Electrochemical preparation of epinephrine/Nafion chemically modified electrodes and their electrocatalytic oxidation of ascorbic acid and dopamine

Two types of epinephrine and cyclized epinephrine quinone films have been prepared using cyclic voltammetry from the epinephrine in the strong acidic solutions and neutral aqueous solutions over different scanning potential ranges. The cyclic voltammogram of the epinephrine film is characterized by one redox couple at about +0.5 V (versus Ag|AgCl) and cyclized epinephrine quinone film exhibits one redox couples at about −0.15 V (versus Ag|AgCl) .In addition to cyclic voltammetry and an electrochemical quartz crystal microbalance (EQCM) were used to study the growth mechanism of the epinephrine and cyclized epinephrine quinone molecules. The electrocatalytic oxidation of catecholamines (dopamine and norepinephrine) and also ascorbic acid were investigated in acidic aqueous solutions using epinephrine films. The rotating ring-disk electrode technique was used to investigate the mechanism of electrochemical oxidation of dopamine and ascorbic acid.     

The characterization and bioelectrocatalytic properties of hemoglobin by direct electrochemistry of DDAB film modified electrodes

Direct electrochemistry of hemoglobin can be performed in acidic and basic aqueous solutions in the pH range 1-13, using stable, electrochemically active films deposited on a didodecyldimethylammonium bromide (DDAB) modified glassy carbon electrode. Films can also be produced on gold, platinum, and transparent semiconductor tin oxide electrodes. Hemoglobin/DDAB films exhibit one, two, and three redox couples when transferred to strong acidic, weak acidic and weak basic, and strong basic aqueous solutions, respectively. These redox couples, and their formal potentials, were found to be pH dependent. An electrochemical quartz crystal microbalance and cyclic voltammetry were used to study the in situ deposition of DDAB on gold disc electrodes and hemoglobin deposition on DDAB film modified electrodes. A hemoglobin/DDAB/GC modified electrode is electrocatalytically reduction active for oxygen and H₂O₂, and electrocatalytically oxidation active for S₂O₄²⁻ through the Fe(III)/Fe(II) redox couple. In the electrocatalytic reduction of S₄O₆²⁻, S₂O₄²⁻, and SO₃²⁻, and the dithio compounds of 2,2′-dithiosalicylic acid and 1,2-dithiolane-3-pentanoic acid, the electrocatalytic current develops from the cathodic peak of the redox couple at a potential of about −0.9 V (from the Fe(II)/Fe(I) redox couple) in neutral and weakly basic aqueous solutions. Hemoglobin/DDAB/GC modified electrodes are electrocatalytically reduction active for trichloroacetic acid in strong acidic buffered aqueous solutions through the Fe(III)/Fe(II) redox couple. However, the electrocatalytic current developed from the cathodic peak of the redox couple at a potential of about −0.9 V (from the Fe(II)/Fe(I) redox couple) in weak acidic and basic aqueous solutions. The electrocatalytic properties were investigated using the rotating ring-disk electrode method.     

Separation and concentration effect of f-MWCNTs on electrocatalytic responses of ascorbic acid, dopamine and uric acid at f-MWCNTs incorporated with poly (neutral red) composite films

A novel conductive composite film containing functionalized multi-walled carbon nanotubes (f-MWCNTs) with poly (neutral red) (PNR) was synthesized on glassy carbon electrodes (GC) by potentiostatic method. The composite film exhibited promising electrocatalytic oxidation of mixture of biochemical compounds such as ascorbic acid (AA), dopamine (DA) and uric acid (UA) in pH 4.0 aqueous solutions. It was also produced on gold electrodes by using electrochemical quartz crystal microbalance technique, which revealed that the functional properties of composite film were enhanced because of the presence of both f-MWCNTs and PNR. The surface morphology of the polymer and composite film deposited on transparent semiconductor tin oxide electrodes were studied using scanning electron microscopy and atomic force microscopy. These two techniques showed that the PNR was fibrous and incorporated on f-MWCNTs. The electrocatalytic responses of neurotransmitters at composite films were measured using both cyclic voltammetry (CV) and differential pulse voltammetry (DPV). These experiments revealed that the difference in f-MWCNTs loading present in the composite film affected the electrocatalysis in such a way, that higher the loading showed an enhanced electrocatalytic activity. From further electrocatalysis studies, well separated voltammetric peaks were obtained at the composite film modified GC for AA, DA and UA with the peak separation of 0.17 V between AA-DA and 0.15 V between DA-UA. The sensitivity of the composite film towards AA, DA and UA in DPV technique was found to be 0.028, 0.146 and 0.084 μA μM⁻¹, respectively.     

Capability of a carbon-polyvinylchloride composite electrode for the detection of dopamine, ascorbic acid and uric acid

In this work, the composite carbon-polyvinylchloride (C-PVC) was used as an electrode for the detection of dopamine, ascorbic acid, uric acid and their mixtures by differential pulse voltammetry (DPV). The results showed that the untreated C-PVC electrode was selective and stable for the oxidation of dopamine in a mixture containing uric acid and an excess of ascorbic acid in acidic medium. The pre-treated C-PVC electrode in a neutral medium exhibited good resolution of the mixture components in the micro molar concentration range of DA. The ageing of the C-PVC electrode during longer time periods did not affect the peak potential and the detection of dopamine, uric acid and ascorbic acid in 0.1 M H₂SO₄. The practical analytical utility of the C-PVC electrode was demonstrated by the measurement of uric acid in human urine and serum samples without any preliminary pre-treatment.     

Voltammetric resolution of dopamine in the presence of ascorbic acid and uric acid at poly (calmagite) film coated carbon paste electrode

The poly (calmagite) film was synthesized on the surface of carbon paste electrode by electrochemical method. The synthesized polymer film coated electrode exhibits excellent electrocatalytic activity towards the detection of dopamine at neutral pH. The scan rate effect was found to be adsorption controlled electrode process. The concentration effect of dopamine was studied. The redox peak potentials of dopamine were depend on pH. This polymer film coated electrode was very good at simultaneous study of dopamine in the presence of high concentrated ascorbic acid and uric acid. The incorporation study was done by varying the concentration of one species while other two are kept constant. The proposed method was applied to the detection of dopamine in injection samples.     

Preparation and characterization of osmium hexacyanoferrate films and their electrocatalytic properties

Osmium hexacyanoferrate films have been prepared using repeated cyclic voltammetry, and the deposition process and the films’ electrocatalytic properties in electrolytes containing various cations have been investigated. The cyclic voltammograms recorded the deposition of osmium hexacyanoferrate films directly from the mixing of Os³⁺ and Fe(CN)₆³⁻ ions from solutions containing various cations. An electrochemical quartz crystal microbalance, cyclic voltammetry, and UV-visible spectroscopy were used to study the growth mechanism of the osmium hexacyanoferrate films. The osmium hexacyanoferrate films showed a single redox couple, and the redox reactions included “electron transfer” and “proton transfer” with a formal potential that demonstrates a proton effect in acidic solutions up to a 12 M aqueous HCl solution. The electrochemical and electrochemical quartz crystal microbalance results indicate that the redox process was confined to the immobilized osmium hexacyanoferrate film. The electrocatalytic reduction of dopamine, epinephrine, norepinephrine, S₂O₃²⁻, and SO₅²⁻ by the osmium hexacyanoferrate films was performed. The preparation and electrochemical properties of co-deposited osmium(III) hexacyanoferrate and copper(II) hexacyanoferrate films were determined, and their two redox couples showed formal potentials that demonstrated a proton effect and an alkaline cation effect, respectively. Electrocatalytic reactions on the hybrid films were also investigated.     

The bioelectrocatalytic properties of cytochrome C by direct electrochemistry on DNA film modified electrode

The direct electrochemistry of cytochrome C can be performed in weak acidic and basic aqueous solutions. Cytochrome C can be deposited as a stable and electrochemically active film on a deoxyribonucleic acid (DNA) modified glassy carbon electrode. These films can also be produced on gold, platinum, and transparent semiconducting tin oxide electrodes. Two-layer modified electrodes containing cytochrome C and a DNA film were prepared by the deposition of cytochrome C on a DNA film modified electrode. The cytochrome C/DNA film was electrocatalytically oxidation active for l-cysteine in a pH 8.3 tris(hydroxymethyl)aminomethane (TRIS)-buffered aqueous solution through both Fe^III and Fe^IV species. The electrocatalytic oxidation current developed from the anodic peak of the redox couple. The electrocatalytic oxidation properties of ascorbic acid, NH₂OH, N₂H₄, and SO₃²⁻ by a cytochrome C/DNA film were also determined, and shown to be electrocatalytically active. An electrochemical quartz crystal microbalance, cyclic voltammetry, and direct spectroelectrochemistry were used to study in situ DNA deposition on a gold disc electrode and cytochrome C deposition on DNA/Au and DNA/GC films. The direct electrochemistry of cytochrome C can also be performed, and it can be deposited as a stable and electrochemically active film on polyvinyl sulfonate, polystyrene sulfonate, TiO₂, and polyethylene glycol modified glassy carbon electrodes. The results show that cytochrome C interacts with, and deposits on, a DNA film modified electrode, and that the cytochrome C (Fe^III) oxidized form is more easily deposited on a DNA film than the cytochrome C (Fe^II) reduced form.     

Fabrication of a PANI/Au nanocomposite modified nanoelectrode for sensitive dopamine nanosensor design

Polyaniline/Au nanocomposite modified nanoelectrodes based dopamine nanosensors have been developed. The polyaniline/Au nanocomposite film was deposited at the exposed end of the nanoelectrode tip by a surface-graft polymerization method to fabricate a desired modified nanoelectrode. With this modified method, the nanocomposites firmly adhered on the electrode surface and the modified nanoelectrode still had a sharp tip, which was proved by the scanning electron microscope. The electrochemical measurement shows the polyaniline/Au nanocomposite modified film has a good and stable redox activity in neutral solution. The modified nanoelectrode exhibits the excellent electrocatalytic activity towards the oxidations of ascorbic acid and dopamine in phosphate buffer solution. The separation of anodic peak potential of dopamine and ascorbic acid reaches 250 mV. Differential pulse voltammograms results illustrate that dopamine can be selectively determined in the presence of thousands times higher concentration of ascorbic acid with a wide linear range from 200 to 0.3 μM and the detection limit is 0.1 μM. This study provides a simple method for the construction of dopamine nanosensors that have a good sensitivity, wide linear range and stable response. The nanosensors are hopeful to be applied to the detection of dopamine in vivo.     

Preparation, characterization and electrocatalytic properties of poly(luminol) and polyoxometalate hybrid film modified electrodes

Hybrid films composed of poly(luminol) and nanometer-sized clusters of polyoxometalate, SiMo₁₂O₄₀⁴⁻ and PMo₁₂O₄₀³⁻ have been prepared in acidic aqueous solutions. These films are stable and electrochemically active, and produced on glassy carbon, platinum, gold and transparent semiconductor tin oxide electrodes. The electrochemical quartz crystal microbalance and cyclic voltammetry were used to study in situ growth of the hybrid poly(luminol)/SiMo₁₂O₄₀⁴⁻ and poly(luminol)/PMo₁₂O₄₀³⁻. Both the poly(luminol)/SiMo₁₂O₄₀⁴⁻ and poly(luminol)/PMo₁₂O₄₀³⁻ hybrid films showed four redox couples and the electrochemical properties were compared to SiMo₁₂O₄₀⁴⁻ and PMo₁₂O₄₀³⁻. When transferred to various acidity aqueous solutions, the four redox couples and the formal potentials of two hybride film were observed to be pH-dependent. The electrocatalytic reduction of ClO₃⁻, BrO₃⁻, IO₃⁻, S₂O₈²⁻ and NO₂⁻ by a poly(luminol)/PMo₁₂O₄₀³⁻ hybrid film in an acidic aqueous solution showed an electrocatalytic reduction activity of IO₃⁻ > BrO₃⁻ and ClO₃⁻. The electrocatalytic oxidation of dopamine and epinephrine by a poly(luminol)/PMo₁₂O₄₀³⁻ hybrid film was also investigated.     

Preparation, characterization and electrocatalytic behavior of zinc oxide/zinchexacyanoferrate and ruthenium oxide hexacyanoferrate hybrid film-modified electrodes

Polynuclear mixed-valent hybrid films of zinc oxide/zinchexacyanoferrate and ruthenium oxide hexacyanoferrate (ZnO/ZnHCF-RuOHCF) have been deposited on electrode surfaces from H₂SO₄ solution containing Zn(NO₃)₂, RuCl₃ and K₃[Fe(CN)₆] by potentiodynamic cycling method. Simultaneous cyclic voltammetry and electrochemical quartz crystal microbalance (EQCM) measurements demonstrate the steady growth of hybrid film. Surface morphology of hybrid film was investigated using scanning electron microscopy (SEM). Energy dispersive spectrometer (EDS) data confirm existence of zinc oxide and ruthenium oxide hexacyanoferrate (RuOHCF) in the hybrid film. The effect of type of monovalent cations on the redox behavior of hybrid film was investigated. In pure supporting electrolyte, electrochemical responses of Ru^II/III redox transition occurring at negative potential region resemble with that of a surface immobilized redox couple. The electrocatalytic activity of ZnO/ZnHCF-RuOHCF hybrid film was investigated towards oxidation of epinephrine, dopamine and l-cysteine, and reduction of S₂O₈²⁻ and SO₅²⁻ as well as IO₃⁻ using cyclic voltammetry and rotating ring disc electrode (RRDE) techniques.     

Electrochemical evaluation of ferrocene carboxylic acids confined on surfactant-clay modified glassy carbon electrodes: oxidation of ascorbic acid and uric acid

We report on the electrochemical behavior of chemically modified glassy carbon (GC) electrodes by using surfactant/clay films, [cetyltrimethylammonium bromide (CTAB)/hydrotalcite-like], containing ferrocenecarboxylic (FC) or ferrocenedicarboxylic (FDC) acid. The results show that the surfactant molecules incorporated into the clay could increase the permeability and the positive surface of the film. The FDC-CTAB-clay-GC modified electrode showed greater stability and redox electroactivity than the FC-CTAB-clay-GC modified electrode. Low concentrations of ascorbic acid (H₂A) and uric acid (UA) in aqueous solution were easily oxidized on the FDC-surfactant-clay-GC modified electrode. The kinetic of the catalytic reactions were investigated by using cyclic voltammetry and rotating disk electrode. The results suggest that the oxidation of H₂A on FDC-CTAB-clay-GC electrode is limited by kinetics while the oxidation of UA is mass transport-limited. The FDC-CTAB-clay-GC modified electrode allows to determine H₂A in presence of UA, and shows good anti-fouling properties towards surface active materials.     

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.     

The microstructure and electrochemical properties of boron-doped nanocrystalline diamond film electrodes and their application in non-enzymatic glucose detection

Boron-doped nanocrystalline diamond (BDND) films were deposited on Si(100) by microwave plasma chemical vapor deposition using trimethyl boron as boron source. The surface morphology, microstructure, and electrochemical properties of the BDND films were investigated. Cyclic voltammograms indicated that the BDND film electrode exhibited good reversibility and repeatability of electrode reaction using [Fe(CN)₆]^3?/4? as redox couple. The non-enzymatic glucose sensor based on the as-prepared BDND film electrode without any modification was developed, and the selective detection of glucose in alkaline solution containing interference species of ascorbic acid and uric acid was demonstrated. The results showed that glucose can be directly oxidized with a wide linear range and high sensitivity, and selectively detected in the presence of uric acid and ascorbic acid in alkaline solution using the as-prepared BDND film electrode.     

Poly(malachite green) film: Electrosynthesis, characterization, and sensor application

Poly(malachite green) films were synthesized electrochemically on the glassy carbon electrode in the potentiodynamic mode. The characterization and growth mechanism of as-prepared films were studied with FT-IR spectroscopy, UV-vis spectroscopy, cyclic voltammetry, chronocoulometry, and electrochemical impedance spectroscopy. Charge transfer and ion transport of poly(malachite green) films were investigated in the aqueous solutions with different types of supporting electrolytes. The poly(malachite green) film coated glassy carbon electrode showed catalytic ability towards ascorbic acid and dopamine. The difference of the anodic peak potential of ascorbic acid on the poly(malachite green) film modified electrode from that of dopamine was 180 mV. Based on their voltammetric responses, the poly(malachite green) film coated glassy carbon electrode was utilized as an electrochemical sensor for the content determination of ascorbic acid and dopamine simultaneously and separately in pharmaceutical and injections.     

Preparation and characterization of an AuCu3 alloy electrode for electrocatalytic applications

We report here preparation and characterization of an AuCu₃ alloy electrochemical sensing platform fabricated on an easy for mass production barrel-plated gold electrode (AuBPE). Note that the AuBPE consists of Cu main body with successive plating of a very thin layer of Ni and Au (i.e., Cu–Ni–Au multilayer). By suitably manipulating the grain boundary diffusion between individual metallic layers of Cu–Ni–Au by means of thermal annealing treatment, AuCu₃ alloy film can be formed directly on the outer surface of the AuBPE. Electrochemical activation in alkaline solution can further generate a nanostructured AuCu₃ alloy film. This facile and novel approach is promising to prepare sensors for electroanalytical applications, e.g., glucose oxidation in pH-neutral solutions and simultaneous detection of uric acid, dopamine and ascorbic acid.     

The interaction of water-soluble iron porphyrins with DNA films and the electrocatalytic properties for inorganic and organic nitro compounds

The electrochemistry of water-soluble iron porphyrins (Fe(n-TMPyP)) (where n=2 and 4) was studied as an electrochemically active film on DNA modified glassy carbon, gold, platinum, and transparent semiconductor tin oxide electrodes in solutions of various pH values. The two layers of the modified electrode containing the iron porphyrin and the DNA film were prepared by depositing the iron porphyrin on a DNA film modified electrode. The Fe(4-TMPyP)/DNA film was electrocatalytic reductive for p-nitrobenzoic acid in a weak acidic, or neutral aqueous solution through an Fe^II species, and the electrocatalytic reduction peak potential became more negative than the cathodic peak of the Fe^III/II redox couple. The electrocatalytic reduction properties by the Fe(2-TMPyP)/DNA film as catalysts for nitrite reduction have also been determined, and shown to be active through an Fe^I species and to be pH-dependent. The electrocatalytic oxidation properties of nitrite by Fe(n-TMPyP)/DNA (for n=2 and 4) film have also been determined and shown to be active through an Fe^IV species with the electrocatalytic oxidation efficiency of NO₂⁻ with Fe^IV(O)(n-TMPyP) being higher than with (HO)Fe^IV(O)(n-TMPyP). The electrocatalytic oxidation efficiency of NO₂⁻ by iron porphyrin is pH-dependent. The electrocatalytic reduction of p-nitrophenol by Fe(2-TMPyP)/DNA film are also discussed.     

Maltose-Containing Polyurethane Films: Synthesis,Characterization, and Their Use for Determination of Dopamine in the Presence of the Electroactive and Nonelectroactive Interferents

A series of polyurethanes were prepared from the maltose-ethylene glycol-diphenylmethane diisocyanate and used to construct a novel polyurethane electrode for the detection of dopamine. The polyurethanes were characterized by FT-IR, differential scanning calorimetry, and thermogravimetric analysis. The intrinsic viscosity and adhesive properties were also evaluated. Selectivity behaviour of films prepared from polyurethane solutions containing 1%, 3%, 5%, and 10% maltose to electroactive and nonelectroactive substances was examined by DPV. The results demonstrated that polymer electrode by 2 µL polyurethane solutions containing 3% maltose was allowed penetration of dopamine while blocking the permeation of ascorbic acid and uric acid through film.     

A highly selective amperometric sensor for ascorbic acid based on mesopore-rich active carbon-modified pyrolytic graphite electrode

A kind of new mesopore-rich active carbon (MRAC) was firstly prepared by carbonizing bamboo micro-particles, which was utilized for constructing MRAC-modified pyrolytic graphite electrode (MRAC/PGE). The electrochemical behavior of ascorbic acid (AA) was in detail investigated at the MRAC/PGE. The proposed MRAC/PGE showed an excellent electrocatalytic response towards AA oxidation in neutral buffer solution. The oxidation potential of AA significantly decreased at MRAC/PGE. The oxidation current of AA obtained at the MRAC/PGE is 4.6-fold higher than that of the bare PGE. Using amperometric method, the anodic current is linear with AA concentration in the range of 0.5-2000 μM, with a detection limit about 0.3 μM. Furthermore, the proposed electrode can also avoid major interferences such as dopamine, uric acid, urea, and so on. This new method has been successfully applied for AA assay in urine and pharmaceutical preparations.     

The electrochemical synthesis of polyaniline/polysulfone composite films and electrocatalytic activity for ascorbic acid oxidation

Polyaniline (PANI)/polysulfone (PSF) composite films with asymmetric porous structure were successfully prepared by electropolymerization. The back face (in contact with the electrode) of the freestanding composite film is green while the outer face is white. The chemical component and the morphology of the surfaces were characterized by FTIR spectra and scanning electron microscopy, respectively. It was shown that replicate films gave reproducible voltammetry in 0.5 M H₂SO₄. The influence of the electrolyte and the acidic concentration on the redox peak currents of polyaniline were investigated in detail. The composite film electrode showed good electrocatalytic activity for ascorbic acid, which the anodic overpotential was evidently reduced compared with that obtained at bare Pt electrode. The diffusion coefficient of ascorbic acid was 1.38 × 10⁻⁶ cm² s⁻¹.     

Electrochemical detection of dopamine and cytochrome c at a nanostructured gold electrode

A nanostructured gold surface consisting of closely packed outwardly growing spikes is investigated for the electrochemical detection of dopamine and cytochrome c. A significant electrocatalytic effect for the electrooxidation of both dopamine and ascorbic acid at the nanostructured electrode was found due to the presence of surface active sites which allowed the detection of dopamine in the presence of excess ascorbic acid to be achieved by differential pulse voltammetry. By simple modification with a layer of Nafion, the enhanced electrocatalytic properties of the nanostructured surface was maintained while increasing the selectivity of dopamine detection in the presence of interfering species such as excess ascorbic and uric acids. Also, upon modification of the nanostructured surface with a monolayer of cysteine, the electrochemical response of immobilised cytochrome c in two distinct conformations was observed. This opens up the possibility of using such a nanostructured surface for the characterisation of other biomolecules and in bio-electroanalytical applications.