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161.
Dynamic light scattering experiments in acid-catalyzed silica sols are discussed. It is shown that in spite of limited parameter accuracy and limited absolute knowledge of the particle sizes, the scattering data from various experiments are comparable with one another and give information about structural differences. Measurements at various angles indicate changes between non-spherical and nearly spherical particles and allow the estimation of gelling times before gelation. 相似文献
162.
Vapor pressure,speciation, and chemical activities in highly concentrated sodium borate solutions at 277 and 317°C 总被引:2,自引:0,他引:2
Oleh Weres 《Journal of solution chemistry》1995,24(5):409-438
The system H2O-B2O3-Na2O has been studied experimentally at 277 and 317°C. The activities of water and boric acid have been determined at mole ratios Na/B from 0 to 1.5, and total dissolved solids 3 to 80 weight percent. The activity of boric acid has been fitted to within experimental error using a speciation model with eight complex species. This model is consistent with the model previously published by Mesmer et al. The electrolyte properties of the liquid are modeled using the Pitzer-Simonson model of very concentrated electrolyte solutions. The calculated values of water activity agree with experiment, and the activity of NaOH and pOH have also been calculated. The potassium borate system also was briefly studied at 317°C, and is adequately described by a model with five complex species. The potassium borate liquid is more alkaline at K/B= 1 than a sodium borate liquid at the same mole ratio, but pOH in the two systems is the same at lower mole ratios. 相似文献
163.
Chiral α,ω-diesters react under high-pressure conditions (10 kbar) with α,ω-diamines to give chiral cyclic tetraamides of C2-symmetry. The complexation properties of tetraamides towards alkali metal cations (Li+, Na+, K+, Rb+ and Cs+) were estimated on the basis of ESI-MS spectra. 相似文献
164.
Horn M Ihringer J Glink PT Stoddart JF 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(17):4046-4054
A template-directed dynamic clipping procedure has generated a library of nine [2]rotaxanes that have been formed from three dialkylammonium salts-acting as the dumbbell-shaped components-and three dynamic, imino bond-containing, [24]crown-8-like macrocycles-acting as the ring-shaped components-which are themselves assembled from three dialdehydes and one diamine. The rates of formation of these [2]rotaxanes differ dramatically, from minutes to days depending on the choice of dialkylammonium ion and dialdehyde, as do their thermodynamic stabilities. Generally, [2]rotaxanes formed by using 2,6-diformylpyridine as the dialdehyde component, or bis(3,5-bis(trifluoromethyl)benzyl)ammonium hexafluorophosphate as the dumbbell-shaped component, assembled the most rapidly. Those rotaxanes containing this particular electron-deficient dumbbell-shaped unit, or 2,5-diformylfuran units in the macroring, were the most stable thermodynamically. The relative thermodynamic stabilities of all nine of the [2]rotaxanes were determined by competition experiments that were monitored by (1)H NMR spectroscopy. 相似文献
165.
166.
The solubility of glycine,
-alanine,
-valine,
-leucine, and
-isoleucine in water was measured at 298.15 K and pressures up to 400 MPa. The standard deviation of the logarithm of the solubility is 0.001–0.003, equal to or better than the accuracy of atmospheric pressure measurement in the literature (0.001–0.05). A variety of solubility phenomena were observed. The solubility of glycine decreased with increasing pressure, whereas that of
-alanine increased. The
-valine and
-isoleucine have a solubility maximum at around 100 MPa, and
-leucine seems to exhibit a solid-phase phase transition at around 200 MPa. Pressure coefficient of the solubilities at 0.10 MPa is compared with that thermodynamically estimated in reference to aqueous density measurements of glycine and
-alanine at 298.15 K and 0.10 MPa, supporting a reliability of our high-pressure measurements. 相似文献
167.
A highly sensitive and selective liquid chromatography-mass spectrometry (LC-MS) method has been developed for the determination of epirubicin in serum and cell specimens using daunorubicin as an internal standard. Using atmospheric pressure chemical ionisation (APCI), the epirubicin metabolites were readily distinguishable by their fragmentation pattern in the mass spectrometer. Selected reaction monitoring (SRM) mode was employed for quantitation of epirubicin and the metabolites. Following extraction, chromatography was performed on a C18 column with a mobile phase consisting of water-acetonitrile-formic acid, pH 3.2, with a flow rate of 200 μl/min. The limit of detection (LOD) and the limit of quantitation (LOQ) of this method in serum were determined to be 1.0 and 2.5 ng/ml, respectively. Linearity of the method was verified over the concentration range of 2.5-2000 ng/ml, with a high correlation coefficient (R2 ≥ 0.998). For the extraction procedure, an aliquot of 500 μl serum, spiked with internal standard, was extracted using a chloroform-2-isopropanol (2:1, v/v) mixture. The method has been applied to the analysis of epirubicin in cancer cell samples and the identification of known and unknown metabolites in clinical trial patient serum samples. 相似文献
168.
The results of NMR-spectroscopy studies of the structure, dynamic stereochemistry, and intermolecular interactions in solutions
of organic derivatives of penta-and hexacoordinated silicon, germanium, and tin containing amidomethyl, lactamomethyl, and
related bidentate ligands are surveyed.
For the series of works “Dynamic stereochemistry of hypervalent compounds of silicon, germanium, and tin,” the author was
awarded the Academia Europea Prize for young scientists from CIS in 1996.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1912–1934. November, 1997. 相似文献
169.
The solubility of argon in pure liquid water was measured at ca. 100 kPa and from 2 to 40°C using an analytical method characterized by an imprecision of about ±0.05%. From the experimental results, Henry fugacities H
2,1
(T,P
s,1
) (also known as Henry's Law constants or Henry coefficients) at the vapor pressure P
s,1
of water as well as Ostwald coefficients L
2,1
at infinite dilution were obtained. Measurements were made at roughly 0.5°C and/or 1° intervals between 2 and 8°C (region I), and at 5°C intervals above 10°C (region II). A difference plot lnH
2,1
/T suggests an unusual temperature dependence in region I, i.e., between 2 and 8°C. Because of this, the data were treated separately in two parts corresponding to these two regions. Our results are compared with the recent high-precision data of Krause and Benson (Henry fugacities), and with calorimetrically determined quantities (enthalpies and heat capacities of solution). Finally, experimental results are compared with values calculated via scaled particle theory.Communicated in part at the 2nd International Symposium on Solubility Phenomena in Newark, New Jersey, August 12–15, 1986, and at the 4th ISSP in Troy, New York, July 20–August 3, 1990. 相似文献
170.
The title sterically crowded di-9-anthrylethyne derivative with 3,5-iPr2-phenyl groups at 1-position showed a barrier to rotation about the acetylenic axis of 18.0 kcal mol−1 based on a dynamic NMR study, which is an extremely high value for acyclic diarylethynes. The mechanism of the dynamic stereochemistry and the substituent effect on the rotational barrier are discussed. 相似文献