PREPARATION AND PROPERTIES OF POLYPYRROLE FILM DOPED WITH A DAWSON-TYPE HETEROPOLYANION

The electropolymerization of pyrrole in the presence of Dawson-type tungstophosphate yields a polypyrrole (PPy) film doped with tungstophosphate anions on the electrode surfaces. The electrochemical behaviour of this film was described, and the stability

Application of electrochemical impedance spectroscopy for monitoring allergen-antibody reactions using gold nanoparticle-based biomolecular immobilization method

Gold nanoparticles were used to enhance the immobilization amount and retain the immunoactivity of recombinant dust mite allergen Der f2 immobilized on a glassy carbon electrode (GCE). The interaction between allergen and antibody was studied by electrochemical impedance spectroscopy (EIS). Self-assembled Au colloid layer (Phi = 16 nm) deposited on (3-mercaptopropyl)trimethoxysilane (MPTS)-modified GCE offered a basis to control the immobilization of allergen Der f2. The impedance measurements were based on the charge transfer kinetics of the [Fe(CN)(6)](3-/4-) redox pair, compared with bare GCE, the immobilization of allergen Der f2 and the allergen-antibody interaction that occurred on the electrode surface altered the interfacial electron transfer resistance and thereby slowed down the charge transfer kinetics by reducing the active area of the electrode or by preventing the redox species in electrolyte solution from approaching the electrode. The interactions of allergen with various concentrations of monoclonal antibody were also monitored through the change of impedance response. The results showed that the electron transfer resistance increased with increasing concentrations of monoclonal antibody.

AMPEROMETRIC BIOSENSORS BASED ON THE IMMOBILIZATION OF OXIDASES IN A PRUSSIAN BLUE FILM BY ELECTROCHEMICAL CODEPOSITION

Prussian blue has been formed by cyclic voltammetry onto the basal pyrolytic graphite surface to prepare a chemically modified electrode which provides excellent electrocatalysis for both oxidation and reduction of hydrogen peroxide. It is found for the first time that glucose oxidase or D-amino oxidase can be incorporated into a Prussian blue film during its electrochemical growth process. Two amperometric biosensors were fabricated by electrochemical codeposition, and the resulting sensors were protected by coverage with a thin film of Nafion. The influence of various experimental conditions was examined for optimum analytical performance. The glucose sensor responds rapidly to substrates with a detection limit of 2 x 10(-6) M and a linear concentration range of 0.01-3 mM. There was no interference from 2 mM ascorbic acid or uric acid. Another (D-amino acid) sensor gave a detection limit of 3 x 10(-5) M D-alanine, injected with a linear concentration range of 7.0 x 10(-5)-1.4 x 10(-2) M. Glucose and D-amino acid sensors remain relatively stable for 20 and 15 days, respectively. There is no obvious interference from anion electroactive species due to a low operating potential and excellent permselectivity of Nafion.

Immobilization and electrochemical properties of anionic complexes on a V2O5/surfactant nanocomposite

in this work, we report a new way of modifying an electrode by combining the intrinsic conductivity property of vanadium pentoxide xerogel with its water insolubility in the presence of the cationic surfactant N-cetyl-N,N,N,trimethyl-ammonium bromide (CTA(+)Br(-)). The obtained hybrid compound enables the immobilization of electroactive anions such as hexacyanoferrate (III) ([Fe(CN)(6)](3-)) and its analogue pentacyanonitrosylferrate (II) ([Fe(CN)(5)NO](2-)), rather than cations. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Electrochemical detection of benzo(a)pyrene and related DNA damage using DNA/hemin/nafion-graphene biosensor

A novel electrochemical biosensor, DNA/hemin/nafion–graphene/GCE, was constructed for the analysis of the benzo(a)pyrene PAH, which can produce DNA damage induced by a benzo(a)pyrene (BaP) enzyme-catalytic product. This biosensor was assembled layer-by-layer, and was characterized with the use of cyclic voltammetry, electrochemical impedance spectroscopy (EIS) and atomic force microscopy. Ultimately, it was demonstrated that the hemin/nafion–graphene/GCE was a viable platform for the immobilization of DNA. This DNA biosensor was treated separately in benzo(a)pyrene, hydrogen peroxide (H2O2) and in their mixture, respectively, and differential pulse voltammetry (DPV) analysis showed that an oxidation peak was apparent after the electrode was immersed in H2O2. Such experiments indicated that in the presence of H2O2, hemin could mimic cytochrome P450 to metabolize benzo(a)pyrene, and a voltammogram of its metabolite was recorded. The DNA damage induced by this metabolite was also detected by electrochemical impedance and ultraviolet spectroscopy. Finally, a novel, indirect DPV analytical method for BaP in aqueous solution was developed based on the linear metabolite versus BaP concentration plot; this method provided a new, indirect, quantitative estimate of DNA damage.

Adsorption of human serum albumin onto gold: a combined electrochemical and ellipsometric study

Human serum albumin adsorption onto gold surfaces was investigated by electrochemical and ellipsometric methods. Albumin adsorption onto gold was confirmed by the change of the open circuit potential of gold and by the ellipsometric parameter variation during albumin immobilization. In both experiments the parameters reached stable values within 10-15 min. The albumin adsorption layer thickness measured with the ellipsometer was about 1.5 nm. The adsorption of albumin Under applied potential was also investigated and it was found that both positive and negative applied potential promote albumin adsorption. Changes in the optical parameters of bare gold and albumin adsorbed onto gold surface under applied potential were investigated with in Situ ellipsometry. The similarity and reversibility of the optical changes showed that adsorbed albumin was stable on the gold surface Under the applied potential range (-200-600 mV). The cyclic voltammograms of K3Fe(CN)(6) on the modified gold surface showed that albumin Could partly block the oxidation and reduction reaction. (C) 2004 Elsevier Inc. All rights reserved.

Bis(2,2 '-bipyridine)(5,6-epoxy-5,6-dihydro-[1,10] phenanthroline)ruthenium: Synthesis and electrochemical and electrochemiluminescence characterization

In this work, an electrochemiluminescence (ECL) reagent bis(2,2'-bipyridine)(5,6-epoxy-5,6-dihydro-[1,10]phenanthroline)ruthenium complex (Ru-1) was synthesized, and its electrochemical and ECL properties were characterized. The synthesis of Ru-1 was confirmed by IR spectra, element analysis, and H-1 NMR spectra. For further study, its UV-vis absorption and fluorescence emission spectra were investigated. Ru-1 also exhibited quasi-reversible Ru-II/Ru-III redox waves in acetonitrile solution. The aqueous ECL behaviors of Ru-1 were also studied in the absence and in the presence of tripropylamine.

Fabrication and electrochemical characterization of electrostatic assembly of polyelectrolyte-functionalized ionic liquid and Prussian blue ultrathin films

Polyelectrolyte-functionalized ionic liquid (PFIL) and Prussian blue (PB) nanoparticles were used to fabricate ultrathin films on the ITO substrate through electrostatic layer-by-layer assembly method. Multilayer growth was examined by UV-vis spectroscopy and cyclic voltammetry. The resulting ITO/(PFIL/PB)n electrode showed two couples of well-defined redox peaks and good electrocatalytical activity towards the reduction of hydrogen peroxide.

Organic-inorganic hybrid material for the cells immobilization: Long-term viability mechanism and application in BOD sensors

In this paper, organic-inorganic hybrid material, which is composed of silica and the grafting copolymer of poly (vinyl alcohol) and 4-vinylpyridine (PVA-g-P(4-VP)), was employed to immobilize Trichosporon cutaneum strain 2.570 cells. Cells entrapped into the hybrid material were found to keep a long-term viability. The mechanism of such a long-term viability was investigated by using confocal laser scanning microscopy (CLSM). Our studies revealed that arthroconidia produced in the extracellular material might play an important role in keeping the long-term viability of the immobilized microorganism. After the arthroconidia were activated, an electrochemical biochemical oxygen demand (BOD) sensor based on cell/hybrid material-modified supporting membrane was constructed for verifying the proposed mechanism.

Electrochemical impedance detection of DNA hybridization based on dendrimer modified electrode

Bioactive ultrathin films with the incorporation of amino-terminated G4 PAMAM dendrimers have been prepared via layer-by-layer self-assembly methods on a gold electrode and used for the DNA hybridization analysis. Surface plasmon resonance (SPR), X-ray photoelectron spectroscopy (XPS), and electrochemical impedance spectroscopy (EIS) are used to characterize the successful construction of the multicomponent film on the gold substrate. The dendrimer-modified surfaces improve the immobilization capacity of the probe DNA greatly, compared to the AET (2aminoethanethiol) SAM sensor surfaces without dendrimer molecules. DNA hybridization analysis is monitored by EIS. The dendrimer-based electrochemical impedance DNA biosensor shows high sensitivity and selectivity for DNA hybridization assay. The multicomponent films also display a high stability during repeated regeneration and hybridization cycles.

Carbon nanotubes and glucose oxidase bionanocomposite bridged by ionic liquid-like unit: Preparation and electrochemical properties

For their biocompatibility and potential bionanoelectronic applications, integration of carbon nanotubes (CNTs) with biomolecules such as redox enzyme is highly anticipated. Therein, CNTs are expected to act not only as an electron transfer promoter, but also as immobilizing substrate for biomolecules. In this report, a novel method for immobilization of biomolecules on CNTs was proposed based on ionic interaction, which is of universality and widespread use in biological system. As illustrated, glucose oxidase (GOD) and single-walled carbon nanotubes (SWNTs) were integrated into a unitary bionanocomposite by means of ionic liquid-like unit on functionalized SWNTs. The resulted bionanocomposite illustrated better redox response of immobilized GOD in comparison of that prepared by weak physical absorption without ionic interaction. As a potential application of concept, the electrochemical detection of glucose was exemplified based on this novel bionanocomposite.

Immobilization of the nanoparticle monolayer onto self-assembled monolayers by combined sterically enhanced hydrophobic and electrophoretic forces

The immobilization of surface-derivatized gold nanoparticles onto methyl-terminated self-assembled monolayers (SAMs) on gold surface was achieved by the cooperation of hydrophobic and electrophoretic forces. Electrochemical and scanning probe microscopy techniques were utilized to explore the influence of the SAM's structure and properties of the nanoparticle/SAM/gold system. SAMs prepared from 1-decanethiol (DT) and 2-mercapto-3-n-octylthiophene (MOT) were used as hydrophobic substrates. The DT SAM is a closely packed and organized monolayer, which can effectively block the underlying gold and inhibit a variety of solution species including organic and inorganic molecules from penetrating, whereas the MOT monolayer is poorly packed or disorganized (because of a large difference in dimension between the thiophene head and the alkylchain tail) and permeable to many organic probes in aqueous solution but not to inorganic probes. Thus, the MOT monolayer provides a more energetically favorable hydrophobic surface for the penetration and adsorption of organic species than the DT monolayer.

Electrochemical and electrogenerated chemiluminescence of clay nanoparticles/Ru(bpy)(3)(2+) multilayer films on ITO electrodes

The electrochemical and electrogenerated chemiluminescence of Ru(bpy)(3)(2+) immobilized in {clay/Ru(bpy)(3)(2+)}(n) multilayer films by layer-by-layer assembly were investigated. The stable multilayer films of clay and Ru(bpy)(3)(2+) were assembled by alternate adsorption of negatively charged clay platelets and positively charged Ru(bpy)(3)(2+) from their aqueous dispersions. UV-vis spectroscopy, quartz crystal microbalance (QCM), cyclic voltammetry, and electrogenerated chemiluminescence (ECL) were used to monitor the immobilization of Ru( bpy)(3)(2+) and the regular growth of the {clay/Ru( bpy)(3)(2+)}(n) multilayer films. The multilayer films modified electrode was used for the ECL detection of tripropylamine ( TPA) and oxalate. The proposed novel immobilized method exhibited good stability, reproducibility and high sensitivity for the determination of TPA and oxalate, which mainly resulted from the contributing of clay nanoparticles with appreciable surface area, special structural features and unusual intercalation properties.

Immobilization and direct electrochemistry of copper-containing enzymes on active carbon

Two typical and important copper-containing enzymes, laccase (Lac) and tyrosinase (Tyr), have been immobilized on the surface of active carbon with simple adsorption method. The cyclic voltammetric results indicated that the active carbon could promote the direct electron transfer of both Lac and Tyr and a pair of well-defined and nearly symmetric redox peaks appeared on the cyclic voltammograms of Lac or Tyr with the formal potential, E-0', independent on the scan rate. The further experimental results showed that the immobilized copper-containing oxidase displayed an excellent electrocatalytic activity to the electrochemical reduction of O-2. The immobilization method presented here has several advantages, such as simplicity, easy to operation and keeping good activity of enzyme etc., and could be further used to study the direct electrochemistry of other redox proteins and enzymes and fabricate the catalysts for biofuel cell.