Electrochemical study of the interfacial characteristics of redox-active viologen thiol self-assembled monolayers

The electrochemical behavior of the electroactive self-assembled monolayers (SAMs) of thiol-functionalized viologen, CH3(CH2)(9)V2+(CH2)(8)SH, where V2+ is a viologen group, on the gold electrodes is examined by cyclic voltammetry and electrochemical a.c. impedance. A monolayer of viologen is immobilized on the gold electrode surface via the Au-S bond and the normal potentials corresponding to the two successive one-electron transfer processes of the viologen active centers are -310 mV and -652 mV (vs. Ag/AgCl) in 0.1 mol l(-1) phosphate buffer solution (pH 6.96) respectively. These results suggest that the viologen SAMs are stable and well-behaved monolayers. The experimental impedance data corresponding to different forms of viologen group have been fitted to equivalent electrical circuits, and the surface capacitances and resistances have been given. The heterogenous electron transfer rates of the first and the second redox processes are 7.57 s(-1) and 1.49 s(-1) respectively through a.c. impedance.

A study of the electrochemical characteristics of the Co(salen)-Nafion modified electrode

A Co(salen)-Nafion modified electrode was prepared by immersing a glassy carbon electrode coated with the Nafion film into the aqueous solution with saturated Co(salen), The modified electrode showed a stable electrochemical reaction of Co(salen) at about 0 V(vs, SCE), The result of XPS indicated the valence of cobalt in Co(salen) changes from +2 before to +3 after Co(salen) enters the Nafion film, It is due to forming axis coordination of cobalt with sulfonic group in Nafion film, It was found that the mode of electron transfer in Co(salen)-Nafion modified electrode was controlled by physical diffusion and electron hopping, It was also found that the modified electrode could catalyze the reduction of O-2 to H2O2. The real catalyst may be the adduct of Co-I(salen) and O-2.

Charge transport of indigo-carmine doped polypyrrole

Charge transport in polypyrrole doped with indigo-carmine was investigated by the method of electrochemical alternating current impedance. By the nonlinear least square fitting, the equivalent circuit and parameter of each component are obtained. The apparent diffusion coefficients and heterogeneous electron transfer constants are given. It is found that, along with the increasing of film thickness, D-app and k(0) increase also.

Viologen-thiol self-assembled monolayers for immobilized horseradish peroxidase at gold electrode surface

A stable, well-behaved self-assembled monolayer (SAM) of viologen-functionalized thiol was used to immobilize and electrically connect horseradish peroxidase (HRP) at gold electrode. Viologen groups in SAMs facilitated the electron transfer from the electrode to the protein active site so that HRP exhibited a quasi-reversible redox behavior. HRP adsorbed in the SAMs is very stable, and close to a monolayer with the surface coverage of 6.5 x 10(-11) mol/cm(2). The normal potential of HRP is -580 mV vs Ag/AgCl corresponding to ferri/ferro active center and the standard electron transfer rate constant is 3.41 s(-1) in 0.1 M phosphate buffer solution (pH 7.1). This approach shows a great promise for designing enzyme electrodes with other redox proteins and practical use in tailoring a variety of amperometric biosensor devices. Copyright (C) 1997 Elsevier Science Ltd.

Luminescent properties of Ba-3(PO4)(2):Eu, Tb phosphors

Luminescence of europium (III), europium(II) and terbium(III) has been observed in Ba-3(PO4)(2):Eu, Tb phosphors which are synthesized in air atmosphere. The valence state of europium is influenced by amount of terbium. It is notable that the relative intensity of the emission spectra peaks corresponding to Eu2+ is increased if the amount of Tb3+ is increased. These phenomena can be explained by an electron transfer mechanism. We predict a new kind of two-rare-earth codoped trichromatic phosphors in Ba-3(PO4)(2) matrix.

The spectral properties of BaB8O13:Eu,Tb phosphors

The luminescence properties of BaB8O13:xEu,yTb phosphors which were synthesized in air atmosphere have been studied. The emissions of europium(III), terbium(III) and europium(II) have been observed in BaB8O13:xEu, yTb phosphors. Electron paramagnetic resonance (EPR) studies were carried out. The intensities of EPR peaks of europium(II) are increased if terbium(III) is increased in BaB8O13:Eu3+,yTb(3+) phosphors. So the valence state of europium is influenced by terbium(III). These phenomena can be explained by an electron transfer mechanism. We found a new kind of method to prepare trichromatic phosphor that two rare earth ions activated in a BaB8O13 matrix.

In situ electrochemical scanning tunneling microscopy investigation of renewing graphite surface accompanied by electrochemical reaction

In situ electrochemical scanning tunneling microscopy (ECSTM) has been employed to follow the renewal process of a graphite electrode accompanied by flavin adenine dinucleotide (FAD) electrochemical reaction which involves adsorption of the reduced form (FADH(2)) and desorption of the oxidized form (FAD). The renewal process initiates from steps or kinks on the electrode surface, which provide high active sites for adsorption. This renewal depends on the working electrode potential, especially in the range near the FAD redox potential. Our experiment suggests that delamination of the graphite surface is caused by interaction between the substrate and adsorbed molecules. A simple model is proposed to explain this phenomenon.

The electrochemical behavior of Eastman AQ/meldola blue-coated microelectrodes

Eastman-AQ 55D was coated onto a carbon fiber microelectrode surface, and the resulting modified electrodes exhibited high stability. Substantial improvement in the stability was observed as a result of good adhesion and the strong binding of large hydrophobic cations of Eastman AQ 55D. The electrode reaction of meldola blue bound in the polymer film showed a reversible, one-electron transfer process. The effects of solution pH and influence of supporting electrolyte on the modified carbon fiber microelectrode are discussed. The diffusion coefficient of meldola blue in the AQ polymer film determined by chronoamperometry is 2.3 x 10(-18) cm(2) s(-1), and the heterogeneous rate constant of meldola blue at the AQ polymer film/electrode determined by normal pulse voltammetry is 3.97 x 10(-3) cms(-1).

Luminescence properties of SrB4O7: Eu, Tb phosphors

In this paper, the luminescence properties of SrB4O7: xEu, yTb phosphors were investigated. The SrB4O7: xEu, yTb phosphors were first synthesized in air atmosphere, and the emission spectra of Eu2+, Eu3+ and Tb3+ ions have been observed in phosphors. We found that the relative intensity of the emission of Eu2+ ion in the same matrix are increased when Tb3+ is incorporated in SrB4O7:Eu phosphor. So the valence state of europium is influenced by terbium. These phenomena can be explained using an electron transfer theory.

In situ electrochemical scanning tunnelling microscopy investigation of structure for horseradish peroxidase and its electrocatalytic property

Immobilization of protein molecules is a fundamental problem for scanning tunnelling microscopy (STM) measurements with high resolution. In this paper, an electrochemical method has been proved to be an effective way to fix native horseradish peroxidase (HRP) as well as inactivated HRP from electrolyte onto a highly oriented pyrolytic graphite (HOPG) surface. This preparation is suitable for both ex situ and in situ electrochemical STM (ECSTM) measurements. In situ STM has been successfully employed to observe totally different structures of HRP in three typical cases: (1) in situ ECSTM reveals an oval-shaped pattern for a single molecule in neutral buffer solution, which is in good agreement with the dimension determined as 6.2 x 4.3 x 1.2. nm(3) by ex situ STM for native HRP; (2) in situ ECSTM shows that the adsorbed HRP molecules on HOPG in a denatured environment exhibit swelling globes at the beginning and then change into a V-shaped pattern after 30 min; (3) in situ ECSTM reveals a black hole in every ellipsoidal sphere for inactivated HRP in strong alkali solution. The cyclic voltammetry results indicate that the adsorbed native HRP can directly catalyse the reduction of hydrogen peroxide, demonstrating that a direct electron transfer reduction occurred between the enzyme and HOPG electrode, whereas the corresponding cyclic voltammograms for denatured HRP and inactivated HRP adsorbed on HOPG electrodes indicate a lack of ability to catalyse H2O2 reduction, which confirms that the HRP molecules lost their biological activity. Obviously, electrochemical results powerfully support in situ STM observations.

Effect of structures of modifiers on electrochemistry of di-mu-oxo dimanganese 2,2'-bipyridine complex

The gold electrodes modified with 2-picolinic acid , nicotinic acid, iso-nicotinic or thiophene were prepared using membrane transfer method, The electrochemistry of di-mu-oxodimanganese 2,2'-bipyridine complex was studied in the acetic acid buffer solution at different modified gold electrodes, It was found that the modifiers which can promote the electrochemical reaction of the complex should be of at least two functional groups, One group can be bound to the electrode surface and the other can form electron transfer pathway between the modifier and the complex through sal; bridge or hydrogen bond, In addition, the mechanism of the electrochemical reaction was discussed.

Dynamic spectroelectrochemical measurement for the conformational transition of cytochrome c induced by bromopyrogal red

The conformational transition of horse heart cytochrome c induced by bromopyrogal red (BPR) in very low concentration has been firstly investigated by dynamic spectroelectrochemical technique, both at the BPR adsorbed platinum gauze electrode and at a bare platinum gauze electrode in a solution containing BPR. The effect of BPR on the structure of cytochrome c was studied by UV-visible and Fourier transform IR spectroscopy. The unfolded cytochrome c behaves simply as an electron transfer protein with a formal potential of -142 mV vs. a normal hydrogen electrode. The difference between the formal potentials of the native and unfolded cytochrome c is coupled to a difference in conformational energy of the two states of about 40 kJ mol(-1), which agrees well with the result reported. The stability and slow refolding of the unfolded cytochrome c are discussed.

Ac voltammetric and square wave voltammetric study of the self-assembled monolayers of thiol-functionalized viologen derivative

Electroactive self-assembled monolayers (SAMs) containing viologen group are formed through the adsorption of thiol-functionalized viologen compound CH3(CH2)(9)V2+(CH2)(8)SH, where V2+ is N,N'-dialkylbipyridinium (i.e. a viologen group), onto gold electrodes from methanol/water solution and its electrochemical behavior is investigated ty Ac voltammetry and square wave voltammetry, which have the high sensitivity against background charging. The viologen SAM formed is a sub-monolayer and the normal potentials corresponding to the two successive one-electron transfer processes of the active centers (viologen) are -360 mV and -750 mV (vs. Ag/AgCl) in 0.1 mol/L phosphate buffer solutions (pH 6.96) respectively, and the standard electron transfer rate constant is 9.0 s(-1). The electrochemical behavior of this SAM in various solutions has been preliminarily discussed.

The direct electrochemistry of cryo-hydrogel immobilized myoglobin at a glassy carbon electrode

A cryo-hydrogel membrane (CHM) immobilized at a glassy carbon (GC) electrode is reported for the direct electron transfer of redox proteins. The most attractive characteristics of this CHM were its hydrophilic micro-environment for incorporated proteins to retain their activities, its high ability for protection against interference of denatured and adsorbed proteins at the electrode, its potential applications for various proteins or enzymes, as well as its high mechanical strength and thermal stability. A clear well developed and stable redox wave was obtained for commercially available horse heart myoglobin without further purification, giving a peak to peak separation Delta E(p) = 93 mV at 5 mV s(-1) and the formal electrode potential E(0)' = -0.158 V (vs. Ag/AgCl). The formal heterogeneous electron transfer rate constant was calculated as k(0)' = 5.7 X 10(-4) cm s(-1) at pH 6.5, showing rapid electron transfer was achieved. The pH controlled conformational equilibria, acid state --> natural state --> basic I state --> basic II state, of myoglobin at the CHM GC electrode in the pH range 0-13.8 were also observed and are discussed in detail.