Interfacial behavior of primary amine N1923 and the kinetics of thorium(IV) extraction in sulfate media

The influences of additive, diluents, temperature, acidity of the aqueous phase on the interfacial behavior of primary amine N1923 in sulfate media have been investigated using the Du Nouy ring method. In addition, the effect of concentration of thorium(IV) loaded in the organic phase on the interfacial tension has also been studied. The interfacial tension isotherms are processed by matching different adsorption equations such as the Gibbs and the Szyszkowski. The surface excess at the saturated interface (Gamma (max)) and the minimum bulk concentration of the extractant necessary to saturate the interface (C-min) under different conditions are calculated according to two adsorption equations to be presented in comprehensive tables and figures. It appears that primary amine N1923 has strong interfacial activity and behaves very differently in various diluents systems. The surface excess at saturated interface increase with the type of diluerits in the following order: chloroform < aromatic hydrocarbons < aliphatic hydrocarbons. The relationship between the interfacial activity and kinetics of thorium extraction by primary amine N1923 has been discussed by considering different factors. However, the interfacial activity of primary amine N1923 is only a qualitative parameter suggesting the interfacial mechanism for thorium extraction, it cannot give strong evidence quantitatively supporting this mechanism.

Co-assembly of ferrocene-terminated and alkylthiophene thiols on gold and its redox chemistry modulated by surfactant adsorption

Coadsorption of ferrocene-terminated alkanethiols (FcCO(2)(CH2)(8)SH, Fc=(mu(5)-C5H5)Fe(mu(5)-C5H4)) with alkylthiophene thiols (2-mercapto-3-n-octylthiophene) yields stable, electroactive self-assembled monolayers on gold. The resulting mixed monolayer provides an energetically favorable hydrophobic surface for the adsorption of the surfactant aggregates in aqueous solution. The adsorptions have been characterized via their effect on the redox properties of ferrocenyl alkanethiols immobilized as minority components in the monolayers and on the interfacial capacitance of the electrode. Surfactant adsorption causes a decrease in the overall capacitance at the electrode and dramatically shifts the redox potential for ferrocene oxidation in a positive or negative direction depending on the identity of the surfactant employed. A structural model is proposed in which the alkane chains of the adsorbed surfactants interdigitate with those of the underlying self-assembled monolayer, leading to the formation of a hybrid bilayer membrane.

An effective layer-by-layer adsorption and polymerization method to the fabrication of polyoxometalate-polypyrrole nanoparticle ultrathin films

A layer-by-layer (LbL) adsorption and polymerization method was developed for the controllable preparation of polypyrrole (PPy) nanoparticles within ultrathin films. By repetitive adsorption of pyrrole and subsequent polymerization with 12-molybdophosphoric acid, the polyelectrolyte multilayer films containing PPy nanoparticles were fabricated. UV-visible absorption spectrocopy, Fourier transform infrared (FTIR) spectroscopy, atomic force microscopy (AFM), transmission electron microscopy (TEM) and cyclic voltammograras (CVs) were used to characterize the PPy nanoparticles and their multilayer thin films. UV-visible spectra indicate that the growth of PPy nanoparticles was regular and occurred within the polyelectrolyte films. The size of prepared PPy nanoparticles was found by TEM to increase with the increasing of polymerization cycles. The electrochemistry behavior of the multilayer thin films was studied in detail on ITO. The results suggest that the LbL adsorption and polymerization method developed herein provides an effective way to prepare PPy nanoparticles in the polymer matrix.

Interfacial behavior of DEHEHP and the kinetics of cerium(IV) extraction in nitrate media

The effects of diluents, temperature, acidity, and ionic strength of the aqueous phase on the interfacial properties of DEHEHP have been extensively investigated using the Du Nouy ring method. In addition, the effect of cerium(IV) concentration loaded in the organic phase on the interfacial tension has also been studied. With the increase of DEHEHP concentration, the value of interfacial tension (gamma) decreases in the studied system, which shows that DEHEHP has interfacial activity as a kind of surfactant. The surface excess at the saturated interface (Gamma(max)) and the minimum bulk concentration of the extractant necessary to saturate the interface (C-min) under the different conditions are calculated according to two adsorption equations such as the Gibbs and Szyszkowski functions to be presented in comprehensive tables and figures. The relationship between the interfacial activity of DEHEHP and cerium(IV) extraction kinetics by DEHEHP has been discussed by considering different factors such as the effects of diluents and temperature. However, the interfacial activity parameter of extractant only is a qualitative parameter, but cannot provide strong enough evidence to quantitatively explain the relationship between extraction kinetics and interfacial properties of an extractant.

Photochromic behavior and luminescent properties of novel hybrid organic-inorganic film doped with Preyssler's heteropoly acid H-12[EuP5W30O110] and polyvinylpyrrolidone

A novel hybrid photochromic composite film composed of Preyssler's heteropoly acid H-12[EuP5W30O110] (EuP5W30) and polyvinylpyrrolidone (PVP) was prepared by dip-coating method. Atomic force microscopy (AFM) was used to investigate the surface topography. The change of characteristic peak in the infrared spectra (IR) was investigated. The TG curve showed three steps of weight loss and approximately revealed the composition of the hybrid film. Ultraviolet-visible adsorption spectra (UV-VIS) and electron resonance spectrum (ESR) were used to investigate the photochromic behavior and mechanism of hybrid film. The photoluminescent behavior of the film at room temperature was investigated to show the characteristic Eu3+ emission pattern of D-5(o)-F-7(J). The occurrence of photoluminescent activity confirms the potential for creating luminescent thin film with polyoxometalates (POMs).

Comparative studies on electrochemical behavior and electrocatalytic properties of heteropolyanion-containing multilayer films prepared by two methods

Two modification methods for multilayer formation, i.e. immersion growth and electrochemical growth, were studied comparatively for their influence on the electrochemical behavior and the electrocatalytic properties of the thus-fabricated SiMo11V-containing multilayer films. Electrochemical growth was proven to be a more suitable method than immersion growth in preparing uniform ultrathin multilayer self-assemblies with good functions. We investigated the effects of scan rate and pH on the electrochemical behavior of the monolayer and multilayer films. We also compared the electrocatalytic effects on the reduction of BrO3- and HNO2 by the multilayer films prepared by the two methods. Moreover, the influence of multilayer thickness and the identity of the outermost layer on the electrocatalytic properties were studied. Much higher catalytic currents appeared on the thicker multilayer films than those on the thinner ones. On the other hand, the catalytic currents became smaller when the multilayer films with SiMo11V as the outermost layer were covered with an additional quarternized poly(4-vinylpyridine) layer partially complexed with osmium bis(2,2'-bypyridine) chloride (QPVP-Os layer). These influences were believed to be due to the different quantities of electrocatalyst loaded in the multilayer films and the blocking effect of the QPVP-Os outermost layer. (C) 2000 Elsevier Science S.A. All rights reserved.

In-situ FTIR study on adsorption and oxidation of native and thermally denatured calf thymus DNA at glassy carbon electrodes

In-situ Fourier transform infra-red (FTIR) spectra of native and thermally denatured calf thymus DNA (CT DNA) adsorbed and/or oxidized at a glassy carbon (GC) electrode surface are reported. The adsorption of native DNA occurs throughout the potential range (-0.2 similar to 1.3 V) studied, and the adsorbing state of DNA at electrode surface is changed from through the C=O band of bases and pyrimidine rings to through the C=O of cytosine and imidazole rings while the potential shifts negatively from 1.3 V to -0.2 V. An in-situ FTIR spectrum of native CT DNA adsorbed at GC electrode surface is similar to that of the dissolved DNA, indicating that the structure of CT DNA is not distorted while it is adsorbed at the GC electrode surface. In the potential range of -0.2 similar to 1.30 V, the temperature-denatured CT DNA is adsorbed at the electrode surface first, then undergoes electrochemical oxidation reaction and following that, diffuses away from the electrode surface. (C) 2001 Elsevier Science B.V. All rights reserved.

Study of electrochemical behavior of ergosterol by in situ thin layer circular dichroic spectroelectrochemistry

The electroxidation of ergosterol was studied by in situ circular dichroic (CD) spectroelectrochemistry with a long optical path length thin layer cell. It was confirmed that the oxidation of ergosterol in ethanol solution is a two-electron irreversible electrochemical process with strong adsorption of an electroinactive product at the glassy carbon electrode, which blocks the electrochemical reaction. The CD spectroelectrochemical data were treated by the double logarithm method together with nonlinear regression, from which the formal potential, E-0 = 1.00 V, alpha n(alpha) = 0.302, the standard electrochemical rate constant, k(0) = 6.1(+/-0.4) x 10(-4) cm s(-1) and the adsorption constant, beta = 19 +/- 1, were obtained. The number of electrons transferred (n = 1.86) was estimated by cyclic voltammetry.

Electrochemical behavior of 3,4-dihydroxybenzoic acid in self-assembled monolayer electrode system

The self-assembled monolayer of cystamine was prepared on gold electrode and 3,4-dihydroxybenzoic acid (DHBA) was electrochemically deposited on cystamine surface as a functional group by electrostatic adsorption, namely, molecular deposition. It shows that the MD/SAM structure has a higher stability, and E-1/2 of the DBAH in MD/SAM shifts more negative than that of on naked gold electrode, The n-decanethiol was also used to fill defects in MD/SAM, it results in much better cyclic voltermmetric behavior.

Electrochemical quartz crystal microbalance study of the electrochemical behavior of riboflavin at gold electrodes

The electrochemical and adsorption behaviors of riboflavin (RF) at gold electrodes has ken studied by using an electrochemical quartz crystal microbalance (EQCM). Useful information is obtained not only about electrochemical behavior but also about mass changes on the electrode surface. The electrochemical properties and frequency shifts were investigated in RF solutions at different pH values, concentrations and scan rates. Reversible voltammograms were observed for pH less than or equal to 9.71. There was no electrochemical reaction for pH > 9.71. The maximum current response was obtained at about pH 8. The current response was proportional to the square root of scan rates when the concentration of RF was lower than 1.0 x 10(-4) mol L-1 (pH 6.92). On the contrary, at concentrations higher than 1.0 x 10(-4) mol L-1 (pH 6.92), it was proportional to the scan rates.

The electrochemical behavior of colloidal polypyrrole

The electrochemical behavior and charge transport of colloidal polypyrrole particles (without stabilizer) modified electrode have been investigated. The voltametric results show that the electrochemical behavior of colloidal polypyrrole is different from that of polypyrrole synthesized electrochemically. The strong adsorption of the colloidal particles on substrate makes it easy to form a polypyrrole modified electrode. The charge transport of polypyrrole is controlled by the diffusion of counterions.

Characterization and catalytic behavior of La2-x(Sr,Th)(x)CuO4+/-lambda in reaction NO+CO

Two mixed oxide systems La2-xSrxCuO4+/-lambda(0.0 less than or equal to x less than or equal to 1.0) and La2+xThxCuO4+/-lambda(0.0 less than or equal to x less than or equal to 0.4) with K2NiF4 structure were prepared by varying re values; Their crystal structures were studied by means of XRD and IR spectra. The average valence of Cu ion at B site, nonstoichiometric oxygen (A) and the chemical composition in the bulk and on the surface of the catalysts were measured by means of chemical analysis and XPS. The catalytic behavior in reaction CO + NO was investigated under the regular change of average valence of Cu ion at B site and nonstoichiometric oxygen (lambda). Meanwhile, the adsorption and activation of the small molecules NO and the mixture of NO + CO over the mixed oxide catalysts were studied by means of MS-TPD. The catalytic mechanism of reaction NO + CO over these oxide catalysts were proposed; and it has been found that, at lower temperatures the activation of NO is the rate determining step and the catalytic activity is related to the lower valent metallic ion and its concentration, while at higher temperatures the adsorption of NO is the rate determining step and the catalytic activity is related to the oxygen vacancy and its concentration.

Electrochemical behavior of FAD at a gold electrode studied by electrochemical quartz crystal microbalance

The electrochemical behavior of flavine adenine dinucleotide (FAD) at a gold electrode involving adsorption of the reduced form FADH(2) and desorption of the oxidized form FAD has been studied by using electrochemical quartz crystal microbalance (EQCM). EQCM can present information not only about the electrochemical behavior but also about the mass changes on the electrode surface. The electrochemical properties and frequency shifts were investigated in FAD solutions at different pH values, concentrations and scan rates. Reversible voltammograms were observed when pH<4.5 and irreversible voltammograms were found when pH greater than or equal to 4.5. It is found to be a diffusion controlled process when the concentration of FAD is lower than 2x10(-4) moll(-1) (pH 1.5). On the contrary, at concentrations higher than 2x10(-4) moll(-1) (pH 1.5), it is found to be an adsorption controlled process.

Electrochemical behavior of molybdotungsate heteropoly complex with neodymium K10H3[Nd(SiMo7W4O39)(2)]xH(2)O in aqueous solution

The voltammetric behavior of the titled compound (denoted as Nd (SiMo7W4)(2)(13-)) in aqueous solution had been studied. An unusual pH response was discussed. The adsorption of the anion on the dropping mercury electrode and a self-inhibition influence of the adsorbed anions on the redox process of those anions dissolved in solution were found. The electrocatalytic effects of the anion on the bromate reduction were investigated.

Electrochemical behavior of the molybdotungstate heteropoly complex with neodymium, K10H3[Nd(SiMo7W4O39)(2)]center dot xH(2)O in aqueous solution

The electrochemical behavior of the title compound (denoted Nd(SiMo7W4)(2)(13-)) in aqueous solution has been studied using cyclic voltammetry, sampled d.c. voltammetry, differential pulse voltammetry and bulk electrolysis with coulometry, The stable pH range of Nd(SiMo7W4)(2)(13-) is determined with UV-visible spectra. In the potential range between 0.70 and -0.45 V vs. SCE, the anion in pH 3.8 aqueous solution undergoes one-, one-, two- and two-electron steps of four redox processes attributed to electron addition and removal from the molybdate-oxo framework. The adsorption of the anion on the dropping mercury electrode and a self-inhibition influence of the adsorbed anions on the redox process of those anions dissolved in solution are found. The unusual dependence of the formal potentials on pH is explained with the competition of the protonation and ion-pair formation due to the high negative charge of Nd(SiMo7W4)(2)(13-) and its reduced forms. The electrocatalytic effects of the anion on the bromate are investigated.