to make a gel microelectrode for studies of the oxidation of nitric oxide (NO). The Faraday response of the gel microelectrode was contributed from two components: an outside‐surface microdisk and a thin‐layer cell formed by inner porous electrode materials, and enhanced by the thin‐layer effect. An EC mechanism, electrochemical NO oxidation followed by a chemical oxidation, was proposed. The gel microelectrode with a Nafion coating eliminated interferences from nitrite and some biomolecules, improved stability, and had a linear response range from 100 nM to 100 μM.