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11.
The enthalpies and free energies of proton affinity (PA) were calculated by the PM3 method for 27 thiophenoxide anions. For thiophenols, linear correlation has been found between the PAs and the values of pK
a
measured by different authors in aqueous acetone, aqueous ethanol, and methanol media. The dependences found permit one to predict a priori the protolytic properties of thiophenols. The differential effects of aqueous ethanol media with different ethanol contents on thiophenol acidity were evaluated based on quantum-chemical data.Original Russian Text Copyright © 2004 by A. N. Pankratov and A. V. Shalabai__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 5, pp. 800–806, September–October, 2004. 相似文献
12.
We study a system of quasilinear equations describing one-dimensional flow of a viscous compressible heat-conducting medium with a nonmonotone state function and mass force. The large-time behavior of solutions is considered for arbitrarily large initial data. In spite of possible nonuniqueness and discontinuity of the stationary solution, we prove L2-stabilization for the stress and heat flux as t → ∞ along with corresponding global energy estimates for them. The new method of proof utilizes a combination of energy type equalities for the stress and heat flux. Consequently, H1-stabilization of the velocity and temperature along with global estimates for their derivatives are valid as well. 相似文献
13.
Precipitate-forming chemical reactions have been studied in chemically cross-linked poly(vinyl alcohol) gel medium. One of the reactive components was incorporated into the gel, the other was allowed to diffuse into it. Depending on the experimental conditions the reaction-diffusion process often results in patterns of different type. Experiments performed in tubes and in thin layers were carried out in order to investigate the effects of various factors (cross-linking density, swelling degree as well as the concentrations of the outer and inner electrolytes) on the morphologies of the precipitate patterns. It was found that precipitation occurs not only in the Liesegang bands, but also between bands. Beside Liesegang-type structures, tree-like patterns have been observed, showing a characteristic periodicity in the density profile obtained by digitalized image analyses. 相似文献
14.
S. Fumeron P. Ben-Abdallah 《Journal of Quantitative Spectroscopy & Radiative Transfer》2006,97(2):195-208
The aim of this paper is to present several features of the couplings occurring between radiative transfer and the kinetics of a moving dielectric. After determining how the velocity field affects the apparent thermo-optical properties of matter, the energy transport problem is investigated in instationary regime and the general form of transient radiative transfer equation inside a moving medium is built. Then, the model is applied to the particular case of turbulent flows: a system of two equations for mean and fluctuating radiative energies is presented, and the resolution of this system is finally carried out. 相似文献
15.
16.
Monot Frédéric Benoit Yves Ballerini Daniel Vandecasteele Jean-Paul 《Applied biochemistry and biotechnology》1990,(1):375-386
Utilization of lipases for synthesis of esters of hydrophilic polyols has been investigated. The choice of a suitable solvent
is crucial in this type of reaction. An interesting case is fatty acid esters from neopentylpolyols, such as trimethylolpropane,
which are of great interest as high temperature lubricants. Enzymatic synthesis of trimethylolpropane tricaprylate was studied
as an alternative to chemical manufacturing. Triester production occurred only if the water produced by esterification was
continuously removed from the medium. In these condition, kinetics of appearance and transformation of mono-, di- and triesters
were determined in order to define optimal conditions. 相似文献
17.
A theory is developed for the potential distribution around a charged spherical colloidal particle carrying ionized groups on the particle surface in a medium containing its counterions (i.e., counterions produced from dissociation of the particle surface groups) and a small amount of added salts on the basis of the theory of Imai and Oosawa. Numerical solutions to the Poisson–Boltzmann equation for the potential distribution are obtained for the case of dilute (but not infinitely dilute) particle suspensions of volume fraction 1 for
a1 (where is the Debye–Hückel parameter and a is the particle radius). Here we have taken into account the effects of (i) counterions from the particle surface groups, and (ii) the finite particle volume fraction. These effects, which are usually neglected in the conventional Poisson–Boltzmann equation, are found to be important. It is found that, as in the case of completely salt-free media, there is a certain critical value of the particle charge (which is the same as that for the completely salt-free case). When the particle charge is lower than the critical value, the potential is given by a Coulomb potential. If the particle charge is higher than the critical value, then counterions are accumulated in the vicinity of the particle surface (counterion condensation) and the potential becomes less dependent on the particle charge. The above behaviors can be observed even for the case where the electrolyte concentration is higher than the concentration of counterions from the particle surface groups, if the conditions
1 and a1are both satisfied. 相似文献
18.
合成了6种氨基酸水杨醛席夫碱(Sal-AA):Sal-Gly(甘氨酸)、Sal-Phe(苯丙氨酸)、Sal-Arg(精氨酸)、Sal-Tyr(酪氨酸)、Sal-Met(甲硫氨酸)、Sal-Glu(谷氨酸)及其金属铜配合物。并分别在2种不同介质(三氯甲烷和甲醇)中,与四苯基卟啉TPP进行反应,研究了其紫外可见光谱性质,讨论了卟啉作为人工信号转导体系的传递介质,与氨基酸水杨醛席夫碱铜配合物的反应中,实现信号分子铜离子进一步传递的可能性以及溶剂对该信号传递的影响。结果表明,在三氯甲烷为溶剂时,除了Sal-Met的铜配合物之外,其余均能被TPP夺取而形成Metal TPP。而在以甲醇为溶剂时,只有Sal-Gly的铜配合物能被TPP所夺取。 相似文献
19.
In this article, the results of calculations of scattering spectra of low-absorptive spherical particles are presented. It was obtained using different approximate and numerical methods. The comparative evaluations of application of single scattering approximation, the average field approximation and of the methods of computer modeling on the basis of Monte-Carlo method on various scattering multiplicity were performed. The comparison demonstrates the good agreement of calculated results with experimental scattering spectra of eye lens. By using the obtained spectral data the colour coordinates are calculated. The regularities of changes in colour characteristics in dependence of disperse system parameters are analyzed. 相似文献
20.
The purpose of this study is to investigate the influence of nickel, which is an alloying element in commonly used metallic biomaterials, on the biomaterials mineralization process. An electrochemical method was developed to quantify this metal ion in osteoblast-like cell culture medium (OST) by performing adsorptive cathodic stripping voltammetry (CSV) with dimethylglyoxime (DMG) at a mercury film microelectrode (MFM). The optimized analytical conditions and the square-wave CSV parameters for the analysis are: DMG concentration: 5.00 × 10−4 mol L−1; ammonium chloride buffer: 0.10 mol L−1 (pH 9.2); frequency: 50 Hz, amplitude 20 mV; step: 2 mV; adsorption time: 10 s, deposition potential: −0.70 V and reduction potential: −1.20 V. The limit of detection was 7.70 × 10−9 mol L−1 for an adsorption time of 10 s. The results achieved by CSV using the MFM were compared to those obtained by atomic absorption spectrometry (AAS) to ensure the reliability of the electrochemical method. The mineralization process was evaluated by biochemical and histochemical assays. 相似文献