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991.
Enn?LustEmail author Alar?J?nes Tanel?P?rn Priit?Nigu 《Journal of Solid State Electrochemistry》2004,8(4):224-237
Electrochemical characteristics for the nanoporous carbon|Et4NBF4+acetonitrile interface have been studied by cyclic voltammetry and impedance spectroscopy methods. The influence of the electrolyte concentration and thickness of the nanoporous electrode material on the shape of the cyclic voltammetry and impedance curves has been established and the reasons for these phenomena are discussed. A value of zero charge potential, depending slightly on the structure and concentration of the electrolyte, the region of ideal polarizability and other characteristics have been established. The nanoporous nature of the carbon electrodes introduces a distribution of resistive and capacitive elements, giving rise to complicated electrochemical behaviour. Analysis of the complex plane plots shows that the nanoporous carbon|Et4NBF4+acetonitrile electrolyte interface can be simulated by an equivalent circuit, in which two parallel conduction paths in the solid and liquid phases are interconnected by the double-layer capacitance in parallel with the complex admittance of the hindered reaction of the charge transfer or of the partial charge transfer (i.e. adsorption stage limited) process. The values of the characteristic frequency depend on the electrolyte concentration and electrode potential, i.e. on the nature of the ions adsorbed at the surface of the nanoporous carbon electrode. The value of the solid state phase resistance established is independent of the thickness of the electrode material. 相似文献
992.
Kazimierz?DarowickiEmail author Juliusz?Orlikowski Anna?Arutunow 《Journal of Solid State Electrochemistry》2004,8(6):352-359
Electrochemical impedance spectroscopy allows the examination of corrosion susceptibility and resistance for different construction materials, in particular the determination of the properties of their passive films. This technique makes possible the analysis of electrochemical processes in time domain, including rapid phenomena such as changes in the properties of passive films, but it has never been used for passive layer cracking examination. In many cases, fracture of the passive film under tensile stresses leads to stress corrosion cracking. Therefore, investigations of passive layer cracking on austenitic stainless steels under tensile stresses facilitate the understanding of the mechanism of stress corrosion cracking in these common engineering materials. The effect of static tensile stresses on the passive film cracking behaviour of type 304L stainless steel immersed in 0.5 M NaCl solution at room temperature has been investigated. This paper presents the impedance spectra obtained for 304L stainless steel samples at different potential values.Contribution to the 3rd Baltic Conference on Electrochemistry, Gdansk-Sobieszewo, Poland, 23–26 April 2003Dedicated to the memory of Harry B. Mark, Jr. (28 February 1934–3 March 2003) 相似文献
993.
A chemiluminescence signal at 425 nm was observed when ferric state myoglobin was mixed with luminol in alkaline medium. Because the signal was remarkably enhanced in the presence of Fe(CN)6
4–, analytical applications were investigated in a flow-injection system. The increase in chemiluminescence was linearly dependent on myoglobin concentration in the range 0.1 to 100 nmol L–1, and the limit of detection was 0.04 nmol L–1 with relative standard deviation 3.2% (3). It was also found that binding of Mb with the ligands CN–, SCN–, and F– significantly inhibited the chemiluminescence reaction. The linear dynamic ranges for the ligands were 1.0–300.0, 0.1–3.0, and 0.5–100.0 nmol L–1, and the limits of detection (S/N=3) 0.4, 0.04, and 0.2 nmol L–1, for F–, CN–, and SCN–, respectively. The relative standard deviations were 5.32%, 6.13%, and 3.38% for 0.1 nmol L–1 CN–, 0.5 nmol L–1 SCN–, and 1.0 nmol L–1 F–, respectively. At a flow rate of 2.0 mL min–1 the assay could be accomplished in 1 min, including sampling and washing. The method has been successfully applied to the determination of myoglobin in human urine and F– in water samples. A possible mechanism of chemiluminescence production by myoglobin and luminol is presented. 相似文献
994.
Ahmad?ShaabaniEmail author Mohammad Bagher?Teimouri Hamid Reza?Bijanzadeh 《Monatshefte für Chemie / Chemical Monthly》2004,135(5):589-593
Summary. The environment-friendly one-pot three-component condensation reactions of 4-hydroxycoumarin or 4-hydroxy-6-methylpyrone, p-substituted benzaldehyde, and alkyl or aryl isocyanides to afford furocoumarines or furopyranones in water in good yields after about one hour at 75°C are reported. 相似文献
995.
Jing CHAO Xing Yuan ZHANG Jia Bing DAI Zhen GE Lin Lin FENG 《中国化学快报》2006,17(8):1121-1124
Aqueous acrylic-polyurethane dispersions have become one of the major types of materials used in coating, paint and adhesive industries, because of excellent properties and environmental advantages1-5. However, some properties for cured film such as water… 相似文献
996.
β-Nitro-5,10,15,20-tetraphenylporphyrin and its zinc complex, or 2,7-dinitro-5,10,15,20-tetraphenylporphyrin, react with 1,3-dihydrobenzo[c]thiophene 2,2-dioxide in refluxing 1,2,4-trichlorobenzene, giving rise to chlorins, bacteriochlorins or isobacteriochlorins. The products obtained are attractive intermediates for further functionalization of porphyrins and may be of potential use as sensitizers in photodynamic therapy. 相似文献
997.
A fully deprotonated 2-bromo-1,4-benzenedicarboxylate copper(II) complex, [Cu(bbdc)(2,2′-bipy)](H2O) (bbdc= 2-bromo-1,4-benzenedicarboxylate dianion, 2,2′-bipy=2,2′-bipyridine), was synthesized under hydrothermal conditions.
This compound also can be prepared from the partly deprotonated [Cu(Hbbdc)2(2,2′-bipy)] under basic and hydrothermal conditions. The crystal structure consists of infinite chains of [Cu2(μ4-bbdc)]2+ building blocks connected by bis-monodentate bbdc ligands and exhibits an extended 2-D architecture.
Electronic supplementary material Electronic supplementary material is available for this article at
and accessible for authorised users. 相似文献
998.
Chitta RK Rempel DL Gross ML 《Journal of the American Society for Mass Spectrometry》2005,16(7):1031-1038
The dimerization of gramicidin, a 15-residue membrane peptide, in solution can be viewed as a model for protein-protein interactions. We reported previously that the dimer can be observed when electrosprayed from organic solvents and that the abundances of the dimer depends on the dielectric constant of the solvent. Here, we report an effort to determine an affinity constant for the dimerization of gramicidin by using gas-phase abundance. Two issues affecting the determination are the electrospray-induced dissociation of the dimer and discrimination in the electrospray of the dimer compared with the monomer. Other methods developed for the purpose of determining affinity from mass spectral abundance do not address the dissociation of the complex in the gas phase or can not be applied for cases of low affinity constant, K(a). We present a mathematical model that uses the ratio of the signal intensities of the dimer and the monomer during a titration. The model also incorporates the dissociation and an electrospray ionization-response factor of the dimer for extracting the affinity constant for the dimerization of gramicidin. The dimerization constants from the new method agree within a factor of two with values reported in the literature. 相似文献
999.
The dependent relation between temperature and pressure of supercritical CO2+ ethanol binary system under the pressure range from 5 to 10 MPa with the variety of densities and mole fractions of ethanol
that range from 0 to 2% was investigated by the static visual method in a constant volume. The critical temperature and pressure
were experimentally determined simultaneously. The PTρ figures at different ethanol contents were described based on the determined pressure and temperature data, from which pressure
of supercritical CO2 + ethanol binary system was found to increase linearly with the increasing temperature. P-T lines show certain convergent feature in a specific concentration of ethanol and the convergent points shift to the region
of higher temperature and pressure with the increasing ethanol compositions. Furthermore, the effect of density and ethanol
concentration on the critical point of CO2 + ethanol binary system was discussed in details. Critical points increase linearly with the increasing mole fraction of
ethanol in specific density and critical points change at different densities. The critical compressibility factors Zc of supercritical CO2 + ethanol binary systems at different compositions of ethanol were calculated and Z
c
-ρ figure was obtained accordingly. It was found from Z
c
-ρ figure that critical compressibility factors of supercritical CO2 unitary or binary systems decline linearly with the increasing density, by which the critical point can be predicted precisely. 相似文献
1000.
Alternative mobile phases for the reversed-phase high-performance liquid chromatography of peptides and proteins 总被引:2,自引:0,他引:2
The use of a high content of acetic acid as mobile phase additive for the reversed-phase high-performance liquid chromatography (RP-HPLC) of several proteins and extracts of biological tissues was evaluated for a divinylbenzene (DVB)-based stationary phase, and the separations obtained with acetic acid gradients in acetonitrile, isopropanol or water were compared with classical polypeptide RP-HPLC on silica C4 with trifluoroacetic acid (TFA)-acetonitrile. The separation patterns for recombinant derived interleukin-1 beta (IL-1 beta) on the C4 column eluted with TFA-acetonitrile and the DVB column eluted with acetic acid-acetonitrile were similar, but only the polymeric column was able to separate the components present in an iodinated IL-1 beta preparation. Neither eluent had any harmful effect on the biological activity of IL-1 beta isolated after RP-HPLC. Several standard proteins could be separated when the polymeric column was eluted with acetic acid gradients in acetonitrile, isopropanol or water and, although the separation efficiency with acetic acid in water was lower than that in combination with classical organic modifiers, insulin, glucagon and human growth hormone (hGH) were eluted as sharp, symmetrical peaks. The recoveries of insulin and hGH were comparable for all three mobile phases (80-90%). The separation patterns obtained from a crude acetic acid extract of a normal and a diabetic, human pancreas analysed using acetic acid gradients with or without organic modifiers were found to be similar and comparable to those obtained on a silica C4 column eluted with an acetonitrile gradient in TFA. The principal differences resulted from the use of different UV wavelengths (215 nm for TFA-acetonitrile, 280 nm for acetic acid). Acetic acid extracts of recombinant derived hGH-producing Escherichia coli were separated on the DVB column eluted with an acetic acid gradient in water. Although the starting material was a highly complex mixture, the hGH isolated after this single-step purification was surprisingly pure (as judged by sodium dodecyl sulphate-polyacrylamide gel electrophoresis). Consequently several (pure) polypeptides and complex biological samples were separated on a polymeric stationary phase eluted with acetic acid gradients in water without the use of organic modifiers. 相似文献