Preparation and electrochemistry of cadmium pentacyanonitrosylferrate film modified glassy carbon electrode

A glassy carbon (GC) electrode surface was modified with a cadmium pentacyanonitrosylferrate (CdPCNF) film as a novel electrode material. The modification procedure of the GC surface includes two consecutive procedures: (i) the electrodeposition of metallic cadmium on the GC electrode surface from a CdCl₂ solution and (ii) the chemical transformation of the deposited cadmium to the CdPCNF films in 0.05 M Na₂[Fe(CN)₅NO] + 0.5 M KNO₃ solution. The modified GC electrode showed a well-defined redox couple due to [Cd^IIFe^III/II(CN)₅NO]^0/−1 system. The effects of supporting electrolytes and solution pH were studied on the electrochemical behavior of the modified electrode. The diffusion coefficients of alkali-metal cations in the film (D), the transfer coefficient (α) and the charge transfer rate constant at the modifying film | electrode interface (k_s), were calculated in the presence of various alkali-metal cations. The stability of the modified electrode was investigated under various experimental conditions.     

Electrochemical characteristics of dopamine oxidation at palladium hexacyanoferrate film, electroless plated on aluminum electrode

A novel electrode material was obtained at an aluminum electrode (Al) by a simple electroless method including two consecutive procedures: (i) the electroless deposition of metallic palladium on the Al electrode surface from PdCl₂ + 25% ammonia solution and (ii) the chemical transformation of deposited palladium to the palladium hexacyanoferrate (PdHCF) films in a solution containing 0.5 M K₃[Fe(CN)₆]. The modified Al electrode demonstrated a well-behaved redox couple due to the redox reaction of the PdHCF film. The PdHCF film showed an excellent electrocatalytic activity toward the oxidation of dopamine (DA). The effect of solution pH on the voltammetric response of DA has been investigated. A linear calibration graph was obtained over the DA concentration range 2-51 mM. The rate constant k and transfer coefficient α for the catalytic reaction and the diffusion coefficient of DA in the solution D, were found to be 4.67 × 10² M⁻¹ s⁻¹, 0.63 and 2.5 × 10⁻⁶ cm² s⁻¹, respectively. The interference of ascorbic acid was investigated and greatly reduced using a thin film of Nafion on the modified electrode. The modified electrode indicated reproducible behavior and a high level stability during electrochemical experiments, making it particularly suitable for the analytical purposes.     

Preparation and electrocatalytic oxidation properties of a nickel pentacyanonitrosylferrate modified carbon composite electrode by two-step sol-gel technique: improvement of the catalytic activity

The sol-gel technique was used to construct nickel pentacyanonitrosylferrate (NiPCNF) modified composite ceramic carbon electrodes (CCEs). This involves two steps: forming a CCE containing Ni powder and then immersing the electrode into a sodium pentacyanonitrosyl-ferrate solution (electroless deposition). The cyclic voltammograms of the resulting surface modified CCE under optimum conditions show a well-defined redox couple due to the [Ni^IIFe^III/II(CN)₅NO]^0/−1 system. The electrochemical properties and stability of the modified electrode were investigated by cyclic voltammetry. The apparent electron transfer rate constant (k_s) and transfer coefficient (α) were determined by cyclic voltammetry being about 1.1 s⁻¹ and 0.55, respectively. Sulfite has been chosen as a model to elucidate the electrocatalytic ability of NiPCNF-modified CCE prepared by one- or two-step sol-gel technique. The modified electrode showed excellent electrocatalytic activity toward the SO₃²⁻ electro oxidation in pH range 3-9 in comparison with CCE modified by homogeneous mixture of graphite powder, Ni(NO₃)₂ and Na₂[Fe(CN)₅NO] (one-step sol-gel technique). Sulfite was determined amperometrically at the surface of this modified electrode in pH 7. Under the optimized conditions the calibration curve is linear in the concentration range 2 μM to 2.0 mM. The detection limit (signal-to-noise is 3) and sensitivity are 0.5 μM and 13.5 nA/μM. The modified carbon ceramic electrode containing nickel pentacyanonitrosylferrate shows good repeatability, short response time, t (90%) <2 s, long-term stability (3 months), and it is renewed by simple mechanical polishing and its immersing in Na₂[Fe(CN)₅NO] solution. The advantages of the SO₃²⁻ amperometrically detector based on the nickel pentacyanonitrosylferrate-doped CCE is high sensitivity, inherent stability at wide pH range, excellent catalytic activity and less expense and simplicity of preparation. This sensor can be used as amperometric detector in chromatographic instruments.     

Glassy carbon electrode modified with Nafion-Au colloids for clenbuterol electroanalysis

Stable Nafion-Au colloids were immobilized on a glassy carbon electrode (GCE) for detection of β-agonist clenbuterol by electroanalysis. The Au colloids were prepared by a one-step electrodeposition onto GCE, with obvious electrocatalytic activity present. The negatively charged Nafion film was an efficient barrier to negatively charged interfering compounds, resulting in accumulation of positively charged clenbuterol at the Nafion film. The electrochemical characters of the electrode during various modified steps in a redox probe system of K₄[Fe(CN)₆]/K₃[Fe(CN)₆] were confirmed by cyclic voltammetry (CV) and AC-impedance. In Britton-Robinson (B-R) buffer solution (pH = 2.0) and the potential range of −0.2 to 1.2 V, the Nafion-Au colloid modified electrode, compared to a bare GCE, exhibits obvious electrocatalytic activity towards the redox of clenbuterol by greatly enhancing the peak current with a linear calibration curve from 8.0 × 10⁻⁷ to 1.0 × 10⁻⁵ mol/L and a detection limit of (1.0 × 10⁻⁷ mol/L) (R = 0.996). The modified electrode shows high sensitivity, selectivity and reproducibility. The recovery for detecting clenbuterol (∼10⁻⁶ mol/L) in human serum is up to 98.19%.     

Electropolymerization of aniline in acid media on the bare and chemically pre-treated aluminum electrodes: A comparative characterization of the polyaniline deposited electrodes

The electrosynthesis of polyaniline on the bare aluminum and pre-treated aluminum surface achieved in aqueous H₂PtCl₆ solution saturated with NaF for few seconds is described. The effect of some factors such as pre-treatment time, aniline and sulfuric acid concentrations on the electropolymerization process was investigated and optimum conditions were obtained. The stability of polyaniline film on the pre-treated aluminum electrode (Al-Pt) was studied as function of the potential imposed on the electrode. For applied electrode potentials of 0.1-0.7 V, the first-order degradation rate constant, k, of polyaniline film varies between 1 × 10⁻⁶ and 2 × 10⁻⁵ s⁻¹, and a relatively low slope (i.e. 2.1) was obtained for the plot of log k versus E. The coatings were characterized by scanning electron microscopy (SEM), and cyclic voltammetric behavior of the polyaniline-deposited Al electrode (Al/PANI) and polyaniline-deposited Al-Pt electrode (Al-Pt/PANI) in 0.1 H₂SO₄ solutions is described. The electrocatalytic activity of the Al-Pt/PANI electrode against para-benzoquinone/hydroquinone (Q/H₂Q) and Fe(CN)₆³⁻/Fe(CN)₆⁴⁻ redox systems was investigated and the obtained results are compared with those obtained on Al/PANI and bulk Pt electrodes.     

Electrochemical properties of modified copper-thallium hexacyanoferrate electrode in the presence of different univalent cations

The preparation of copper(II) hexacyanoferrate (CuHCF) films on the surface of gold electrodes as well as their characterization in solutions of various alkali metal and NH₄⁺ cations and in the presence of thallium(I) are described. The electrochemical quartz crystal microbalance and cyclic voltammetric techniques were used. In 0.50 M lithium nitrate, even at submillimolar concentration of Tl(I), the formal potential of CuHCF was shifted to more positive values. At higher Tl(I) concentrations, the formal potential of the CuHCF redox reaction changed linearly with the logarithm of Tl(I) concentration (in the 0.50 M solution of lithium or another alkali metal nitrate). From such dependencies, selectivity coefficients K_Tl/M were calculated, and they show that the CuHCF film on the gold electrode interacts preferentially with Tl(I). High affinity of Tl(I) to copper hexacyanoferrate, that was observed in the presence of alkali metal cations, was explained by relatively strong donor-acceptor interactions of Tl(I) ions with nitrogen in CN groups of the CuHCF film.It was also shown for simple M₄[Fe(CN)₆] metal ferrocyanate salts (where M = Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺ and Tl⁺) that there is a preferential interaction of Tl⁺ with CN group consistent with formation of a Tl-NC-Fe bridge.     

Electrocatalytic oxidation of ascorbic acid by [Fe(CN)6] redox couple electrostatically trapped in cationic N,N-dimethylaniline polymer film electropolymerized on diamond electrode

Multinegatively charged metal complex, hexacyanoferrate ([Fe(CN)₆]⁴⁻), was electrostatically trapped in the cationic polymer film of N,N-dimethylaniline (PDMA) which was electrochemically deposited on the boron-doped diamond (BDD) electrode by controlled-potential electro-oxidation of the monomer. This ferrocyanide-trapped PDMA film was used to catalyze the oxidation of ascorbic acid (AA). Increase in the oxidation current response with a negative shift of the anodic peak potential was observed at the cationic PDMA film-coated BDD (PDMA|BDD) electrode, compared with that at the bare BDD electrode. A more drastic enhancement in the oxidation peak current as well as more negative shift of oxidation potential was found at the ferrocyanide-trapped PDMA film-coated BDD ([Fe(CN)₆]^3−/4−|PDMA|BDD) electrode. This [Fe(CN)₆]^3−/4−|PDMA|BDD electrode can be used as an amperometric sensor of AA. Ferrocyanide, electrostatically trapped in the polymer film shows more electrocatalytic activity than that coordinatively attached to the polymer film or dissolved in the solution phase. The electrocatalytic current depends on the surface coverage of ferricyanide, Γ_Fe, within the polymer film. Diffusion coefficient (D) of AA in the solution was estimated by rotating disk electrode voltammetry: D = (5.8 ± 0.3) × 10⁻⁶ cm² s⁻¹. The second-order rate constant for the catalytic oxidation of AA by ferricyanide was also estimated to be 9.0 × 10⁴ M⁻¹ s⁻¹. In the hydrodynamic amperometry using the [Fe(CN)₆]^3−/4−|PDMA|BDD electrode, a successive addition of 1 μM AA caused the successive increase in current response with equal amplitude and the sensitivity was calculated as 0.233 μA cm⁻² μM⁻¹.     

Electrocatalysis Characteristics of a Polynuclear Cyanide Complex, Ruthenium Purple, for Dihydrogen Oxidation

An electrocatalytic dihydrogen oxidation was found to take place on an electrode coated with iron(III) ruthenocyanide (i.e., repeating unit cell structure: Fe^III ₄[Ru^II(CN)₆]₃ or MFe^III[Ru^II(CN)₆] and M = alkali metal counter ion) called ruthenium purple (RP). It was shown by voltammetric study that an electrocatalytic dihydrogen oxidation is induced on oxidizing the Fe^II ion in the cyanometallate. When the electrocatalysis characteristics of RP were investigated by voltammetry, especially in terms of the kinds of electrolyte used (K⁺ or Na⁺), RP exhibited a more efficient electrocatalysis in the K⁺ than in the Na⁺ electrolyte system. While a one-electron electro-oxidation of Fe^II to Fe^III occurs, there is also a release of hydrated alkali metal cation(s) from the anionic RP (i.e., reduced RP) to compensate for charge. Moreover, cation transport through the cyanometallate network is more facile for the K⁺ electrolyte system (cf., size of hydrated cation: Na⁺ at 0.36 nm lattice channel of RP at 0.35 nm > K⁺ at 0.24 nm). Therefore, it was most probable that the present electrocatalysis is kinetically dominated by the electro-oxidation.     

Micromolar determination of sulfur oxoanions and sulfide at a renewable sol-gel carbon ceramic electrode modified with nickel powder

The sol-gel technique was used to fabricate nickel powder carbon composite electrode (CCE). The nickel powder successfully used to deposit NiO_x thin film on conductive carbon ceramic electrode for large surface area catalytic application. Repetitive cycling in potential range −0.2 to 1.0 V was used to form of a thin nickel oxide film on the surface carbon composite electrode. The thin film exhibits an excellent electro-catalytic activity for oxidation of SO₃²⁻, S₂O₄²⁻, S₂O₃²⁻, S₄O₆²⁻ and S²⁻ in alkaline pH range 10-14. Optimum pH values for detection of all sulfur derivatives is 13 and catalytic rate constants are in range 2.4 × 10³-8.9 × 10³ M⁻¹ s⁻¹. The hydrodynamic amperometry at rotating modified CCE at constant potential versus reference electrode was used for detection of sulfur derivatives. Under optimized conditions the calibration plots are linear in the concentration range 10 μM-15 mM and detection limit 1.2-34 μM and 0.53-7.58 nA/μM (sensitivity) for electrode surface area 0.0314 cm². The nickel powder doped modified carbon ceramic electrode shows good reproducibility, a short response time (2.0 s), remarkable long term stability, less expense, simplicity of preparation, good chemical and mechanical stability, and especially good surface renewability by simple mechanical polishing and repetitive potential cycling. This sensor can be used into the design of a simple and cheap chromatographic amperometry detector for analysis of sulfur derivatives.     

Electrochemical characterization of cetyltrimethyl ammonium bromide modified carbon paste electrode and the application in the immobilization of DNA

A cetyltrimethyl ammonium bromide modified carbon paste electrode (CTAB/CPE) was developed in this work based on the surface modification method. The improved electrochemical response of K₄Fe(CN)₆ at this electrode indicated that CTAB could change the surface property of carbon paste electrodes (CPEs), which was demonstrated by the electrochemical impedance spectroscopy (EIS). In 0.1 mM [Fe(CN)₆]^3−/4−, a low exchange current (i₀) of 2.72×10⁻⁷ A at bare CPE was observed while that at CTAB/CPE was 6.79×10⁻⁵ A. The effect of CTAB concentration on the electrode quality revealed that CTAB formed a compact monolayer on the electrode surface with high density of positive charges directed outside the electrode. This electrode showed strong accumulation ability toward Fe(CN)₆⁴⁻ and can also accumulate Co(phen)₃²⁺ by the adsorption of the organic ligands in the hydrophobic area of the monolayer. The electrode was applied to the immobilization of DNA, which was characterized by the isotherm adsorption of Co(phen)₃²⁺.     

Evaluation of the pseudocapacitance in RuO2 with a RuO2/GC thin film electrode

The pseudocapacitance of nanocrystalline RuO₂ with BET surface area of 42 m² g⁻¹ was evaluated using a RuO₂ modified Glassy Carbon (RuO₂/GC) thin film electrode. The charge storage behavior of the RuO₂/GC thin film electrode was studied from fast to slow scan cyclic voltammetry between various potential windows. The utilization of the thin film electrode method for nanocrystalline RuO₂ with known specific surface area allowed a semi-quantitative understanding of the electric double-layer capacitance (C_dl), adsorption related charge (C_ad), and the irreversible redox related charge (C_irr) per unit mass and surface area of RuO₂. Comparison of the cyclic voltammograms between different voltage windows revealed that the contribution from C_irr is especially dominant below 0.4 V (versus RHE) at slow scan rates.     

Electrooxidation of sulfide by cobalt pentacyanonitrosylferrate film on glassy carbon electrode by cyclic voltammetry

A glassy carbon (GC) electrode was modified with cobalt pentacyanonitrosylferrate (CoPCNF) film. Cyclic voltammetry (CV) of the CoPCNF onto the GC (CoPCNF/GC) shows a redox couple (Fe^III/Fe^II) with a standard potential (E^0′) of 580 mV. The current ratio I_pa/I_pc remains almost 1, and a peak separation (ΔE_p) of 106 mV is observed in 0.5 M KNO₃ as the supporting electrolyte. Anodic peak currents were found to be linearly proportional to the scan rate between 10 and 200 mV s⁻¹, indicating an adsorption-controlled process. The redox couple of the CoPCNF film presents an electrocatalytic response to sulfide in aqueous solution. The analytical curve was linear in the concentration range of 7.5 × 10⁻⁵ to 7.7 × 10⁻⁴ M with a detection limit of 4.6 × 10⁻⁵ M for sulfide ions in 0.5 M KNO₃ solution.     

Preparation of polypyrrole/ferrocyanide films modified carbon paste electrode and its application on the electrocatalytic determination of ascorbic acid

Functionalized polypyrrole film were prepared by incorporation of (Fe(CN)₆)⁴⁻ as doping anion, during the electropolymerization of pyrrole onto a carbon paste electrode (CPE) in aqueous solution by using potentiostatic method. The electrochemical behavior of the (Fe(CN)₆)³⁻/(Fe(CN)₆)⁴⁻ redox couple in polypyrrole was studied by cyclic voltammetry and double step potential chronoamperometry methods. In this study, an obvious surface redox reaction was observed and dependence of this reaction on the solution pH was illustrated. The electrocatalytic ability of polypyrrole/ferrocyanide films modified carbon paste electrode (Ppy/FCNMCPEs) was demonstrated by oxidation of ascorbic acid. It has been found that under optimum condition (pH 7.00), the oxidation of ascorbic acid at the surface of such electrode occurs at a potential about 540 mV less positive than unmodified carbon paste electrode. The kinetic parameters such as electron transfer coefficient, α and catalytic reaction rate constant, k_h′, were also determined by using various electrochemical approaches.The catalytic oxidation peak current showed a linear dependent on the ascorbic acid concentration and a linear calibration curve was obtained in the range of 4.5×10⁻⁴ to 9.62×10⁻³ M of ascorbic acid with a correlation coefficient of 0.9999. The detection limit (2σ) was determined as 5.82×10⁻⁵ M.     

Electrochemical behavior of a novel palladium pentacyanonitrosylferrate modified aluminum electrode

Novel inorganic film modified electrodes have been prepared by chemical deposition of a thin palladium pentacyanonitrosylferrate (PdPCNF) film on the surface of aluminum substrate. The modification process including the electroless deposition of metallic palladium on the aluminum electrode surface from PdCl₂+25% ammonia solution and chemical derivatization of deposited palladium to the PdPCNF film in 0.1 M Na₂[Fe(CN)₅NO]+0.5 M KNO₃+HNO₃ solution (pH 1.5-2.5), are described. The aluminum-based modified electrodes exhibit, one pair of well-defined voltammetric peaks which correspond to the Fe(III)/Fe(II) transition in complex structure. The effect of pH, ammonium, alkali metal and alkaline earth metal cations of supporting electrolyte on the electrochemical characteristics of the modified electrode was studied in detail. Diffusion coefficients of hydrated ammonium and alkali metal cations in the film (D), transfer coefficient (α) and transfer rate constant for electron (k_s), were determined. The high stability of this modified electrode makes it attractive in practical application.     

Poly(o-aminophenol) film prepared in the presence of sodium dodecyl sulfate: Application for nickel ion dispersion and the electrocatalytic oxidation of methanol and ethylene glycol

Poly(o-aminophenol) (POAP) was formed by successive cyclic voltammetry in monomer solution in the presence of sodium dodecyl sulfate (SDS) on the surface of a carbon paste electrode. The electrochemical behavior of the SDS-POAP carbon paste electrode has been investigated by cyclic voltammetry in 0.5 M HClO₄ and 5 mM K₄[Fe(CN)₆]/0.1 M KCl solutions as the supporting electrolyte and model system, respectively. Ni(II) ions were incorporated into the electrode by immersion of the polymeric modified electrode having amine groups in 0.1 M Ni(II) ion solution. Cyclic voltammetric and chronoamperometric experiments were used for the electrochemical study of this modified electrode. A good redox behavior of the Ni(III)/Ni(II) couple at the surface of electrode can be observed. The electrocatalytic oxidations of methanol and ethylene glycol (EG) at the surface of the Ni/SDS-POAP electrode were studied in a 0.1 M NaOH solution. Compared to bare carbon paste and POAP-modified carbon paste electrodes, the SDS-POAP electrode significantly enhanced the catalytic efficiency of Ni ions for methanol oxidation. Finally, using a chronoamperometric method, the catalytic rate constants (k) for methanol and ethylene glycol were found to be 2.04 × 10⁵ and 1.05 × 10⁷ cm³ mol⁻¹ s⁻¹, respectively.     

Electrochemistry and electrocatalysis of hemoglobin on multi-walled carbon nanotubes modified carbon ionic liquid electrode with hydrophilic EMIMBF4 as modifier

The direct electrochemistry of hemoglobin (Hb) on multi-walled carbon nanotubes (MWCNTs) modified carbon ionic liquid electrode (CILE) was achieved in this paper. By using a hydrophilic ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIMBF₄) as the modifier, a new CILE was fabricated and further modified with MWCNTs to get the MWCNTs/CILE. Hb molecules were immobilized on the surface of MWCNTs/CILE with polyvinyl alcohol (PVA) film by a step-by-step method and the modified electrode was denoted as PVA/Hb/MWCNTs/CILE. UV-vis and FT-IR spectra indicated that Hb remained its native structure in the composite film. Cyclic voltammogram of PVA/Hb/MWCNTs/CILE showed a pair of well-defined and quasi-reversible redox peaks with the formal potential (E^0′) of −0.370 V (vs. SCE) in 0.1 mol/L pH 7.0 phosphate buffer solution (PBS), which was the characteristic of the Hb heme Fe^III/Fe^II redox couples. The redox peak currents increased linearly with the scan rate, indicating the direct electron transfer was a surface-controlled process. The electrochemical parameters of Hb in the film were calculated with the results of the electron transfer coefficient (α) and the apparent heterogeneous electron transfer rate constant (k_s) as 0.49 and 1.054 s⁻¹, respectively. The immobilized Hb in the PVA/MWCNTs composite film modified CILE showed excellent electrocatalytic activity to the reduction of trichloroacetic acid (TCA) and hydrogen peroxide. So the proposed electrode showed the potential application in the third generation reagentless biosensor.     

Development of a sensor based on tetracyanoethylenide (LiTCNE)/poly-l-lysine (PLL) for dopamine determination

The catalytic oxidation of dopamine (DA) at a LiTCNE (lithium tetracyanoethylenide) film modified electrode is studied by electrochemical approaches. The immobilization of LiTCNE was performed by a polymer (poly-l-lysine) to prepare this modified electrode and its application for dopamine (DA) determination is described in detail. The modified electrode showed a high activity for the electrooxidation of dopamine (DA) at E_p = 0.20 V versus SCE. The modified electrode presented a wide linear response range for DA from 0.01 up to 10 μmol l⁻¹ by differential pulse voltammetry (DPV) with a detection limit of 0.5 nmol l⁻¹. The repeatability of the proposed sensor evaluated in term of relative standard deviation was 3.2% for n = 10. The sensor was applied for the determination of dopamine in pharmaceutical formulations and the average recovery for these samples was 101.9 (±0.1)%.     

Influencing factors on electrochromic hysteresis performance of ruthenium purple produced by a WO3/Tris(2,2′-bipyridine)ruthenium(II)/polymer hybrid film

A [Ru(bpy)₃]²⁺ (bpy = 2,2′-bipyridine)/WO₃ hybrid (denoted as Ru-WO₃) film was prepared as a base layer on an indium tin oxide electrode by electrodeposition from a colloidal solution containing peroxotungstic acid, [Ru(bpy)₃]²⁺ and poly(sodium 4-styrenesulfonate). A ruthenium purple (RP, Fe^III₄[Ru^II(CN)₆]₃, denoted as Fe^III-Ru^II) layer was electrodeposited on a neat WO₃ film or a Ru-WO₃ film from an aqueous RP colloid solution to yield a WO₃/RP bilayer film or a Ru-WO₃/RP bilayer film, respectively. The spectrocyclic voltammetry measurement reveals that Fe^II-Ru^II is oxidized to Fe^III-Ru^II by a geared reaction of [Ru(bpy)₃]^2+/3+ and Fe^III-Ru^II is reduced by a geared reaction of H_xWO₃/WO₃ in the Ru-WO₃/RP film. These geared reactions produced electrochromic hysteresis of the RP layer. However, the absorbance change in the hysteresis was smaller than that for the Ru-WO₃/Prussian blue bilayer film reported previously, resulting from the lower electroactivities of any redox component for the Ru-WO₃/RP film. The lower electroactivities could be explained by the specific interface between the Ru-WO₃ and RP layers. It might contribute to either an increase of the interfacial resistance between the Ru-WO₃ and RP layers, or formation of the physically precise interface between the layers to make it difficult for counter ions to be transported in the interfacial liquid phase involved in the redox reactions in the film. The specific interface at the Ru-WO₃ and RP layers could be formed possibly by the electrostatic interaction between [Ru(bpy)₃]²⁺ and terminal [Ru(CN)₆]⁴⁻ moieties of RP. It could be suggested by the decreased redox potential of [Ru(bpy)₃]²⁺ in the Ru-WO₃ layer from 1.03 to 0.61 V by formation of the RP layer.     

Electrocatalytic oxidation of deoxyguanosine on a glassy carbon electrode modified with a ruthenium oxide hexacyanoferrate film

The electrocatalytic oxidation of deoxyguanosine on a ruthenium hexacyanoferrate (RuOHCF) glassy carbon (GC) modified electrode was investigated in acid medium by using rotating disc electrode (RDE) voltammetry. Chronoamperometric experiments allowed information on the charge transport rate through the RuOHCF film and at a very short time window a diffusion-like behavior was observed with a D_ct value of 2.7 × 10⁻¹¹ cm² s⁻¹ for a film with Γ = 4.47 × 10⁻⁹ mol cm⁻². The influence of systematic variation of rotation rate, film thickness and the electrode potential indicates that the rate of cross-chemical reaction between Ru(IV) centers immobilized into the film and deoxyguanosine controls the overall electrodic process and the value of the rate constant was found to be 3.2 × 10⁶ mol⁻¹ L¹ s⁻¹. The relatively high rate constant of the cross-reaction, the facile penetration of the substrate through the film and the fast transport of electrons suggest that the electrocatalytic process occurs throughout the film layer.     

Development of a biomimetic chitosan film-coated gold electrode for determination of dopamine in the presence of ascorbic acid and uric acid

A gold electrode surface was modified using a dinuclear copper complex [Cu^II₂ (Ldtb)(μ-OCH₃)](BPh₄) and then coated with a chitosan film. This biomimetic polymer film-coated electrode was employed to eliminate the interference from ascorbic acid and uric acid in the sensitive and selective determination of dopamine. The optimized conditions obtained for the biomimetic electrode were 0.1 M phosphate buffer solution (pH 8.0), complex concentration of 2.0 × 10⁻⁴ M, 0.1% of chitosan and 0.25% of glyoxal. Under the optimum conditions, the calibration curve was linear in the concentration range of 4.99 × 10⁻⁷ to 1.92 × 10⁻⁵ M, and detection and quantification limits were 3.57 × 10⁻⁷ M and 1.07 × 10⁻⁶ M, respectively. The recovery study gave values of 95.2-102.6%. The lifetime of this biomimetic sensor showed apparent loss of activity after 70 determinations. The results obtained with the modified electrode for dopamine quantification in the injection solution matrix were in good agreement with those of the pharmacopoeia method.