Direct electrochemistry and surface plasmon resonance characterization of alternate layer-by-layer self-assembled DNA-myoglobin thin films on chemically modified gold surfaces

Alternate layer-by-layer (L-by-L) polyion adsorption onto gold electrodes coated with chemisorbed cysteamine gave stable, electroactive multilayer films containing calf thymus double stranded DNA (CT ds-DNA) and myoglobin (Mb). Direct, quasi-reversible electron exchange between gold electrodes and proteins involved the Mb heme Fe2+/Fe3+ redox couple. The formation of L-by-L (DNA/Mb), films was characterized by both in situ surface plasmon resonance (SPR) monitoring and cyclic voltammetry (CV). The effective thickness of DNA and Mb monolayers in the (DNA/Mb)l bilayer were 1.0 +/- 0.1 and 2.5 +/- 0.1 mn, corresponding to the surface coverage of similar to65% and similar to89% of its full packed monolayer, respectively. A linear increase of film thickness with increasing number of layers was confirmed by SPR characterizations. At pH 5.5, the electroactive Mb in films are those closest to the electrode surface; additional protein layers did not communicate with the electrode. CV studies showed that electrical communication might occur through hopping conduction via the electrode/base pair/Mb channel, thanks to the DNA-Mb interaction. After the uptake of Zn2+, a special electrochemical behavior, where MbFe(2+) acts as a DNA-binding reduction catalyst in the Zn2+-DNA/Mb assembly, takes place.

Conformational transition of DNA in electroreduction studied by in situ UV and CD thin layer spectroelectrochemistry

Electrochemically induced three conformational transitions of calf thymus DNA from B-10.4 to Z(10.2)-DNA and from B-10.2 to B-10.4 and to C-DNA in 10 mM phosphate buffer solution (pH 7.21) at glassy carbon electrode are found and studied by in situ circular dichroism (CD) thin layer spectroelectrochemistry with singular value decomposition least square (SVDLS) analysis. It indicates that the so-called B-10.2 form and the C-form of DNA may be composed of B-10.4 and left-A DNA and of B-10.4 and right-A DNA, respectively. The irreversible electrochemical reduction of adenine and cytosine groups in the DNA molecule is studied by UV-Vis spectroelectrochemistry. Some electrochemical parameters alphan = 0.17, E-0' = -0.70 V (vs. Ag/AgCl), and the standard heterogeneous electron transfer rate constant, k(0) = 1.8 x 10(-5) cm s(-1) are obtained by double logarithmic analysis and non-linear regression. (C) 2000 Elsevier Science B.V. All rights reserved.

Green electroluminescence generated from the thin film based on a soluble lanthanide complex

Electroluminescent (EL) devices based on a soluble complex Tb(MDP)(3) [Tris-(monododecyl phthalate)Terbium] doped with poly (N-vinylcarbazole) (PVK), (2-(4-biphenyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole) (PBD) were fabricated. The device structures of ITO/PVK/PVK:PBD:Tb(MDp)(2)/Aiq(3)/Al and ITO/PVK:PBD:Tb(MDP)(3)/Alq(3)/Al were employed. The Tb(MDP), as emissive layer was spin-coated. The EL cell exhibited characteristic emission of terbium ion. (C) 2000 Elsevier Science S.A. All rights reserved.

Electrochemical and spectroscopic study of vitamin D-2 by in situ thin layer CD spectroelectrochemistry

The electrooxidation of vitamin D-2 (VD2) was studied by cyclic voltammetry and in situ circular dichroic (CD) spectroelectrochemistry for the first time, The mechanism of electrooxidation and some useful kinetic and adsorption parameters were obtained. The results showed that the oxidation of VD2 in ethanol solution is an irreversible diffusion controlled process following a weak adsorption of the electroinactive product at a glassy carbon electrode, which blocks the electrochemical reaction. The electrooxidation occurs mainly at the triene moieties of the VD2 molecule. The CD spectroelectrochemical data were treated by the double logarithm method together with nonlinear regression, from which the formal potential E-0 = 1.08 V, alphan = 0.245, the standard electrochemical rate constant k(0) = 4.30( +/- 0.58) x 10(-4) cm s(-1) and the adsorption constant beta = 1.77(+/- 0.25) were obtained. (C) 2001 Elsevier Science B.V. All rights reserved.

A double logarithmic method in thin-layer spectroelectrochemistry for distinction among mechanisms of an irreversible electrochemical process

A simple double logarithmic method in potential-controlled thin-layer spectroelectrochemistry for an irreversible electrochemical process has been studied by numerical analysis and examined by experimental examples. This simple algorithm has a novel function offering some important information about the mechanism of a complex electrochemical process directly from a limited amount of potential-spectrum data, and can be used to distinguish different reaction mechanisms such as E, EC, EE, as well as to determine the electron-transfer coefficient, a, and the kinetically modified E-0'. Combination of the double logarithmic method with nonlinear regression provides a powerful tool to examine the proposed mechanism and also to estimate other thermodynamic and kinetic parameters. (C) 1999 The Electrochemical Society. S0013-4651(98)06-090-X. All rights reserved.

THEORETICAL-ANALYSIS OF NERNSTIAN PLOTS IN THE THIN-LAYER SPECTROPOTENTIOSTATIC TECHNIQUE

The Nernstian plots in a spectropotentiostatic experiment for complex electrode processes were studied theoretically. The plots are linear for an electron transfer process coupled with a preceding or succeeding chemical reaction, and the electron stoichio

AMPEROMETRIC DETECTION AT A CARBON-FIBER ARRAY RING GLASSY-CARBON DISK ELECTRODE IN A WALL-JET CELL

A wall-jet cell incorporating a carbon fibre array ring/glassy-carbon disk electrode has been constructed, and characterized by the cyclic voltammetry and flow-injection techniques. The ring (composed of several microdisks) and glassy-carbon disk electrode, can be used separately for different purposes, e.g., detection in solution without a supporting electrolyte, collection/shielding detection with dual-electrode and voltammetric/amperometric detection with series dual-electrode. The electrode shows better collection and shielding effects than usual ring-disk electrode in quiescent solution and the series dual-electrode in a thin-layer flow-through cell. The detection limit at the ring electrode is comparable with that at a conventional-size electrode, and has been used in the mobile phase without a supporting electrolyte, proving to be a promising detector for normal-phase liquid chromatography.

THIN-LAYER ELECTROCHEMICAL DETECTOR COATED WITH NAFION FILM

Electrochemical detection of the flow system has attracted considerable interest in recent years due to its high sensitivity and selectivity towards electroactive compounds. However, the improvement of sensitivity and selectivity is still a desire for practical application. In this note, a thin-layer electrochemical detector of the

Fabrication and testing of a doped lanthanum gallate electrolyte thin-film solid oxide fuel cell

A supported lanthanum gallate (LSGM) electrolyte thin-film solid oxide fuel cell with Ni-YSZ cermet anode and strontium-doped lanthanum manganite (LSM)-yttria stabilized zirconia (YSZ) composite cathode was, for the first time, fabricated and tested. The cell was prepared by an unconventional approach, in which an LSGM thin film (about 15 mum thick) was first deposited on a porous substrate such as a porous YSZ disk by a wet process and sintered at a high temperature (above 1400degrees C). NiO was then incorporated into the porous substrate by a carefully controlled impregnation process and fired at a much lower temperature. In this way, the severe reaction between LSGM and NiO at a high temperature, which is required for the full densification of LSGM film, can be avoided. A strontium-doped LaMnO3 (LSM)-YSZ composite cathode was screen printed on the surface of the LSGM film and then fired at 1250degrees C. The electrolyte resistances of the SOFC single cells fabricated by this approach are much lower compared to those of thick LSGM film supported cells. A maximum output power density of over 0.85 W/cm(2) at 800degreesC with H-2 as fuel and air as oxidant for a fabricated cell was achieved. (C) 2002 The Electrochemical Society.

Influence of electrode structure on the performance of a direct methanol fuel cell

Direct methanol fuel cells (DMFCs) consisting of multi-layer electrodes provide higher performance than those with the traditional electrode. The new electrode structure includes a hydrophilic thin film and a traditional catalyst layer. A decal transfer method was used to apply the thin film to the Nafion(R) membrane. Results show that the performance of a cell with the hydrophilic thin film is obviously enhanced. A cell with the optimal thin film electrode structure operating at I M CH3OH, 2 atm oxygen and 90degreesC yields a current density of 100 mA/cm(2) at 0.53 V cell voltage. The peak power density is 120 mW/cm(2). The performance stability of a cell in a short-term life operation was also increased when the hydrophilic thin film was employed. (C) 2002 Elsevier Science B.V. All rights reserved.