Electrochemical and ESR study of the mechanism of oxidation of phenazine-di-N-oxide in the presence of cyclohexanol on glassy carbon and single-walled carbon nanotube electrodes

The mechanism of oxidation of phenazine-di-N-oxide in the presence of cyclohexanol was studied by cyclic voltammetry on glassy carbon (GC) and single-walled carbon nanotube (SWCNT) electrodes in 0.1 M LiClO₄ solutions in acetonitrile. The effect of cyclohexanol on the shape of the cyclic voltammograms of phenazine-di-N-oxide and the intensity of the ESR signal of its radical cation was investigated. It was shown by ESR that the products of the one-electron oxidation and reduction of phenazine-di-N-oxide were radical cations and anions. The catalytic currents were recorded during the oxidation of phenazine-di-N-oxide on the SWCNT and GC electrodes in the presence of cyclohexanol. The results were explained in terms of the E₁C₁E₂C₂ mechanism of the two-stage electrode process characterized by the catalytic current recorded at the second electrode stage. The overall two-electron catalytic oxidation of cyclohexanol in the complex with the phenazine-di-N-oxide radical cation was assumed to occur. It was shown that SWCNT electrodes can be used in the electrocatalytic oxidation of organic compounds in the presence of the electrochemically generated phenazine-di-N-oxide radical cation.     

Carbon nanotube detectors for microchip CE: comparative study of single-wall and multiwall carbon nanotube, and graphite powder films on glassy carbon, gold, and platinum electrode surfaces

The performance of microchip electrophoresis/electrochemistry system with carbon nanotube (CNT) film electrodes was studied. Electrocatalytic activities of different carbon materials (single-wall CNT (SWCNT), multiwall CNT (MWCNT), carbon powder) cast on different electrode substrates (glassy carbon (GC), gold, and platinum) were compared in a microfluidic setup and their performance as microchip electrochemical detectors was assessed. An MWCNT film on a GC electrode shows electrocatalytic effect toward oxidation of dopamine (E(1/2) shift of 0.09 V) and catechol (E(1/2) shift of 0.19 V) when compared to a bare GC electrode, while other CNT/carbon powder films on the GC electrode display negligible effects. Modification of a gold electrode by graphite powder results in a strong electrocatalytic effect toward oxidation of dopamine and catechol (E(1/2) shift of 0.14 and 0.11 V, respectively). A significant shift of the half-wave potentials to lower values also provide the MWCNT film (E(1/2) shift of 0.08 and 0.08 V for dopamine and catechol, respectively) and the SWCNT film (E(1/2) shift of 0.10 V for catechol) when compared to a bare gold electrode. A microfluidic device with a CNT film-modified detection electrode displays greatly improved separation resolution (R(s)) by a factor of two compared to a bare electrode, reflecting the electrocatalytic activity of CNT.     

A sensitive and selective nitrite sensor based on a glassy carbon electrode modified with gold nanoparticles and sulfonated graphene

We describe a highly sensitive and selective amperometric sensor for the determination of nitrite. A glassy carbon electrode was modified with a composite made from gold nanoparticles (AuNPs) and sulfonated graphene (SG). The modified electrode displays excellent electrocatalytic activity in terms of nitrite oxidation by giving much higher peak currents (at even lower oxidation overpotential) than those found for the bare electrode, the AuNPs-modified electrode, and the SG-modified electrode. The sensor has a linear response in the 10 μM to 3.96 mM concentration range, a very good detection sensitivity (45.44 μA mM^?1), and a lower detection limit of 0.2 μM of nitrite. Most common ions and many environmental organic pollutants do not interfere. The sensor was successfully applied to the determination of nitrite in water samples, and the results were found to be consistent with the values obtained by spectrophotometry.

Glassy carbon electrode modified with poly-Neutral Red for photoelectrocatalytic oxidation of NADH

A new approach is described for the photoelectrocatalytic oxidation of Reduced ß-Nicotinamide Adenine Dinucleotide (NADH). It is based on a glassy carbon electrode (GCE) modified with a film of poly-Neutral Red (poly-NR) that is obtained by electropolymerization. Electrochemical measurements revealed that the modified electrode displays electrocatalytic and photo-electrocatalytic activity towards oxidation of NADH. If irradiated with a 250-W halogen lamp, the electrode yields a strongly increased electrocatalytic current compared to the current without irradiation. Amperometric and photo-amperometric detection of NADH was performed at +150 mV vs. Ag/AgCl/KCl_sat and the currents obtained are linearly related to the concentration of NADH. Linear calibration plots are obtained in the concentration range from 1.0 μM to 1.0 mM for both methods. However, the slope of the current-NADH concentration curve of the photo-electrocatalytic procedure was 2-times better than that obtained without irradiation.

Electrochemical determination of nitrite via covalent immobilization of a single-walled carbon nanotubes and single stranded deoxyribonucleic acid nanocomposite on a glassy carbon electrode

A novel method has been developed for determination of nitrite by modifying the surface of a glassy carbon electrode (GCE) using single-walled carbon nanotubes with covalently immobilized single-strand deoxyribonucleic acid. The modified electrodes were characterized by field emission scanning electron microscopy, X-ray photoelectron spectroscopy, and electrochemical techniques. The results demonstrate that the nanotube-DNA nanocomposite has been successfully immobilized on the surface of the GCE. The new electrode, under optimum conditions at room temperature, exhibits excellent electrocatalytic activity towards the oxidation of nitrite, with a significantly reduction of the overpotential. The linear range for the detection of nitrite is from 0.6 to 540 μM, with a sensitivity of 0.216 μA?μM^?1, and a detection limit as low as 0.15 μM. The electrode showed good reproducibility and high stability and was successfully used to analyze nitrite in water and sausage samples.     

Glassy carbon electrodes modified with single walled carbon nanotubes and cobalt phthalocyanine and nickel tetrasulfonated phthalocyanine: Highly stable new hybrids with enhanced electrocatalytic performances

We report here a fast procedure to modify glassy carbon (GC) electrode using commercially available unsubstituted cobalt phthalocyanine (CoPc) and tetrasulfonated substituted nickel phthalocyanine (NiTSPc) simply adsorbed on oxidized single walled carbon nanotubes SWCNT. The electrocatalytic activity of the resulting SWCNT-MPc nanocomposite materials was evaluated toward the oxidation of two biologically relevant molecules, namely 2-mercaptoethanol (2-ME) and nitric oxide (NO). The obtained electrodes are highly stable under hydrodynamic conditions and the tailored hybrid surfaces allow enhancing electron transfer for the electrocatalytic oxidation of 2-ME and NO.     

A novel nitrite sensor fabricated through anchoring nickel-tetrahydroxy-phthalocyanine and polyethylene oxide film onto glassy carbon electrode by a two-step covalent modification approach

In this paper, we present a two-step covalent modification approach to fabricate a novel nitrite sensor through anchoring nickel-tetrahydroxy-phthalocyanine (NiPc(OH)₄) and polyethylene oxide (PEO) onto a glassy carbon electrode (GCE). The surface morphology of the prepared NiPc(OH)₄/PEO composite films under different dry conditions was characterized by scanning electron microscopy (SEM). The electrochemical behavior of NiPc(OH)₄/PEO composite film modified GCE toward the catalytic oxidation of nitrite in pH 7.0 phosphate buffer solution (PBS) was investigated by cyclic voltammetry (CV). After drying under an infrared lamp, the fabricated sensor showed a pronounced electrocatalytic activity improvement toward the oxidation of nitrite and led to a significant decrease in the anodic overpotentials compared with bare GCE, which should be ascribed to the synergistic effect of NiPc(OH)₄ and PEO, as well as the enlarged electrochemical effective surface area after drying. Using differential pulse voltammetry (DPV), the sensor gave a linear response to nitrite over the concentration range of 0.1–5,300 μM, with a detection limit of 0.0522 μM. The nitrite sensor exhibits good sensitivity, selectivity, and stability and has been applied for the determination of nitrite in water samples.     

Copper hydroxide nanostructure-modified carbon ionic liquid electrode as an efficient voltammetric sensor for detection of metformin: a theoretical and experimental study

The electrocatalytic oxidation of metformin (MET) was investigated at Cu(OH)₂ nanoparticle-modified carbon ionic liquid electrode (Cu(OH)₂/CILE). This electrode exhibited excellent characteristic for the electrocatalytic oxidation of metformin at the potential of +0.6 V with good sensitivity and selectivity. The presence of Cu(OH)₂ nanostructures in the composite electrode leads to the appearance of oxidation peak of MET. Under optimal experimental conditions, the peak current response increased linearly with metformin concentration over the range of 1 µM–4 mM. The detection limit of the method is 0.5 µM. Moreover, the closer look was taken at the electronic properties of MET and its Cu (II) complexes such as frontier molecular orbital (HOMO and LUMO) and binding interaction energies using density functional theory. Effect of pH was also investigated at B3LYP/6-311++g** level. Theoretical results confirmed the experimental evidences of Cu (II) complexation. Therefore, Ease of preparation, wide linear range, low overpotential, high sensitivity and selectivity provide the possibility of applying this method for the detection of MET in biological samples.     

Electrochemical application of titanium dioxide nanoparticle/gold nanoparticle/multiwalled carbon nanotube nanocomposites for nonenzymatic detection of ascorbic acid

Titanium dioxide nanoparticle/gold nanoparticle/carbon nanotube (TiO₂/Au/CNT) nanocomposites were synthesized, and then characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy dispersive X-ray spectroscopy (EDX). A TiO₂/Au/CNT nanocomposite-modified glassy carbon (GC) electrode was prepared using the drop coating method and was investigated using electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), differential pulse voltammetry (DPV), and amperometric current–time response (I-T). The modified material is redox-active. The nonenzymatically detected amount of ascorbic acid (AA) on the TiO₂/Au/CNT electrode showed a linear relationship with the AA concentration, for concentrations from 0.01 to 0.08 μM; the sensitivity was 117,776.36 μA?·?cm^?2?·?(mM)^?1, and the detection limit was 0.01 μM (S/N?=?3). The results indicated that the TiO₂/Au/CNT nanocomposite-modified GC electrode exhibited high electrocatalytic activity toward AA. This paper describes materials consisting of a network of TiO₂, Au, and MWCNTs, and the investigation of their synergistic effects in the detection of AA.     

Electrochemical behavior of methyl parathion and its sensitive determination at a glassy carbon electrode modified with ordered mesoporous carbon

Ordered mesoporous carbon (OMC) was synthesized and used to modify the surface of a glassy carbon (GC) electrode. Due to the unique properties of OMC, a decrease in the overvoltage of the reduction potential of methyl parathion (MP) (to ca. 219 mV) and a 76-fold increase in the peak current are observed (compared with a bare GC electrode). The absorption capacity of the surface of the electrode for MP was determined by chronocoulometry. The results show that the Г value of the modified electrode (2.34?×?10^–9 mol cm^–2) is 9.5 times as large as that of the GC electrode (2.47?×?10^–10 mol cm^–2). The new electrode exhibits synergistic electrocatalytic and accumulative effects on MP. MP can be determined by linear sweep voltammetry (LSV) which displays a linear relationship between peak current and MP concentration in the range from 0.09 to 61 μM, with a detection limit as low as 7.6 nM (at an S/N of 3) and after an accumulation at 0 V for 5 min. The electrode was successfully applied to the determination of MP in spiked lake water samples.

Electrooxidation of Nitric Oxide at a Glass Carbon Electrode Modified with Functionalized Single-walled Carbon Nanotube

The electrocatalytic oxidation of nitric oxide(NO) at a glass carbon electrode(GC) modified with functionalized single-walled carbon nanotubes(SWCNTs) was investigated by cyclic voltammetry(CV) and electrochemical impedance spectroscopy(EIS).It was found that the SWCNT modified electrode could speed greatly up the electron transfer rate compared with the bare GC electrode.After the SWCNT was treated with alkali or mixed acids,the reaction rate and activation energy of NO electrooxidation were changed to different extent.Chemical modification of the SWCNT surface is one of the most powerful methods to change the sensitivity of NO electrooxidation reaction.The modified electrode with SWCNT obtained by the firstly alkali treatment and then the mixed acids treatment was the best one for NO electrooxidation,the result of CV was also confirmed by that of EIS.The anodic processes of NO were recognized more clearly by exploring the reaction mechanism of NO electrooxidation at the SWCNT modified electrode.     

A new sensor architecture based on carbon Printex 6L to the electrochemical determination of ranitidine

A glassy carbon electrode (GCE) modified with carbon Printex 6L (Printex6L/GCE) as a novel sensor is proposed. A morphological study was carried out using scanning electron microscopy, and an electrochemical characterization of the proposed electrode was performed by cyclic voltammetry (CV) using [Fe(CN)₆]^4? as a redox probe. With the incorporation of the carbon Printex 6L film onto the GCE surface, the [Fe(CN)₆]^4? analytical signal was substantially increased and the difference between the oxidation and reduction potentials (ΔE _p) decreased, a characteristic of the electrocatalytic effect. Furthermore, the use of carbon Printex 6L film resulted in an 84 % increase in the oxidation current and a 123 % increase in the reduction current. Faster charge transfer was observed at the proposed electrode/electrolyte interface during CV when compared with GCE. The Printex6L/GCE was tested for ranitidine (RNT) sensing and showed a decrease in the working potential and an increase in the analytical signal, when compared with GCE, again demonstrating an electrocatalytic effect. Under optimized experimental conditions, the developed square-wave adsorptive anodic stripping voltammetry (SWAdASV) method presented an analytical curve that was linear in RNT concentration range from 1.98 × 10^?6 to 2.88 × 10^?5 mol L^?1 with a detection limit of 2.44 × 10^?7 mol L^?1. The developed Printex6L/GCE was successfully applied to the determination of RNT concentrations in human body fluid samples (urine and serum).     

Reduced graphene oxide supported 2D-NiO nanosheets modified electrode for urea detection

Nickel oxide (NiO) nanosheets (NSs) deposited on different amounts (0.025, 0.05, 0.1, and 0.2 wt%) of reduced graphene oxide (rGO) are synthesized through hydrothermal method. The NiO NSs on rGO (rGO-NiO) are characterized by using X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, high resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED) analyses, and electrochemical analysis. Electrocatalytic activity of rGO-NiO nanocomposite modified glassy carbon (GC/rGO-NiO) electrode is examined towards electrocatalytic oxidation of urea in 0.1 M NaOH using cyclic voltammetry and amperometry techniques. The GC/rGO_0.1-NiO nanocomposite modified electrode shows enhanced electrocatalytic oxidation of urea than that of other modified electrodes due to the incorporation of NiO NSs on an optimum amount of rGO. The GC/rGO_0.1-NiO modified electrode is used for designing electrochemical sensor for urea, and the detection limit is estimated as 0.47 μM using the amperometry technique. The sensitivity of GC/rGO_0.1-NiO modified electrode is found to be 2450 μA mM⁻¹ cm⁻². In addition to good electroanalytical performance, the present urea sensor displayed good stability and acceptable anti-interference ability in the presence of 20-fold excess concentration of relevant interferents. The GC/rGO_0.1-NiO nanocomposite modified electrode is successfully used for the determination of urea in water sample.

Schematic representation of electrocatalytic oxidation of urea at GC/rGO-NiO nanocomposite modified electrode.

     

Optical and electrochemical-mediated detection of ascorbic acid using manganese porphyrin and its gold hybrids

The developments concerning new hybrids based on porphyrin derivatives and colloids destined for the detection of ascorbic acid (AA) in the relevant range for medical investigations are presented. Mn(III) tetratolylporphyrin chloride (MnTTPCl), spherical gold colloid (n-Au), and their hybrid (MnTTPCl/n-Au) were chosen to be comparatively investigated by ultraviolet–visible spectroscopy in the presence of AA. The hybrid material (MnTTPCl/n-Au) has the best capacity to detect concentrations of AA in the range of 2.6 × 10^?6–4.38 × 10^?5 M. Modified glassy carbon (GC) electrodes were obtained by thin film deposition of MnTTPCl, n-Au alone, and in successive mixed thin films, comparing their response during the electrochemical oxidation of AA. The electrocatalytic effect of the MnTTPCl on the AA oxidation is justified both by the increase in the peak current density and by the shift toward more negative potentials (0.024 V). The GC/MnTTPCl electrode has the best electrocatalytic effect for the AA oxidation and is promising for sensor applications.     

Chemometrics to evaluate the quality of water sources for human consumption

Multilayer films of multiwalled carbon nanotubes (MWNTs) were homogeneously and stably assembled on a glassy carbon (GC) electrode using the layer-by-layer (LBL) method based on electrostatic interaction between MWNTs (negatively charged) and a biopolymer chitosan (CHIT) (positively charged). Scanning electron microscopy (SEM) image of the resulting {CHIT/MWNTs}₉ film indicated that the substrate was mostly covered with MWNTs in the form of small bundles or single nanotubes. The multilayer film was used to study the electrocatalytic oxidation of NADH. The assembled {CHIT/MWNTs}₉/GC electrode could decrease the oxidation overpotential of NADH by more than 350 mV. The {CHIT/MWNTs}₉/GC electrode exhibited a wide linear response range of 8 × 10⁻⁷ to 1.6 × 10⁻³ mol · L⁻¹ with a correlation coefficient of 0.997 for the detection of NADH. The response time and detection limit (S/N = 3) were determined to be 3 s and 0.3 × 10⁻⁶ mol · L⁻¹, respectively. Another attractive characteristic was that the method was simple and the assembled {CHIT/MWNTs}₉/GC electrode was highly stable.     

Methanol sensor based on the combined electrocatalytic oxidative effect of chitosan-immobilized nickel(II) and the antibiotic cefixime on the oxidation of methanol in alkaline medium

A sensor for methanol was fabricated by incorporating the antibiotic cefixime (CEF) along with Ni(II) ion into a chitosan membrane matrix. Sensing is based on the electrocatalytic effect that the complex membrane exerts on the electro-oxidation of methanol. The resulting CEF-Ni(II)/chitosan glassy carbon (GC) electrode had a good electrocatalytic activity to the electro-oxidation of methanol in alkaline medium. The modified electrode had an immense electrocatalytic activity on the second process of methanol oxidation (methanol oxidation intermediate(s) to the final product). The modified electrode had a wide linear range from 20 μM to 12 mM for the determination of methanol in alkaline medium, and a detection limit of 5.24 μM based on a signal-to-noise ratio of 3. In addition, the sensor exhibited good stability.     

Voltammetric and amperometric determination of hydrogen peroxide using a carbon-ceramic electrode modified with a nanohybrid composite made from single-walled carbon nanotubes and silver nanoparticles

A nanohybrid composite material was prepared from single-walled carbon nanotubes and silver nanoparticles, and used to fabricate a modified carbon-ceramic electrode. The preparation of the composite is facile and efficient. The nanohybrid composite deposited on the carbon-ceramic electrode was characterized by X-ray diffraction and cyclic voltammetry. The new electrode displays favorable electrocatalytic ability towards hydrogen peroxide (H₂O₂) and can be used to electrocatalytically reduce this species. Under the optimum conditions, the current measured during hydrodynamic amperometry is linearly related to the concentration of H₂O₂ over the concentration range from 0.01 to 8 mM, with a detection limit of 2?×?10^?7 M at a signal-to-noise ratio of 3 and sensitivity of 3.23 μA/mM. The electrode exhibits good reproducibility, long-term stability and negligible interference by dopamine, uric acid, and other important biological compounds. The electrode was successfully applied to the determination of H₂O₂ in honey samples, and the recovery was 101.2%.

A biosensor prepared by co-entrapment of a glucose oxidase and a carbon nanotube within an electrochemically deposited redox polymer multilayer

A glucose biosensor based on a nanocomposite made by layer-by-layer electrodeposition of the redox polymer into a multilayer containing glucose oxidase (GOx) and single-walled carbon nanotubes (SWCNT) on a screen-printed carbon electrode (SPCE) surface was developed. The objectives of the electrodeposition of redox polymer are to stabilize further the multilayer using a coordinative cross-linked redox polymer and to wire the GOx. The electrochemistry of the layer-by-layer assembly of the GOx/SWCNT/redox polymer nanocomposite was followed by cyclic voltammetry. The resultant biosensor provided stable and reproducible electrocatalytic responses to glucose, and the electrocatalytic current for glucose oxidation was enhanced with an increase in the number of layers. The biosensor displayed a linear range from 0.5 to 6.0mM, a sensitivity of 16.4μA/(mMcm(2)), and a response time of about 5s. It shows no response to 0.05mM of ascorbic acid, 0.32mM of uric acid and 0.20mM of acetaminophen using a Nafion membrane covering the nanocomposite-modified electrode surface.     

亚硝酸根在纳米金修饰玻碳电极上的电催化氧化行为及其测定

采用直接电化学沉积法制备出纳米金修饰玻碳电极,研究了其对亚硝酸根的电催化氧化作用。结果表明,亚硝酸根在该修饰电极上于0.8 V处出现了一个良好的氧化峰。在最优实验条件下,亚硝酸根的峰电流与其浓度在2×10-6～2×10-3mol/L范围内呈一定的线性关系,检出限为6.0×10-7(S/N=3),提出了用循环伏安法测定亚硝酸根的方法。纳米金修饰电极用于东莞自来水水样中亚硝酸根的测定,回收率在98.1%～101.4%之间。对比本方法,用分光光度法对东莞自来水样中亚硝酸根进行了测定,结果满意。     

Determination of formal potential of NADH/NAD+ redox couple and catalytic oxidation of NADH using poly(phenosafranin)-modified carbon electrodes

The electrochemical regeneration of NADH/NAD⁺ redox couple has been studied using poly(phenosafranin) (PPS)-modified carbon electrodes to evaluate the formal potential and catalytic rate constant for the oxidation of NADH. The PPS-modified electrodes were prepared by electropolymerization of phenosafranin onto different carbon substrates (glassy carbon (GC) and basal-plane pyrolytic graphite (BPPG)) in different electrolytic solutions. The formal potential was estimated to be ? 0.365 ± 0.002 V vs. SHE at pH 7.0. As for the bare carbon electrodes, the oxidation of NADH at the BPPG electrode was found to be enhanced compared with the GC electrode. For the PPS-modified electrodes, it was found that the electrocatalysis of PPS-modified electrodes for the oxidation of NADH largely depends on the carbon substrate and electrolyte solution employed for their preparation, i.e., the PPS-modified BPPG electrode prepared in 0.2 M NaClO₄/acetonitrile solution exhibits an excellent and persistent electrocatalytic property toward NADH oxidation in phosphate buffer solution (pH 7.0) with a diminution of the overpotential of about 740 and 670 mV compared with those at the bare GC electrode and the PPS-modified GC electrode prepared in 0.2 M H₂SO₄ solution, respectively. A quantitative analysis of the electrocatalytic reaction based on rotating disk voltammetry gave the electrocatalytic reaction rate constants of the order of 10³–10⁴ M^?1 s^? 1 depending on the preparation conditions of the PPS-modified electrodes.