Theoretical study of p-d hybridization in Co perovskite

The real-space recursion method and unrestricted Hartree-Fock approximation have been applied to calculate the density of states of various Co perovskite, CeCoO3, SrCoO3 and Sr1-xCexCoO3. We have studied the magnetically ordered states of these Co perovskites in an enlarged double cell, and find its various magnetic structures due to the occupancy of 3d band and its interaction with neighboring Co ions. In this study, we have studied the p-d hybridization of the three Co perovskites, we find t(2g) electrons are localized and the flat e(g) band is responsible for the itinerant behavior, and although the rare earth elements itself contribute little to the DOS at the Fermi energy, the DOS at Fermi energy and the magnetic moment changed consequently because of different valence of Co ions in these compounds and p-d hybridization effect is very important. (C) 2009 Elsevier B.V. All rights reserved.

Energy-Level and Molecular Engineering of Organic D-pi-A Sensitizers in Dye-Sensitized Solar Cells

A series of organic D-pi-A sensitizers composed of different triarylamine donors in conjugation with the thienothiophene unit and cyanoacrylic acid as an acceptor has been synthesized at a moderate yield. Through tuning the number of methoxy substituents on the triphenylamine donor, we have gradually red-shifted the absorption of sensitizers to enhance device efficiencies.

Tris(2,2 '-bipyridyl)ruthenium(II) electrochemiluminescent detection of coreactants containing aromatic diol group by the interaction between diol and borate anion

Previous studies show that aromatic diols inhibited Ru(bpy)(3)(2+) electrochemiluminescence (ECL), and all reported Ru(bpy)(3)(2+) ECL methods for the determination of aromatic diols-containing coreactants are based on inhibition of Ru(bpy)(3)(2+)/tripropylamine ECL. In this study, the interaction between diol and borate anion was exploited for Ru(bpy)(3)(2+) ECL detection of coreactants containing aromatic diol group using epinephrine as a model analyte. The interaction prevented from the inhibition of Ru(bpy)(3)(2+) ECL by aromatic diol group of epinephrine. As a result, epinephrine was successfully detected in the absence of tripropylamine simply by using borate buffer solution as the supporting electrolyte. Under the optimum conditions, the log of the ECL intensity increases linearly with the log of epinephrine concentrations over the concentration range of 1.0x10(-9)-1.0x10(-4) M. The detection limit is 5.0x10(-10) M at a signal-to-noise ratio of three. The proposed method exhibit wider dynamic range and better detection limit than that by inhibited Ru(bpy)(3)(2+) ECL method. The relative standard deviation for 14 consecutive determinations of 5 mu M epinephrine was 3.5%. The strategy by interaction with borate anion or boronate derivatives is promising for the determination of coreactants containing aromatic diol group or aromatic hydroxyl acid group. Such interaction can also be used to avoid interference from aromatic diols or aromatic hydroxyl acids.

Synergistic extraction of zinc(II) and cadmium(II) with mixtures of primary amine N1923 and neutral organophosphorous derivatives

Synergistic extraction of zinc(IT) and cadmium(11) from hydrochloric acid solution with primary amine N1923 and neutral organophosphorus derivatives Cyanex 923 and Cyanex 925 is the focus of this paper. Extraction mechanisms are discussed as well as how the acidity of the aqueous phase, the composition of the organic phase, and the experimental temperature affect the rates of extraction of metal ions. Differences between synergistic efficiency of Zn(II) and Cd(II) with mixtures of primary amines N1923 and either Cyanex 923 or Cyanex 925 are observed. The equilibrium constants, the composition, and the formation constants of the extracted complexes as well as the values of the thermodynamic functions are calculated. According to the synergy coefficient formula, the synergy effect on the extraction of Zn(II) is in the following order:N1923 + Cyanex 925 > N1923 + Cyanex 923 This order is reversed in the case of cadmium(II). For the same synergistic system, the extraction rate follows the order: Zn(II) > Cd(II). Furthermore, the stereochemical structures of the various extractants and their effect on metal ion extraction rate are also investigated.

Direct tris(2,2 '-bipyridyl)ruthenium(II) electrochemiluminescence detection of polyamines separated by capillary electrophoresis

Capillary electrophoresis (CE) with tris(2,2'-bipyridyl) ruthenium (II) (Ru(bpy)(3)(2+)) electrochemiluminescence (ECL) detection technique was developed for the analysis of four polyamines (putrescine (Put), cadaverine (Cad), spermidine (Spd), and spermine (Spm)) analysis. The four polyamines contain different amine groups, which have different ECL activity. There are several parameters which influence the resolution and ECL peak intensities, including the buffer pH and concentrations, separation voltage, sample injection, electrode materials, and Ru(bpy)(3)(2+) concentrations. Polyamines are separated by capillary zone electrophoresis in an uncoated fused-silica capillary (50 cm x 25 mum (ID) filled with acidic phosphate buffer (200 mmol/L phosphate, pH 2.0) - 1 mol/L phosphoric acid (9:1 v/v) and a separation voltage of 5 kV (25 muA), with end-column Ru(bpy)(3)(2+) ECL detection. A 5 mmol/L Ru(bpy)(3)(2+) solution plus 200 mmol/L phosphate buffer (pH 11.0) is added into the reagent reservoir. The calibration curve is linear over a concentration range of two or three orders of magnitude for the polyamines. The analysis time is less than 25 min. Detection limits for Put and Cad are 1.9 x 10(-7) mol/L and 7.6 x 10(-9) mol/L for Spd and Spm, respectively.

Synergistic extraction of zinc(II) with mixtures of CA-100 and cyanex 272

The extraction of zinc(II) from an aqueous chloride medium has been studied using mixtures of sec-nonylphenoxy acetic acid (CA-100) and bis(2,4,4-trimethylpentyl) phosphinic acid (Cyanex 272). The results demonstrate that zinc ion is extracted into heptane as ZnA(2).2HA with CA-100, ZnL2.2HL with Cyanex 272, and ZnA(2)L(2)H(2) with synergistic mixture. The equilibrium constants of the these species have been calculated and extraction mechanisms have been proposed. Thermodynamic parameters of the extraction process were determined by the temperature coefficient of extractability. The synergistic system enhances the extraction efficiency of zinc(II) and also improves the selectivity between zinc(II) and cadmium(II).

Synergistic extraction of zinc(II) by mixtures of primary amine N1923 and Cyanex272

The extraction of zinc(II) and cadmium(II) from chloride solution by mixtures of primary amine N1923 and Cyanex272 (HA) was studied. The synergistic effect was observed for the extraction of zinc(II) while no synergistic effect for cadmium(II), which makes it possible to separate zine(II) and cadmium(II) with the mixtures. The results showed that zinc(II) was extracted as (RNH3Cl)(3) . ZnCIA instead of ZnA(2) . 2HA which was extracted by Cyanex272 alone. The extraction mechanism was discussed and the formation constants and thermodynamic functions were determined. The separation factors between zinc(II) and cadmium(II) were calculated.

Aggregation behavior of amphiphilic D-pi-A molecules bearing recognition group

Aggregation behavior of two amphiphilic D-pi -A molecules bearing barbituric acid as both recogniton group and electron-drawing substituent, 5-(4-dodecyl oxybenzylidene)-(1H, 3H)-2,4,6-pyrimidine trione (PB12) and 5-(4-N,N-didodecyl aminobenzylidene)-(1H,3H)-2,4,6-pyrimidine trione (AB(12)) was studied by UV-visible, fluorescence, and surface voltaic spectroscopies (SPS). The experimental results indicate that PB12 tends to form J-aggregate and AB(12) tends to form H-aggregate under increasing concentration. An intramolecular twisted charge transfer (TICT) emission around 500 nm is observed when J-aggregate is formed between PB12 molecules, and an excimer emission around 600 nm is observed when H-aggregate is formed between AB(12) molecules.

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.

The channel behavior of gramicidin D in the self-assembled monolayer

It was found for the first time that gramicidin D (GD) molecules can be incorporated into the ODM monolayer which is self-assembled on the surface of the gold electrode and form monovalent cation channels.

Electrochemical study of gramicidin D forming ion-permeable channels in the bilayer lipid membranes

Gramicidin within the lipid bilayer matrix is a well-known channel-forming polypeptide, but the mechanism of the ions across the membrane induced by gramicidin is not well understood. We found that at very low concentration of gramicidin in a bilayer lipid membrane, the channel behavior was controlled by the voltage applied across the membrane. When the voltage is higher than 75 mV, the channel is closing, while lower than 75 mV, the channel is opening. But when the concentration of the gramicidin in the BLMs is high, the channel behavior is changed into voltage-independent. (C) 1998 Elsevier Science Ltd. All rights reserved.