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151.
Paul Ruelle Michel Buchmann Hô Nam-Tran Ulrich W. Kesselring 《Journal of computer-aided molecular design》1992,6(5):431-448
Summary The thermodynamics of mobile order is applied to predict the aqueous solubility of liquid and solid aliphatic and polycyclic aromatic hydrocarbons. The solubility values are mainly determined by the magnitude of the hydrophobic effect. However, contrary to the solubilities of the alkanes, the solubilities of polycyclic aromatic hydrocarbons in water predicted in absence of solute-solvent hydrogen (H) bonds are systematically too low. This shows the contribution of weak specific interactions between the OH groups and the electrons of the aromatic substances. According to the theory, these interactions are characterized by a stability bility constant Ko which can be derived from solubility data. At 25°C, this constant amounts to 80 cm3/mol, the order of magnitude of which can be explained by the competition of these intermolecular bonds with the rather weak self-association bonds in the secondary chains of water. 相似文献
152.
A series of “push-pull” porphyrins with 4-nitrophenyl and 4-aminophenyl substituents were synthesized and separated by flash column chromatographic techniques. They were fully characterized by elemental analysis, FAB-MS, FTIR, UV-visible, and 1H NMR spectroscopies. The unsymmetrical π-electron distribution of the porphyrins caused by the donor (amino) and acceptor (nitro) substituents were investigated by 1H NMR technique. The pyrrole-H resonance positions can be correlated to the Hammett σ constants of the substituents. Although with strong donor and acceptor substituents, UV-visible spectra show the push-pull porphyrins have rather weak solvatochromism and hence limited intramolecular charge-transfer character. 相似文献
153.
A. D. Dubonosov V. P. Rybalkin Ya. Yu. Vorob’eva V. A. Bren’ V. I. Minkin S. M. Aldoshin V. V. Tkachev A. V. Tsukanov 《Russian Chemical Bulletin》2004,53(10):2248-2252
It was shown by electron absorption spectroscopy and X-ray diffraction analysis that steric strains in photochromic 2-(N-acyl-N-arylaminomethylene) benzo[b]thiophen-3(2H)-one molecules ortho-substituted in the N-phenyl ring increase the quantum yield of the N→O photoinduced rearrangement in accord with an increase in the steric constant of the ortho-substituent.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2151–2155, October, 2004. 相似文献
154.
The binding constants, K′, for the reaction between some alkyldimethylbenzylammonium bromide homologues (alkyl = methyl, ethyl, propyl, butyl, hexyl,
decyl, and dodecyl, respectively) and β-cyclodextrin in water at 25.0 ± 0.1 ∘C have been determined, by applying the spectral displacement technique with phenolphthalein as the displacing anion. It has
been shown that the ln K′ values increase linearly with the number of carbon atoms in the alkyl chain for the salts whose alkyl chain has at least
four carbon atoms. The ln K′ values estimated for the parent compound benzyltrimetylammonium bromide and its two nearest homologues are distinctly lower
than might be expected by extrapolation of the linear relation found for the higher homologues. Assuming that it is the organic
cation that undergoes association with β-cyclodextrin, then one may suppose that a change occurs in the mode of inclusion of the cation upon passing to higher homologues.
In the case of the lighter homologues, it is the phenylene group that undergoes inclusion. This model of inclusion is confirmed
by analysis of rotating-frame overhauser effect spectroscopy (ROESY) spectra. 相似文献
155.
Felicia Dragan I. Bratu Gh. Borodi Mihaela Toma A. Hernanz S. Simon Gh. Cristea R. Peschar 《Journal of inclusion phenomena and macrocyclic chemistry》2007,59(1-2):125-130
Aqueous-solution complexes of β-cyclodextrin (β-CD) with metoprolol tartrate (MET) have been analysed with 1H NMR and UV–vis spectroscopy. With 1H NMR a [1:1] stoichiometry could be established for the β-CD-MET complex while its stability constant was determined with
UV–vis spectroscopy. Powder diffraction data of a polycrystalline sample of the β-CD-MET complex show that a novel product
has been formed, likely to be a β-CD-MET [1:1] inclusion complex. Also Hyperchem MM+ molecular-dynamics results suggest an
inclusion complex and from 1H NMR data it is inferred that probably the MET is docked in the CD with the formers methoxyethyl-benzene moiety in front.
Mihaela Toma is Socrates/Erasmus student at UNED Madrid 相似文献
156.
Julie L. S. Bell David J. Wesolowski Donald A. Palmer 《Journal of solution chemistry》1993,22(2):125-136
The dissociation quotients of formic acid were measured potentiometrically from 25 to 200°C in NaCl solutions at ionic strengths of 0.1, 0.3 1.0, 3.0, and 5.0 mol-kg–1. The experiments were carried out in a concentration cell with hydrogen electrodes. The resulting molal acid dissociation quotients for formic acid, as well as a set of infinite dilution literature values and a calorimetrically-determined enthalpy of reaction, were fitted by an empirical equation involving an extended Debye Hückel term and seven adjustable parameters involving functions of temperature and ionic strength. This regressional analysis yielded the following thermodynamic quantities for 25°C: logK=–3.755±0.002, Ho=–0.09±0.15 kJ-mol–1, So=–72.2±0.5 J-K–1-mol–1, and C
p
o
=–147±4 J-K–1-mol–1. The isocoulombic form of the equilibrium constant is recommended for extrapolation to higher temperatures. 相似文献
157.
The 25% niobium substituted crystalline titanosilicate with the composition Na1.5Nb0.5Ti1.5O3SiO4·2H2O (Nb-TS) was synthesized under hydrothermal conditions. Its selectivity for radioactive 137Cs and 89Sr was compared with the TS, Na2Ti2O3SiO4·2H2O, having sitinakite topology. The Nb-TS shows significantly higher uptake value for 137Cs but lower for 89Sr than the TS. To investigate the origin of selectivity, the ion exchanged Cs+ and Sr2+ forms with the composition, CsxNaHyNb0.5Ti1.5O3SiO4·zH2O (x=0.1, 0.2 and 0.3, x+y=0.5 and z=1-2) and Sr0.2Na0.6H0.5Nb0.5Ti1.5O3SiO4·H2O, respectively, were structurally characterized from the X-ray powder diffraction data using the Rietveld refinement technique. Simultaneously the kinetics of 137Cs and 89Sr uptake was investigated for the NbV free and doped samples. While the Cs+ and Sr2+ exchanged form of Nb-TS and the Cs+ exchanged form of TS retain the symmetry of the parent compound, the Sr2+ exchanged form of TS undergoes a symmetry change. The differences in the uptake of Cs+ and Sr2+ result from the different coordination environments of cesium and strontium in the eight-ring channel, that result from various hydration sites in the tunnel. The origin of selectivity appears to arise from the higher coordination number of cesium or strontium. Other effects due to NbV substitution are reflected in the increase of both, the a- and c-dimensions and thus the unit cell volume, and the population of water vs. Na+ in the channel to charge-balance the Nb5+↔Ti4+ substitution. 相似文献
158.
Shoichi Katsuta Tokutaro Kimura Yoshihiro Kudo Ryozo Nakagawa Yasuyuki Takeda Mikio Ouchi 《Journal of inclusion phenomena and macrocyclic chemistry》1998,31(2):89-98
The overall extraction constants (Kex) of uni- andbivalent metal picrates with 15-(2,5-dioxahexyl)-15-methyl-16-crown-5(L16C5) were determined between benzene and water at 25°C. TheKex values were analyzed into the constituent equilibriumconstants, i.e., the extraction constant of picric acid, the distributionconstant of the crown ether, the stability constant of the metalion–crown ether complex in water, and the ion-pair extraction constantof the complex cation with the picrate anion. The Kex valuedecreases in the orders Ag+ > Na+ >Tl+ > K+ > Li+ andPb2+ > Ba2+ > Sr2+ for theuni- and bivalent metals, respectively, which are the same as those observedfor 16C5. The extraction selectivity was found to be governed by theselectivity of the ion-pair extraction of the L16C5–metal picratecomplex rather than by that of the complex formation in water. Theextraction ability of L16C5 is smaller for all the metals than that of 16C5,which is mostly attributed to the higher lipophilicity of L16C5. Differencesin the extraction selectivity between L16C5 and 16C5 were observed for thebivalent metals but little for the univalent metals. The side-arm effect onthe extraction selectivity was interpreted on the basis of the negativecorrelation between the effect on the complex stability constant in waterand that on the ion-pair extraction constant. 相似文献
159.
Karolina Kucharska Marta Pilz Krzysztof Bielec Tomasz Kalwarczyk Patrycja Ku
ma Robert Hoyst 《Molecules (Basel, Switzerland)》2021,26(12)
The oxazole yellow dye, YOYO-1 (a symmetric homodimer), is a commonly used molecule for staining DNA. We applied the brightness analysis to study the intercalation of YOYO-1 into the DNA. We distinguished two binding modes of the dye to dsDNA: mono-intercalation and bis-intercalation. Bis-intercalation consists of two consecutive mono-intercalation steps, characterised by two distinct equilibrium constants (with the average number of base pair per binding site equals 3.5): and , respectively. Mono-intercalation dominates at high concentrations of YOYO-1. Bis-intercalation occurs at low concentrations. 相似文献
160.
The molar conductivities (Λ) of solutions of n-tetrabutylammonium tetraphenylborate (NBu4BPh4) in 3-pentanone have been measured in the temperature range from 283.15 to 329.15 K. The conductance data have been analyzed
using the Lee-Wheaton conductivity equation with the distance parameter (a) set at Bjerrum’s pairing distance, and the limiting molar conductivities (Λo) and the association equilibrium constants (K
A) have been derived. The limiting ion conductivities (λ_±o) have been evaluated according to the method of Krumgalz. The λ+
o values have been compared with λ+
o values calculated from the empirical equation of Gill. The thermodynamic functions, Gibbs energy (Δ G
A
o), enthalpy (Δ H
A
o) and entropy (Δ S
A
o) for the process of ion-pair formation as well as the activation energy of the ionic movement (ΔH
∗) have been evaluated. The obtained results are discussed in terms of ion-ion and ion-solvent interactions. 相似文献