Electrocatalytic oxidation of aspirin and acetaminophen on a cobalt hydroxide nanoparticles modified glassy carbon electrode

The electrocatalytic oxidation of aspirin and acetaminophen on nanoparticles of cobalt hydroxide electrodeposited on the surface of a glassy carbon electrode in alkaline solution was investigated. The process of oxidation and the kinetics have been investigated using cyclic voltammetry, chronoamperometry, and steady-state polarization measurements. Voltammetric studies have indicated that in the presence of drugs, the anodic peak current of low valence cobalt species increases, followed by a decrease in the corresponding cathodic current. This indicates that drugs are oxidized on the redox mediator which is immobilized on the electrode surface via an electrocatalytic mechanism. With the use of Laviron’s equation, the values of anodic and cathodic electron-transfer coefficients and charge-transfer rate constant for the immobilized redox species were determined as α _s,a = 0.72, α _s,c = 0.30, and k _s = 0.22 s⁻¹. The rate constant, the electron transfer coefficient, and the diffusion coefficient involved in the electrocatalytic oxidation of drugs were reported. It was shown that by using the modified electrode, aspirin and acetaminophen can be determined by amperometric technique with detection limits of 1.88 × 10⁻⁶ and 1.83 × 10⁻⁶ M, respectively. By analyzing the content of acetaminophen and aspirin in bulk forms using chronoamperometric and amperometric techniques, the analytical utility of the modified electrode was achieved. The method was also proven to be valid for analyzing these drugs in urine samples.     

Electrochemical studies of cytochrome c on gold electrodes with promotor of humic acid and 4-aminothiophenol

p-Aminothiophenol (PATP) and humic acids (HA or HAs) were applied jointly as the electron transfer accelerants of redox reactions of cytochrome c (Cyt c) on gold electrodes. The electrochemical properties of the modified electrodes were studied by field emission scanning electron microscope, ultraviolet-visible spectroscopy, electrochemical impedance spectroscopy, Raman spectroscopy and cyclic voltammetry. The immobilized Cyt c displayed a couple of stable and well-defined redox peaks with a formal potential of −0.101 V (vs. SCE) in pH 7.0 phosphate buffer solution. Cyt c adsorption is in the form of a monolayer with average surface coverage of 5.28 pmol cm⁻². The electron transfer rate constant was calculated to be 2.14 s⁻¹. It indicate that the HA film acted as a good adsorption matrix for Cyt c and an excellent accelerant for the redox of Cyt c. The Cyt c-HA modified gold electrode showed a new couple of well-marked redox peaks when 2,4-dichlorophenol was added to the test solution.     

Direct electron transfer of cytochrome C and its electrocatalytic properties on multiwalled carbon nanotubes/ciprofloxacin films

In this study, stable and homogenous thin films of multiwalled carbon nanotubes (MWCNTs) were obtained on conducting surface using ciprofloxacin (CF, fluoroquinolone antibiotic) as an effective-dispersing agent. Further, MWCNTs/CF film modified electrodes (glassy carbon and indium tin oxide-coated glass electrode) are used successfully to study the direct electrochemistry of proteins. Here, cytochrome C (Cyt-C) was used as a model protein for investigation. A MWCNTs/CF film modified electrode was used as a biocompatible material for immobilization of Cyt-C from a neutral buffer solution (pH 7.2) using cyclic voltammetry (CV). Interestingly, Cyt-C retained its native state on the MWCNTs/CF film. The Cyt-C adsorbed MWCNTs/CF film was characterized by scanning electron microscopy (SEM), UV–visible spectrophotometry (UV-vis) and CV. SEM images showed the evidence for the adsorption of Cyt-C on the MWCNTs/CF film, and UV–vis spectrum confirmed that Cyt-C was in its native state on MWCNTs/CF film. Using CV, it was found that the electrochemical signal of Cyt-C was highly stable in the neutral buffer solution and its redox peak potential was pH dependent. The formal potential (−0.27 V) and electron transfer rate constant (13 ± 1 s⁻¹) were calculated for Cyt-C on MWCNTs/CF film modified electrode. A potential application of the Cyt-C/MWCNTs/CF electrode as a biosensor to monitor H₂O₂ has been investigated. The steady-state current response increases linearly with H₂O₂ concentration from 2 × 10⁻⁶ to 7.8 × 10⁻⁵ M. The detection limit for determination of H₂O₂ has been found to be 1.0 × 10⁻⁶ M (S/N = 3). Thus, Cyt-C/MWCNTs/CF film modified electrode can be used as a biosensing material for sensor applications.     

Electrochemistry and electrocatalytic activity of polypyrrole/ferrocyanide films on a glassy carbon electrode

Functionalized polypyrrole films were prepared by incorporation of Fe(CN)₆ ³⁻ as doping anion during the electropolymerization of pyrrole at a glassy carbon electrode from aqueous solution. The electrochemical behavior of the Fe(CN)₆ ³⁻/Fe(CN)₆ ⁴⁻ redox couple in polypyrrole was studied by cyclic voltammetry. An obvious surface redox reaction was observed and dependence of this reaction on the solution pH was illustrated. The electrocatalytic ability of polypyrrole film with ferrocyanide incorporated was demonstrated by oxidation of ascorbic acid at the optimized pH of 4 in a glycine buffer. The catalytic effect for mediated oxidation of ascorbic acid was 300 mV and the bimolecular rate constant determined for surface coverage of 4.5 × 10⁻⁸ M cm⁻² using rotating disk electrode voltammetry was 86 M⁻¹ s⁻¹. Furthermore, the catalytic oxidation current was linearly dependent on ascorbic acid concentration in the range 5 × 10⁻⁴–1.6 × 10⁻² M with a correlation coefficient of 0.996. The plot of i _p versus v ^1/2 confirms the diffusion nature of the peak current i _p. Received: 12 April 1999 / Accepted: 25 May 1999     

Caffeic acid modified glassy carbon electrode for electrocatalytic oxidation of reduced nicotinamide adenine dinucleotide (NADH)

A new modified electrode was prepared by electrodeposition of caffeic acid (CFA) at the surface of an activated glassy carbon electrode. Cyclic voltammetry was used to investigate the redox properties of this electrode at various solution pH values and at various scan rates. The pH dependence of the electrode response was found to be 58.5 mV/pH, which is very close to the expected Nernstian value. The electrode was also employed to study electrocatalytic oxidation of reduced nicotinamide adenine dinucleotide (NADH), using cyclic voltammetry, chronoamperometry and rotating disk voltammetry as diagnostic techniques. It was found that the modified electrode exhibits potent and persistent electrocatalytic properties toward NADH oxidation in phosphate buffer solution (pH 7.0) with a diminution of the overpotential of about 450 mV compared to the process at an unmodified electrode. The electrocatalytic current increases linearly with NADH concentration in the range tested from 0.05 to 1.0 mM. The apparent charge transfer rate constant and transfer coefficient for electron transfer between the electrode surface and immobilized CFA were calculated as 11.2 s⁻¹ and 0.43, respectively. The heterogeneous rate constant for oxidation of NADH at the CFA-modified electrode surface was also determined and found to be about 3 × 10³ M⁻¹ s⁻¹. Finally, the diffusion coefficient of NADH was calculated as 3.24 × 10⁻⁶ cm² s⁻¹ for the experimental conditions, using chronoamperometric results. Received: 6 January 1999 / Accepted: 11 May 1999     

Electrochemical behavior of uric acid at a penicillamine self-assembled gold electrode

The fabrication and electrochemical characteristics of a penicillamine (PCA) self-assembled monolayer modified gold electrode were investigated. The electrode can enhance the electrochemical response of uric acid (UA), and the electrochemical reaction of UA on the PCA electrode has been studied by cyclic voltammetry and differential pulse voltammetry. Some electrochemical parameters, such as diffusion coefficient, standard rate constant, electron transfer coefficient and proton transfer number have been determined for the electrochemical behavior on the PCA self-assembled monolayer electrode. The electrode reaction of UA is an irreversible process, which is controlled by the diffusion of UA with two electrons and two protons transfer at the PCA/Au electrode. In phosphate buffer (pH 5.0), the peak current is proportional to the concentration of UA in the range of 6.0 × 10⁻⁵–7.0 × 10⁻⁴ mol L⁻¹ and 2.0 × 10⁻⁵–7.0 × 10⁻⁴ mol L⁻¹ for the cyclic voltammetry and differential pulse voltammetry methods with the detection limits of 5.0 × 10⁻⁶ and 3.0 × 10⁻⁶ mol L⁻¹, respectively. The method can be applied to determine UA concentration in real samples.     

Electrochemical deposition of silicate–cetyltrimethylammonium bromide nanocomposite film on glassy carbon electrode for sensing of methyl parathion

A novel electrochemical sensor for methyl parathion based on silicate– cetyltrimethylammonium bromide nanocomposite film has been fabricated by electro-assisted deposition onto glassy carbon electrode in one-step via an electrochemical modulation of pH at the electrode/solution interface to promote controlled gelification of tetraethylorthosilicate sol, and was characterized with scanning electron microscopy, X-ray diffraction, and electrochemical impedance spectroscopy. The electrochemical sensing of methyl parathion on the film-modified electrode was investigated applying cyclic voltammetry and square wave voltammetry. Compared to the unmodified electrode, the shapes of the redox peaks were improved and the peak currents significantly increased. Experimental parameters such as deposition time, pH value, and accumulation conditions have been optimized. A linear relationship between the peak current and methyl parathion concentration was obtained in the range from 1.0 × 10⁻⁷ to 1.0 × 10⁻⁴ mol L⁻¹ with a detection limit of 1.04 × 10 ⁻⁸ mol L⁻¹ (S/N = 3) after accumulation at 0 V for 120 s. The film electrode shows great promise for determination of methyl parathion in real samples.      

Electrochemical behaviour of a lead electrode in phosphoric acid

 A lead electrode was studied in 6 and 12 M H₃PO₄. Oxidation of a freshly polished electrode occurred in the −0.5 to −0.3 V vs. SCE range, and led to PbHPO₄ growth on the electrode surface. The dissolution of this layer by electrochemical reduction occurred between −0.5 and −0.7 V. The influence of temperature (20 °C and 65 °C) was investigated and showed that the anodic and the cathodic peaks were increasing, and more markedly for the 12 M H₃PO₄. The ratio Q _cathodic/Q _anodic (Q=electrical charge flowing through the electrode) was equal or close to the unity at 20 °C and decreased as the temperature was increased. The influence of Cl⁻, Br⁻ and I⁻ ions was also evaluated. The addition of Cl⁻ and Br⁻ predominantly led to Pb₅(PO₄)₃Cl and Pb₅(PO₄)₃Br, respectively, while I⁻ led to a mixture of PbI₂ and PbHPO₄. Received: 18 July 1999 / Accepted: 2 November 1999     

Electrocatalytic oxidation of nitrite at a terpyridine manganese(II) complex modified carbon past electrode

A carbon past electrode modified with [Mn(H₂O)(N₃)(NO₃)(pyterpy)], ( \textpyterpy = 4￠- ( 4 - \textpyridyl ) - 2,2￠:\text6￠,\text2￠￠- \textterpyridine ) \left( {{\text{pyterpy}} = 4\prime - \left( {4 - {\text{pyridyl}}} \right) - 2,2\prime:{\text{6}}\prime,{\text{2}}\prime\prime - {\text{terpyridine}}} \right) complex have been applied to the electrocatalytic oxidation of nitrite which reduced the overpotential by about 120 mV with obviously increasing the current response. Relative standard deviations for nitrite determination was less than 2.0%, and nitrite can be determined in the ranges of 5.00 × 10⁻⁶ to 1.55 × 10⁻² mol L⁻¹, with a detection limit of 8 × 10⁻⁷ mol L⁻¹. The treatment of the voltammetric data showed that it is a pure diffusion-controlled reaction, which involves one electron in the rate-determining step. The rate constant k′, transfer coefficient α for the catalytic reaction, and diffusion coefficient of nitrite in the solution, D, were found to be 1.4 × 10⁻², 0.56× 10⁻⁶, and 7.99 × 10⁻⁶ cm² s⁻¹, respectively. The mechanism for the interaction of nitrite with the Mn(II) complex modified carbon past electrode is proposed. This work provides a simple and easy approach to detection of nitrite ion. The modified electrode indicated reproducible behavior, anti-fouling properties, and stability during electrochemical experiments, making it particularly suitable for the analytical purposes.     

Nanomolar determination of hydrazine by TiO2 nanoparticles modified carbon paste electrode

In the present paper, the use of a novel carbon paste electrode modified by N,N′(2,3-dihydroxybenzylidene)-1,4-phenylene diamine (DHBPD) and TiO₂ nanoparticles prepared by a simple and rapid method for the determination of hydrazine (HZ) was described. In the first part of the work, cyclic voltammetry was used to investigate the redox properties of this modified electrode at various solution pH values and at various scan rates. A linear segment was found with a slope value of about 48 mV/pH in the pH range 2.0–12.0. The apparent charge transfer rate constant (k _s) and transfer coefficient (α) for electron transfer between DHBPD and TiO₂ nanoparticles-modified carbon paste electrode were calculated. In the second part of the work, the mediated oxidation of HZ at the modified electrode was described. It has been found that under optimum condition (pH 8.0) in cyclic voltammetry, a high decrease in overpotential occurs for oxidation of HZ at the modified electrode. The values of electron transfer coefficients (α) and diffusion coefficient (D) were calculated for HZ, using electrochemical approaches. Differential pulse voltammetry exhibited a linear dynamic range from 1.0 × 10⁻⁸ to 4.0 × 10⁻⁶ M and a detection limit (3σ) of 9.15 nM for HZ. Finally, this method was used for the determination of HZ in water samples, using standard addition method.     

Immobilization of Hemoglobin on the Gold Colloid Modified Pretreated Glassy Carbon Electrode for Preparing a Novel Hydrogen Peroxide Biosensor

A novel hydrogen peroxide (H₂O₂) biosensor was developed by immobilizing hemoglobin on the gold colloid modified electrochemical pretreated glassy carbon electrode (PGCE) via the bridging of an ethylenediamine monolayer. This biosensor was characterized by UV-vis reflection spectroscopy (UV-vis), electrochemical impendence spectroscopy (EIS) and cyclic voltammetry (CV). The immobilized Hb exhibited excellent electrocatalytic activity for hydrogen peroxide. The Michaelis–Menten constant (K _m) was 3.6 mM. The currents were proportional to the H₂O₂ concentration from 2.6 × 10⁻⁷ to 7.0 × 10⁻³ M, and the detection limit was as low as 1.0 × 10⁻⁷ M (S/N = 3).     

Simultaneous determination of catechol and hydroquinone based on poly (diallyldimethylammonium chloride) functionalized graphene-modified glassy carbon electrode

Simultaneous determination of catechol (CC) and hydroquinone (HQ) were investigated by voltammetry based on glassy carbon electrode (GCE) modified by poly (diallyldimethylammonium chloride) (PDDA) functionalized graphene (PDDA-G). The modified electrode showed excellent sensitivity and selectivity properties for the two dihydroxybenzene isomers. In 0.1 mol/L phosphate buffer solution (PBS, pH 7.0), the oxidation peak potential difference between CC and HQ was 108 mV, and the peaks on the PDDA-G/GCE were three times as high as the ones on graphene-modified glass carbon electrode. Under optimized conditions, the PDDA-G/GCE showed wide linear behaviors in the range of 1 × 10⁻⁶−4 × 10⁻⁴ mol/L for CC and 1 × 10⁻⁶−5 × 10⁻⁴ mol/L for HQ, with the detection limits 2.0 × 10⁻⁷ mol/L for CC and 2.5 × 10⁻⁷ mol/L for HQ (S/N = 3) in mixture, respectively. Some kinetic parameters, such as the electron transfer number (n), charge transfer coefficient (α), and the apparent heterogeneous electron transfer rate constant (k _s), were calculated. The proposed method was applied to simultaneous determine CC and HQ in real water samples of Yellow River with satisfactory results.     

Sensitive determination of fluphenazine at a dodecanethiol self-assembled monolayer-modified gold electrode, and its electrocatalysis to phenylephrine

Fluphenazine, an important tranquilizer, was found to undergo effective accumulation on dodecanethiol (DDT) self-assembled monolayer modified gold electrode (i.e. DDT/Au) and generated two anodic peaks at about 0.7 and 0.79 V (vs. SCE) in 0.05 M Na₂B₄O₇ (pH = 9.3) buffer solution. Sensitive and quantitative measurement of fluphenazine based on the former anodic peak was established under optimum conditions. The peak current was linear to fluphenazine concentration in the range from 5 × 10⁻⁷ to 5 × 10⁻⁵ M, with a detection limit of 5 × 10⁻⁹ M. This method was successfully applied to the determination of fluphenazine in drug tablets and proved to be reliable compared with UV spectrophotometry. In the presence of fluphenazine, the electrochemical oxidation of phenylephrine was catalyzed. The DDT self-assembled monolayer was characterized by Fourier transform infrared spectroscopy, surface Raman spectroscopy, X-ray photoelectron spectroscopy, electrochemical impedance spectroscopy, and electrochemical probing.     

Immobilization of flavine adenine dinucleotide onto nickel oxide nanostructures modified glassy carbon electrode: fabrication of highly sensitive persulfate sensor

A simple method was used to fabricate flavin adenine dinucleotide (FAD)/NiOx nanocomposite on the surface of glassy carbon (GC) electrode. Cyclic voltammetry technique was applied for deposition nickel oxide nanostructures onto GC surface. Owing to its high biocompatibility and large surface area of nickel oxide nanomaterials with immersing the GC/NiOx-modified electrode into FAD solution for a short period of time, 10–140 s, a stable thin layer of the FAD molecules immobilized onto electrode surface. The FAD/NiOx films exhibited a pair of well-defined, stable, and nearly reversible CV peaks at wide pH range (2–10). The formal potential of adsorbed FAD onto nickel oxide nanoparticles film, E ^o′ vs. Ag/AgCl reference electrode is −0.44 V in pH 7 buffer solutions was similar to dissolved FAD and changed linearly with a slope of 58.6 mV/pH in the pH range 2–10. The surface coverage and heterogeneous electron transfer rate constant (k _s ) of FAD immobilized on NiOx film glassy carbon electrode are 4.66 × 10⁻¹¹ mol cm⁻² and 63 ± 0.1 s⁻¹, indicating the high loading ability of the nickel oxide nanoparticles and great facilitation of the electron transfer between FAD and nickel oxide nanoparticles. FAD/NiOx nanocomposite-modified GC electrode shows excellent electrocatalytic activity toward S₂O₈²⁻ reduction at reduced overpotential. Furthermore, rotated modified electrode illustrates good analytical performance for amperometric detection of S₂O₈²⁻. Under optimized condition, the concentration calibration range, detection limit, and sensitivity were 3 μM–1.5 mM, 0.38 μM and 16.6 nA/μM, respectively.     

Electrochemical behavior and determination of epinephrine at a mercaptoacetic acid self-assembled gold electrode

The electrochemical behavior of epinephrine (EP) at a mercaptoacetic acid (MAA) self-assembled monolayer modified gold electrode was studied. The MAA/Au electrode is demonstrated to promote the electrochemical response of epinephrine by cyclic voltammetry. The possible reaction mechanism is also discussed. The diffusion coefficient D of EP is 6.85 × 10⁻⁶ cm² s⁻¹. In 0.1 mol L⁻¹ phosphate buffer (pH 7.20), a sensitive oxidation peak was observed at 0.177 V, and the peak current is proportional to the concentration of EP in the range of 1.0 × 10⁻⁵–2.0 × 10⁻⁴ mol L⁻¹ and 1.0 × 10⁻⁷–1.0 × 10⁻⁶ mol L⁻¹. The detection limit is 5 × 10⁻⁸ mol L⁻¹. The modified electrode is highly stable and can be applied to the determination of EP in practical injection samples. The method is simple, quick, sensitive and accurate.     

Electrochemical methods for simultaneous determination of trace amounts of dopamine and uric acid using a carbon paste electrode incorporated with multi-wall carbon nanotubes and modified with α-cyclodextrine

In this work, we investigate the electrochemical activity of dopamine (DA) and uric acid (UA) using both a bare and a modified carbon paste electrode as the working electrode, with a platinum wire as the counter electrode and a silver/silver chloride (Ag/AgCl) as the reference electrode. The modified carbon paste electrode consists of multi-walled carbon nanotubes (>95%) treated with α-cyclodextrine, resulting in an electrode that exhibits a significant catalytic effect toward the electro-chemical oxidation of DA in a 0.2-M Britton–Robinson buffer solution (pH 5.0). The peak current increases linearly with the DA concentration within the molar concentration ranges of 2.0 × 10⁻⁶ to 5.0 × 10⁻⁵ M and 5.0 × 10⁻⁵ to 1.9 × 10⁻⁴ M. The detection limit (signal to noise >3) for DA was found to be 1.34 × 10⁻⁷ M, respectively. In this work, voltammetric methods such as cyclic voltammetry, chronoamperometry, chronocuolometry, differential pulse and square wave voltammetry, and linear sweep and hydrodynamic voltammetry were used. Cyclic voltammetry was used to investigate the redox properties of the modified electrode at various scan rates. The diffusion coefficient (D, cm² s⁻¹ = 3.05 × 10⁻⁵) and the kinetic parameters such as the electron transfer coefficient (α = 0.51) and the rate constant (k, cm³ mol⁻¹ s⁻¹ = 1.8 × 10³) for DA were determined using electrochemical approaches. By using differential pulse voltammetry for simultaneous measurements, we obtained two peaks for DA and UA in the same solution, with the peak separation approximately 136 mV. The average recovery was measured at 102.45% for DA injection.     

Electrochemical,microscopic, and EQCM studies of cathodic electrodeposition of ZnO/FAD and anodic polymerization of FAD films modified electrodes and their electrocatalytic properties

Two kinds of chemically modified electrodes were prepared. In the first type of electrodes, zinc oxide (ZnO) and flavin adenine dinucleotide (FAD) molecules were deposited onto the glassy carbon-, gold-, and SnO₂-coated glass electrodes by using cyclic voltammetry from the bath solution containing aqueous 0.1 M zinc nitrate, 0.1 M sodium nitrate, and 1 × 10⁻⁴ M FAD. It was called as ZnO/FAD modified electrodes. The second type of modified electrode was prepared by the electropolymerization method. Electrochemical polymerization of FAD was carried out from the acidic solution containing 1 × 10⁻⁴ M FAD monomers onto electrode surfaces. This poly(FAD)-modified electrode yields a new redox couple in addition to the monomers redox couple. The influence of the concentrations, pH, and electrocatalytic properties of the ZnO/FAD- and poly(FAD)-modified electrodes are investigated by means of the in situ technique electrochemical quartz–crystal microgravimetry (EQCM) combined with cyclic voltammetry and the ex situ technique scanning electron microscopy. From these studies, it appears that the cathodic deposition of ZnO/FAD-modified electrodes gives only one redox couple, and the anodically polymerized FAD film-modified electrodes gives two reversible redox couples. The pH dependence of the redox responses were investigated and the kinetics of electron transfer was evaluated. In addition, the EQCM technique was employed to follow the deposition process of both kinds of modified electrodes in real time as well as the characteristics of the charge transfer associated with the surface-confined redox-active couples. The electrocatalytic activity of the poly(FAD)-modified electrode towards the reduction of hydrogen peroxide and the oxidation of dopamine and ascorbic acid was explored. The important electrocatalytic properties of poly(FAD)-modified electrode were observed for simultaneous separation of dopamine and ascorbic acid in neutral solution. This poly(FAD)-modified electrode has several advantages than the previously reported FAD-modified electrodes.     

Electrochemical behaviors of metol on ionic-liquid-modified carbon paste electrode and its analytical application

The electrochemical behaviors of metol on an ionic liquid N-butylpyridinium hexafluorophosphate modified carbon paste electrode (IL-CPE) were studied in this paper. The results indicated that a pair of well-defined quasi-reversible redox peaks of metol appeared with the decrease of overpotential and the increase of redox peak current, which was the characteristics of electrocatalytic oxidation. The electrocatalytic mechanism was discussed and the electrochemical parameters were calculated with results of the charge-transfer coefficient (α) as 0.45, the electrode reaction rate constant (k _s) as 4.02 × 10⁻³ s⁻¹, and the diffusion coefficient (D) as 6.35 × 10⁻⁵ cm²/s. Under the optimal conditions, the anodic peak current was linear with the metol concentration in the range of 5.0 × 10⁻⁶ ∼ 1.0 × 10⁻³ mol/L (n = 11, γ = 0.994) and the detection limit was estimated as 2.33 × 10⁻⁶ mol/L (3σ). The proposed method was successfully applied to determination of metol content in synthetic samples and photographic solutions.     

Preparation, characterization, and application of electrodes modified with electropolymerized one-dimensional Magnus' green salts: Pt(NH3)4 · PtCl4 and Pt(NH3)4 · PtCl6

We report the modification of various electrode surfaces with electropolymerized Magnus' green salts, [Pt(NH₃)₄ · PtCl₄] _n and [Pt(NH₃)₄ · PtCl₆] _n . The modified electrodes were prepared by cyclic scanning of the electrode potential in an aqueous solution containing Pt(NH₃)₄ ²⁺ and PtCl₄ ²⁻ or PtCl₆ ²⁻ and the supporting electrolyte. The conditions for the film deposition were studied in detail. Several surface analytical techniques, including micro-Raman scattering and X-ray diffraction, were employed to characterize the modifier film. The electrochemical behavior of the modified electrode was studied in detail and the modified electrodes display very good electrocatalytic activity in the oxidation of ascorbic acid, hydrogen peroxide, thiosulfate, and especially nitric oxide. Received: 22 April 1999 / Accepted: 30 June 1999     

Direct electrochemistry and biocatalysis of glucose oxidase immobilized on magnetic mesoporous carbon

A magnetic mesoporous carbon material (i.e., mesoporous iron oxide/C, mesoFe/C) is synthesized for protein immobilization, using glucose oxidase (GOx) as model. Transmission electron microscopy images show that mesoFe/C has highly ordered porous structure with uniform pore size, and iron oxide nanoparticles are dispersed along the wall of carbon. After adsorption of GOx, the GOx-mesoFe/C composite is separated with magnet. The immobilized GOx remains its natural structure according to the reflection–absorption infrared spectra. When the GOx-mesoFe/C composite is coated on a Pt electrode surface, the GOx gives a couple of quasireversible voltammetric peaks at −0.5 V (vs. saturated calomel electrode) due to the redox of FAD/FADH₂. The electron-transfer rate constant (k _s) is ca. 0.49 s⁻¹. The modified electrode presents remarkably amperometric response to glucose at 0.6 V. The response time (t _95%) is less than 6 s; the response current is linear to glucose concentration in the range of 0.2–10 mM with a sensitivity of 27 μA mM⁻¹ cm⁻². The detection limit is 0.08 mM (S/N = 3). The apparent Michaelis–Menten constant (K _m^app) of the enzyme reaction is ca. 6.6 mM, indicating that the GOx immobilized with mesoFe/C has high affinity to the substrate.