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31.
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
32.
Using the linearization of Einstein's equations for weak gravitational fields, a specific model of gravito-magnetofluid is elaborated. The study of wave formation and propagation in such a medium is necessarily connected to the existence of the cosmological constant. 相似文献
33.
34.
B. Y. Myung J. S. Kim J. J. Kim T. H. Yoon 《Journal of polymer science. Part A, Polymer chemistry》2003,41(21):3361-3374
2,2‐Bis[4(4‐aminophenoxy)phenyl]phthalein‐3′,5′‐bis(trifluoromethyl)anilide (6FADAP), containing fluorine and phthalimide moieties, was synthesized via the Williamson ether condensation reaction from 1‐chloro‐4‐nitrobenzene and phenolphthalein‐3′,5′‐bis(trifluoromethyl)anilide, which was followed by hydrogenation. Monomers such as 2,2‐bis[4(4‐aminophenoxy)phenyl]phthalein‐anilide containing phthalimide groups and 2,2‐bis[4(4‐aminophenoxy)phenyl]phthalein containing only phthalein moieties were also synthesized for comparison. The monomers were first characterized by Fourier transform infrared (FTIR), 1H NMR, 19F NMR, elemental analysis, and titration and were then used to prepare polyimides with 2,2‐bis(3,4‐dicarboxyphenyl)hexafluoropropane dianhydride. The polyimides were designed to have molecular weights of 20,000 g/mol via off‐stoichiometry and were characterized by FTIR, NMR, gel permeation chromatography (GPC), differential scanning calorimetry, and thermogravimetric analysis. Their solubility, water absorption, dielectric constant, and refractive index were also evaluated. The polyimides prepared with 6FADAP, containing fluorine and phthalimide moieties, had excellent solubility in N‐methylpyrrolidinone, N,N‐dimethylacetamide, tetrahydrofuran, CHCl3, tetrachloroethane, and acetone, and GPC analysis showed a molecular weight of 18,700 g/mol. The polyimides also exhibited a high glass‐transition temperature (290 °C), good thermal stability (~500 °C in air), low water absorption (1.9 wt %), a low dielectric constant (2.81), a low refractive index, and low birefringence (0.0041). © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3361–3374, 2003 相似文献
35.
Xuming Xie 《Journal of Differential Equations》2004,197(2):349-426
This paper concerns the existence of solutions to a steady needle crystal growth problem in a one-sided model. We rigorously prove that for small nonzero anisotropy γ, analytic symmetric needle crystal solutions exist in the limit of surface tension ε2 if only if the stokes constant S for a relatively simple nonlinear differential equation is zero. This Stokes constant S depends on the parameter β=29/7γε−8/7 and earlier numerical calculations by a number of investigators have shown this to be zero for a discrete set of values of β. It is also proven that for γ=0, there can be no symmetric needle crystal solution in the considered space.The methodology consists of two steps. First, the original problem is reduced to a weak half-strip problem for any γ in a compact set of [0,1) by relaxation of the symmetry condition. The weak problem is shown to have a unique solution in the function space considered for any γ∈[0,γm] for some γm>0. When a symmetry is invoked, the weak problem is shown equivalent to the original needle crystal problem. Next, by considering the behavior of the solution in neighborhood of an appropriate complex turning point for γ∈(0,γm], we extract an exponentially small term in ε as ε→0+ that generally violates the symmetric condition. We prove that the symmetry condition is satisfied for small ε when the parameter β is constrained appropriately. 相似文献
36.
37.
由于含时波包方法具有经典的直观又不乏量子力学的准确 ,选择含时波包方法来处理F +CH2 D2 →CH2 D/CHD2 +DF/HF反应 .把半刚性振转子 (SVRT)模型应用到该反应体系中 ,研究了两个通道中该反应从基态反应物开始在修正过的J1(MJ1)势能面上计算出来了反应几率、积分截面、速率常数 .反应几率随能量变化的图的数值结果给出了振荡结构 ,这些振荡结构是可以和动力学振荡联系起来的 .而这些振荡结构在积分截面随着能量变化的图中就被反应几率求和后的平均结果所掩盖了 .速率常数和实验结果的比较也得到了较好的结果 . 相似文献
38.
Protonation constant of an unsymmetrical Schiff base, salicylidene(N-benzoyl)glycyl hydrazone (SalBzGH), and formation constants
of its complexes have been determined potentiometrically at different temperatures in aqueous dioxane medium. Complexes of
SalBzGH with VO(IV), Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II) have been prepared. Elemental analyses, pH-metric,
molar conductance, magnetic susceptibility, electronic, IR, ESR, XRD (powder) and NMR studies have been carried out to study
the coordination behaviour of SalBzGH toward these metal ions. pH-metric and 1H NMR studies show the presence of two dissociable
protons in the ligand. IR and NMR spectra suggest the tridentate nature of the ligand, coordinating as a uninegative species
in the Mn(II) complex and as a dinegative species in all the other complexes. Presence of two different conformers of the
ligand at room temperature and stabilization of a single conformer upon complex formation have been established from1H NMR spectra of the metal-free ligand, Zn(II) and Hg(II) complexes recorded at 296 K. Electronic and ESR spectra indicate
highly distorted tetragonal geometry for VO(IV) and Cu(II) complexes. XRD powder patterns of the Zn(II) complexes are indexed
for an orthorhombic crystal system. 相似文献
39.
40.
The constants of binding dye molecules with the micelles of sodium dodecyl sulfate are determined using quenching of delayed fluorescence of acridine dyes by sodium iodide in aqueous–micellar solutions. Kinetic equations have been composed that describe the processes of deactivation of the excited states of dyes. By solving these equations at the concentration of the quencher sodium iodide corresponding to the minimum lifetime of triplet states and at the concentration of micelles corresponding to the least value of the delayed fluorescence quenching rate constants, we obtained the constants of binding dyes with micelles equal to 1.3·107, 2.9·107, and 3.1·107 M–1 for trypaflavine, acridine orange, and acridine yellow, respectively. We calculated the rate constants of quenching of the triplet states of the molecules of dyes by iodide ions (I
–) that decreased in transition from trypaflavine to acridine orange and acridine yellow. 相似文献