N-Aryl-N-Hydroxy Urethanes as Peroxidase Substrates

Summary.  N-Aryl-N-hydroxy urethanes (AHUs), which are promising N*OH mediators for oxidoreductase catalysis, are electrochemically active redox compounds with a redox potential of 0.35–0.40 V vs. SCE (0.59–0.64 V vs. NHE). Alkyl substituents in the carbamic acid residue have, as expected, only little influence on the redox potential. The highest potential was noticed for N-hydroxy-N-(4-cyanophenyl)-carbamic acid methyl ester. Recombinant Coprinus cinereus peroxidase (rCiP) catalyzes oxidation of the AHUs with apparent bimolecular constants k _ox of 2.5ċ10⁴–7.5ċ10⁴ M ⁻¹s⁻¹ at pH = 8.5 and 25°C. Structure-function connectivities of the substrates were analysed within the framework of the Marcus cross relationship and by using ab initio quantum chemical calculations. An excellent correlation of the redox potentials and the HOMO energies could be found. However, no correlation of log(k _ox) with redox potential and HOMO energy was indicated as predicted by theory. This was explained by specific docking of the substrates in the active center of rCiP. Received June 26, 2000. Accepted (revised) August 9, 2000     

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.     

A new amperometric H<Subscript>2</Subscript>O<Subscript>2</Subscript> biosensor based on nanocomposite films of chitosan–MWNTs,hemoglobin, and silver nanoparticles

A new H₂O₂ biosensor was fabricated on the basis of nanocomposite films of hemoglobin (Hb), silver nanoparticles (AgNPs), and multiwalled carbon nanotubes (MWNTs)–chitosan (Chit) dispersed solution immobilized on glassy carbon electrode (GCE). The immobilized Hb displayed a pair of well-defined and reversible redox peaks with a formal potential (E ^θ′) of −22.5 mV in 0.1 M pH 7.0 phosphate buffer solution. The apparent heterogeneous electron transfer rate constants (k _s) in the Chit–MWNTs film was evaluated as 2.58 s⁻¹ according to Laviron’s equation. The surface concentration (Γ*) of the electroactive Hb in the Chit–MWNTs film was estimated to be (2.48 ± 0.25) × 10⁻⁹ mol cm⁻². Meanwhile, the Chit–MWNTs/Hb/AgNPs/GCE demonstrated excellently electrocatalytical ability to H₂O₂. Its apparent Michaelis–Menten constant (K _M^app) for H₂O₂ was 0.0032 mM, showing a good affinity. Under optimal conditions, the biosensors could be used for the determination of H₂O₂ ranging from 6.25 × 10⁻⁶ to 9.30 × 10⁻⁵ mol L⁻¹ with a detection limit of 3.47 × 10⁻⁷ mol L⁻¹ (S/N = 3). Furthermore, the biosensor possessed rapid response to H₂O₂ and good stability, selectivity, and reproducibility.     

Electrochemical characterization of 2, 2′-[1, 2-ethanediylbis (nitriloethylidyne)]-bis-hydroquinone-carbon nanotube paste electrode and its application to simultaneous voltammetric determination of ascorbic acid and uric acid

The preparation and electrochemical characterization of a carbon nanotube paste electrode modified with 2,2′-[1,2-ethanediylbis (nitriloethylidyne)]-bis-hydroquinone, referred to as EBNBH, was investigated. The EBNBH carbon nanotube paste electrode (EBNBHCNPE) displayed one pair of reversible peaks at E _pa = 0.18 V and E _pc = 0.115 V vs Ag/AgCl. Half wave potential (E _1/2) and ΔE _p were 0.148 and 0.065 V vs Ag/AgCl, respectively. The electrocatalytic oxidation of ascorbic acid (AA) has been studied on EBNBHCNPE, using cyclic voltammetry, differential pulse voltammetry and chronoamperometry techniques. It has been shown that the oxidation of AA occurs at a potential where oxidation is not observed at the unmodified carbon paste electrode. The heterogeneous rate constant for oxidation of AA at the EBNBHCNPE was also determined and found to be about 1.07 × 10⁻³ cm s⁻¹. The diffusion coefficient of AA was also estimated as 5.66 × 10⁻⁶ cm² s⁻¹ for the experimental conditions, using chronoamperometry. Also, this modified electrode presented the property of electrocatalysing the oxidation of AA and uric acid (UA) at 0.18 and 0.35 V vs Ag/AgCl, respectively. The separations of anodic peak potentials of AA and UA reached 0.17 V. Using differential pulse voltammetry, the calibration curves for AA and UA were obtained over the range of 0.1–800 μM and 20–700 μM, respectively. With good selectivity and sensitivity, the present method provides a simple method for selective detection of AA and UA in biological samples.     

A UV-visible spectroelectrochemical study of the electropolymerisation of N-benzylaniline

The electropolymerisation of N-benzylaniline (NBA) at transparent ITO glass electrodes was investigated with in situ UV-visible spectroelectrochemistry. An intermediate was found to be generated during electrolysis as the precursor of poly(N-benzylaniline) (PNBA). The intermediate, which shows an absorbance band at λ = 460 nm, is able to react spontaneously with NBA, forming a polymeric end product, which is deposited on the electrode surface. UV-Vis spectra were obtained with PNBA-modified electrodes at various electrode potentials. It was shown that the colouration of the PNBA film after a positive-going potential step proceeds ca. 5 times slower than its discolouration after the reverse negative-going potential step. Anodic degradation of PNBA film was shown to proceed when holding the electrode at a sufficiently high positive potential. A linear dependence between the first-order degradation rate constant (k/s⁻¹) and electrode potential (E/V) was found in the potential range of E _RHE = +0.8 to +1.1 V: log k = a + bE, where a = −8.75 and b = 5.45 are empirical coefficients. In the whole spectral range investigated, the degradation of PNBA was found to proceed faster as compared to that of polyaniline (for polyaniline, coefficients a = −12.7 and b = 8.96 were obtained in the potential range of E _RHE = +0.85 to +1.1 V). The electrooxidation of hydroquinone, as well as the electroreduction of benzoquinone, were shown to proceed at PNBA-modified electrodes. In these processes, PNBA was shown to play the role of an electron mediator between the ITO electrode and solution phase redox species. Received: 8 January 1999 / Accepted: 27 January 1999     

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     

Effect of ionic conductivity of a PAN–PC–LiClO<Subscript>4</Subscript> solid polymeric electrolyte on the performance of a TiO<Subscript>2</Subscript> photoelectrochemical cell

A nanoparticle TiO₂ solid-state photoelectrochemical cell has been fabricated. The effect of ionic conductivity of a solid electrolyte of polyacrylonitrile (PAN)–propylene carbonate (PC)–lithium perchlorate (LiClO₄) on the performance of a photoelectrochemical cell of indium tin oxide (ITO)/TiO₂/PAN–PC–LiClO₄/graphite has been investigated. A nanoparticle TiO₂ film was deposited onto ITO-covered glass substrate by controlled hydrolysis technique. A solid electrolyte of PAN–LiClO₄ with PC plasticizer prepared by solution casting technique was used as a redox couple medium. The room temperature conductivity of the electrolyte was determined by AC impedance spectroscopy technique. A graphite electrode was prepared onto a glass slide by electron beam evaporation technique. The device shows a photovoltaic effect under illumination. The short-circuit current density, J _sc, and open-circuit voltage, V _oc, vary with the conductivity of the electrolyte. The highest J _sc of 2.82 μA cm⁻² and V _oc of 0.56 V were obtained at the conductivity of 4.2 × 10⁻⁴ Scm⁻¹ and at the intensity of 100 mW cm⁻².     

Solid state electrochemical of the erbium hexacyanoferrate-modified carbon ceramic electrode and its electrocatalytic oxidation of <Emphasis Type="SmallCaps">l</Emphasis>-cysteine

A kind of erbium hexacyanoferrate (ErHCF)-modified carbon ceramic electrodes (CCEs) fabricated by mechanically attaching ErHCF samples to the surface of CCEs derived from sol–gel technique was proposed. The resulting modified electrodes exhibit well-defined redox responses with the formal potential of +0.215 V [vs saturated calomel electrode (SCE)] at a scan rate of 20 mV s⁻¹ in 0.5 M KCl (pH 7) solution. The voltammetric characteristics of the ErHCF-modified CCEs were investigated by voltammetry. Attractively, the ErHCF-modified CCEs presented good electrocatalytic activity with a marked decrease in the overvoltage about 400 mV for l-cysteine oxidation. The calibration plot for l-cysteine determination was linear at 5.0 × 10⁻⁶–1.3 × 10⁻⁴ M with a linear regression equation of I(A) = 0.558 + 0.148c (μM) (R ² = 0.9989, n = 20), and the detection limit was 2 × 10⁻⁶ M (S/N = 3). At last, the ErHCF-modified CCEs were used for amperometric detection of l-cysteine in real samples.     

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.     

Li-cycling properties of nano-crystalline (Ni1 ? xZnx)Fe2O4 (0 ≤ x ≤ 1)

Sol–gel auto-combustion method is adopted to prepare solid solutions of nano-crystalline spinel oxides, (Ni_1 − x Zn _x )Fe₂O₄ (0 ≤ x ≤ 1).The phases are characterized by X-ray diffraction (XRD), high-resolution transmission electron microscopy, selected area electron diffraction, and Brunauer–Emmett–Teller surface area. The cubic lattice parameters, calculated by Rietveld refinement of XRD data by taking in to account the cationic distribution and affinity of Zn ions to tetrahedral sites, show almost Vegard’s law behavior. Galvanostatic cycling of the heat-treated electrodes of various compositions are carried in the voltage range 0.005–3 V vs. Li at 50 mAg⁻¹ up to 50 cycles. Phases with high Zn content x ≥ 0.6 showed initial two-phase Li-intercalation in to the structure. Second-cycle discharge capacities above 1,000 mAh g⁻¹ are observed for all x. However, drastic capacity fading occurs in all cases up to 10–15 cycles. The capacity fading between 10 and 50 cycles is found to be greater than 52% for x ≤ 0.4 and for x = 0.8. For x = 0.6 and x = 1, the respective values are 40% and 18% and a capacity of 570 and 835 mAh g⁻¹ is retained after 50 cycles. Cyclic voltammetry and ex situ transmission electron microscopy data elucidate the Li-cycling mechanism involving conversion reaction and Li–Zn alloying–dealloying reactions.     

Composite films of polyaniline and molybdenum oxide formed by electrocodeposition in aqueous media

Composite films of polyaniline (PANI) and molybdenum oxide (MoO_x) were afforded through a convenient route of electrocodeposition from aniline and (NH₄)₆Mo₇O₂₄. The composite films showed characteristic redox behaviors of PANI and MoO_x, respectively, on the cyclic voltammograms. Chlorate and bromate were catalytically electroreduced with an enlarged current on the composite film at a potential ca. 0.2 V more positive than that on MoO_x. The potential window for the composite film to display pseudocapacitive properties in 1.0 mol·dm⁻³ NaNO₃ was −0.6 ∼ 0.6 V vs SCE. The cathodic potential limit shifted at least 0.4 V negatively from that of polyaniline (PANI)-based materials reported so far. The specific capacitance was 363.6 F·g⁻¹ when the composite film was charged–discharged at 1.5 mA·cm⁻², about two times of that of the similarly prepared PANI. The composite film was characterized by Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Molybdenum existed in a mixed state of +5 and +6 in the composite film based on XRD and XPS investigations. Figure PANI and (MoO_x) were electrocodeposited in aqueous solutions from aniline and (NH₄)₆Mo₇O₂₄. The composite film obtained displayed catalytic activities toward the electroreduction of oxoanions. The pseudocapacitance of the composite film is nearly two times of that of PANI with the potential window extended negatively up to −0.6 V vs SCE     

Solid state voltammetric characterization of iron hexacyanoferrate encapsulated in silica

We describe a sol-gel approach by which iron hexacyanoferrate is immobilized in silica in a manner suited to investigation by electrochemistry in the absence of a contacting liquid phase. Such physicochemical parameters as concentration of redox sites (C _o) and apparent (effective) diffusion coefficient (D _app) are estimated by performing cyclic voltammetric and potential step experiments in two time regimes, which are characterized by linear and spherical diffusional patterns, respectively. Values of D _app and C _o thereby obtained are 2.0 × 10⁻⁶ cm² s⁻¹ and 1.4 × 10⁻² mol dm⁻³. The D _app value is larger than expected for a typical solid redox-conducting material. Analogous measurements done in iron(III) hexacyanoferrate(III) solutions of comparable concentrations, 1.0 × 10⁻² and 5.0 × 10⁻³ mol dm⁻³, yield D _app on the level of 5–6 × 10⁻⁶ cm² s⁻¹. Thus, the dynamics of charge propagation in this sol-gel material is almost as high as in the liquid phase. The residual water in the silica, along with the pore structure, are important to the overall mechanism of charge transport, which apparently is limited by physical diffusion rather than electron self-exchange. Under conditions of a solid state voltammetric experiment which utilizes an ultramicroelectrode, encapsulated iron hexacyanoferrate redox centers seem to be in the dispersed colloidal state rather than in a form of the rigid polymeric film. Received: 8 April 1999 / Accepted: 13 August 1999     

Kinetic Determination of Iodide Based on its Effect on the Hydrogen Peroxide Oxidation of Triflupromazine

 A new selective, sensitive, and simple kinetic method is developed for the determination of trace amounts of iodide. The method is based on the catalytic effect of iodide on the reaction of triflupromazine (TFP) with H₂O₂. The reaction is followed spectrophotometrically by tracing the oxidation product at 498 nm within 1 min after addition of H₂O₂. The optimum reaction conditions are TFP (0.4 × 10⁻³ M), H₂SO₄ (1.0M), H₃PO₄ (2.0M), and H₂O₂ (1.6M) at 30°C. Following this procedure, iodide can be determined with a linear calibration graph up to 4.5 ng ċ cm⁻³ and a detection limit of 0.04 ng ċ cm⁻³, based on the 3 S_b criterion. The method can also be applied to the determination of iodate and periodate ions. Determination of as little as 0.2, 1.0, 2.0, and 4.0 ng ċ cm⁻³ of I⁻, IO₃ ^-, or IO₄ ^- in aqueous solutions gave an average recovery of 98% with relative standard deviations below 1.6% (n = 5). The method was applied to the determination of iodide in Nile river water and ground waters as well as in various food samples after alkaline ashing treatment. The method is compared with other catalytic spectrophotometric procedures for iodide determination.     

Voltammetric Determination of Folic Acid with a Multi-Walled Carbon Nanotube-Modified Gold Electrode

The voltammetric behavior of folic acid (FA) at a multi-walled carbon nanotube (MWNT) modified gold electrode has been investigated by cyclic voltammetry, chronoamperometry and chronocoulometry. The modified electrode exhibits a good promoting effect on the electrochemical reaction of FA. FA can generate a well-defined anodic peak at around 0.83 V (vs. SCE) in 0.1 M H₃PO₄–NaH₂PO₄ buffer solution of pH 2.5. The peak results from a 2-electron transfer of FA, and the standard potential of FA is estimated to be 0.79 V (vs. SCE). The parameters affecting the response of FA, such as solution pH, accumulation time, accumulation potential, and amount of MWNTs are optimized for the determination of FA. Under the optimum conditions, the peak current changes linearly with FA concentration in the range from 2.0 × 10⁻⁸ M to 1.0 × 10⁻⁶ M. This method has been applied to the determination of FA in drug tablets, and the recovery is 93.9–96.9%. In addition, the influence of some coexistent species is examined. When a Nafion layer is introduced on the gold electrode before deposition of MWNTs, the resulting composite electrode can give better response to FA. At the same time, the interference by some foreign species is suppressed to some extent.     

Voltammetric and Spectrophotometric Determination of Nizatidi ne in Pharmaceutical Formulations

 Two methods are described for quantitative determination of nizatidine. The first is a cathodic stripping voltammetric method which is based on the accumulation of the compound at the hanging mercury drop electrode. The adsorptive stripping response was evaluated with respect of accumulation time, potential, concentration, pH and other variables. A linear calibration graph was obtained over the range 3.0×10⁻⁸–1.0×10⁻⁶ M with a detection limit 3.0×10⁻⁸ M after a 20s accumulation time at −0.2 V accumulation potential. On the other hand, it was found that the detection limit could be lowered to 1.0×10⁻⁸ M after 180s accumulation time at −0.2 V accumulation potential. The relative standard deviation was in the range 1.2−2.0% for six measurements. The tolerance amounts of the common excipients have also been reported. The second is a spectrophotometric method which is based on the formation and extraction of the ion-pair complex formed between nizatidine and either bromocresol green or bromothymol blue. The extracted colored ion-pair complexes absorb at 416 nm. The effect of different factors such as: type of organic solvent, pH, reagent concentration, number of extraction times, shaking time, temperature and the tolerance amount of the common excipients have been reported. The calibration graph was linear in the range 6.0×10⁻⁷–1.8×10⁻⁵ M with a detection limit of 6.0×10⁻⁷ M and molar absorptivity of 2.1×10⁴ lċmol⁻¹ċcm⁻¹ when using bromocresol green, while the calibration graph was linear in the range 3.0×10⁻⁷–1.1×10⁻⁵ M with a detection limit of 3.0×10⁻⁷ M and molar absorptivity of 3.2×10⁴ lċmol⁻¹ċcm⁻¹ when using bromothymol blue. The spectrophotometric methods offer alternative methods with reasonable sensitivity, selectivity and accuracy with relative standard deviation in the range 2.1−6.0% and 1.2−4.7% (for six measurements) when using bromothymol blue and bromocresol green, respectively. The proposed two methods were applied for the determination of nizatidine in commercially available dosage forms. A comparison between the voltammetric and the extraction-spectrophotometric methods was also reported. Received April 19, 1999. Revision August 30, 1999.     

Simple sensor for simultaneous determination of dihydroxybenzene isomers

A simple sensor based on bare carbon ionic liquid electrode was fabricated for simultaneous determination of dihydroxybenzene isomers in 0.1 mol L⁻¹ phosphate buffer solution (pH 6.0). The oxidation peak potential of hydroquinone was about 0.136 V, catechol was about 0.240 V, and resorcinol 0.632 V by differential pulse voltammetric measurements, which indicated that the dihydroxybenzene isomers could be separated absolutely. The sensor showed wide linear behaviors in the range of 5.0 × 10⁻⁷–2.0 × 10⁻⁴ mol L⁻¹ for hydroquinone and catechol, 3.5 × 10⁻⁶–1.535 × 10⁻⁴ mol L⁻¹ for resorcinol, respectively. And the detection limits of the three dihydroxybenzene isomers were 5.0 × 10⁻⁸, 2.0 × 10⁻⁷, 5.0 × 10⁻⁷ mol L⁻¹, respectively (S/N = 3). The proposed method could be applied to the determination of dihydroxybenzene isomers in artificial wastewater and the recovery was from 93.9% to 104.6%.     

Bi5Nb3O15 as a photocatalyst: photocatalytic and photoelectrochemical studies

Bi₅Nb₃O₁₅ was prepared from a stoichiometric mixture of Bi₂O₃ and Nb₂O₅ at 300–500 °C. The prepared photocatalyst was characterized by diffuse reflection spectrum (DRS), X-ray diffraction (XRD), scanning electron microscopy (SEM) and particle size analysis. The band gap, crystal structure and average grain size were determined from the above methods to be 3.25 eV, distorted pyrochlore and 4–5 μm respectively. The photoelectrochemical behavior of hydrogen-reduced Bi₅Nb₃O₁₅ was investigated in 0.1 M Na₂SO₄ and using the Fe(CN)₆ ^3−/4− redox couple for measuring the current-voltage characteristics. The cyclic voltammetric studies revealed that the onset potential for photocurrent generation existed at −0.45 V, which is more negative to water reduction level at pH 7.0, and that of the photocurrent at 1.0 V was observed as 0.58 mA/cm². Photocatalytic hydrogen production has been achieved by using Bi₅Nb₃O₁₅ as a photocatalyst in presence of methyl viologen. The quantum yield for hydrogen production for this system was found to be 0.83. All the studies clearly indicated that Bi₅Nb₃O₁₅ has potential in solar energy conversion. Received: 22 May 1997 / Accepted: 18 September 1997     

Electro-catalysis by immobilised human flavin-containing monooxygenase isoform 3 (hFMO3)

Human flavin-containing monooxygenases are the second most important class of drug-metabolizing enzymes after cytochromes P450. Here we report a simple but functional and stable enzyme-electrode system based on a glassy carbon (GC) electrode with human flavin-containing monooxygenase isoform 3 (hFMO3) entrapped in a gel cross-linked with bovine serum albumin (BSA) by glutaraldehyde. The enzymatic electrochemical responsiveness is characterised by using well-known substrates: trimethylamine (TMA), ammonia (NH₃), triethylamine (TEA), and benzydamine (BZD). The apparent Michaelis–Menten constant (K′_M) and apparent maximum current (I′_max) are calculated by fitting the current signal to the Michaelis–Menten equation for each substrate. The enzyme-electrode has good characteristics: the calculated sensitivity was 40.9 ± 0.5 mA mol⁻¹ L cm⁻² for TMA, 43.3 ± 0.1 mA mol⁻¹ L cm⁻² for NH₃, 45.2 ± 2.2 mA mol⁻¹ L cm⁻² for TEA, and 39.3 ± 0.6 mA mol⁻¹ L cm⁻² for BZD. The stability was constant for 3 days and the inter-electrode reproducibility was 12.5%. This is a novel electrochemical tool that can be used to investigate new potential drugs against the catalytic activity of hFMO3.     

FAD-modified SiO2/ZrO2/C ceramic electrode for electrocatalytic reduction of bromate and iodate

SiO₂/ZrO₂/C carbon ceramic material with composition (in wt%) SiO₂ = 50, ZrO₂ = 20, and C = 30 was prepared by the sol–gel-processing method. A high-resolution transmission electron microscopy image showed that ZrO₂ and the graphite particles are well dispersed inside the matrix. The electrical conductivity obtained for the pressed disks of the material was 18 S cm⁻¹, indicating that C particles are also well interconnected inside the solid. An electrode modified with flavin adenine dinucleotide (FAD) prepared by immersing the solid SiO₂/ZrO₂/C, molded as a pressed disk, inside a FAD solution (1.0 × 10⁻³ mol L⁻¹) was used to investigate the electrocatalytic reduction of bromate and iodate. The reduction of both ions occurred at a peak potential of −0.41 V vs. the saturated calomel reference electrode. The linear response range (lrr) and detection limit (dl) were: BrO₃ ⁻, lrr = 4.98 × 10⁻⁵–1.23 × 10⁻³ mol L⁻¹ and dl = 2.33 μmol L⁻¹; IO₃ ⁻, lrr = 4.98 × 10⁻⁵ up to 2.42 × 10⁻³ and dl = 1.46 μmol L⁻¹ for iodate.     

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.