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131.
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
132.
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
133.
Josinira A. Amorim Osvaldo Chiavone-Filho Márcio L.L. Paredes Krishnaswamy Rajagopal 《Fluid Phase Equilibria》2007
High-pressure density data for cyclohexane + n-hexadecane mixtures at a wide temperature range was modeled with several classical equations of state (EOS) and correlative models. A modification for softening the co-volume and another for a volume scaling of the Peng–Robinson EOS (VS-PR) were proposed. The VS-PR model is able to correlate the pure component experimental data employing only five adjustable parameters, with root-mean-square deviation (RMSD) between calculated and experimental densities essentially within the experimental error. This result is superior to widely used approaches, i.e., a six parameter Tait model and six parameter volume translations (temperature and pressure dependent) for Peng–Robinson and Patel–Teja EOS. The VS-PR model also represents well the isobaric thermal expansion and the isothermal compressibility coefficients of the pure cyclohexane, a small naphthenic substance as well as a long chain n-alkane hydrocarbon, n-hexadecane. When modeling the mixture data, the use of VS-PR model of pure components along with the Redlich–Kister expansion, truncated at the first term, the density was correlated within a RMSD only 60% greater than the experimental error. The proposed model is able to accurately represent all the tested mixture data with a relatively small number of parameters. 相似文献
134.
I. Gascón S. Martín P. Cea M. C. López F. M. Royo 《Journal of solution chemistry》2002,31(11):905-915
Densities and speeds of sound of the binary mixtures 1,3-dioxolane + 1-butanol, 1,3-dioxolane + 2-butanol, 1,4-dioxane + 1-butanol, and 1,4-dioxane + 2-butanol have been measured at 25 and 40°C. The excess molar volumes and excess isentropic compressibility coefficients were calculated from experimental data and fitted to a Redlich–Kister polynomial function. Results were analyzed in terms of molecular interactions and compared with literature data. 相似文献
135.
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
136.
X. N. Yang 《Journal of solution chemistry》1998,27(3):261-272
A diaphragm cell has been used to measure mutual diffusion coefficients at 25°C for four binary nonelectrolyte mixtures: ethylbenzene + n-hexane, carbon tetrachloride + ethylbenzene, cyclohexane + p-xylene, and 1,2-dichloroethane + cyclohexane. A free-volume predictive approach for binary mutual diffusion coefficients was developed and tested. Only infinite dilution diffusion coefficients, some readily available pure substance data, and UNIFAC group contribution parameters are used in the model. No binary equilibrium thermodynamic information is required. For 73 binary systems with an overall average absolute deviation of 5.2%, it has been shown that the developed method is better than two commonly available reference methods for the prediction of liquid diffusion coefficients. 相似文献
137.
W. Kunz J. Barthel L. Klein T. Cartailler P. Turq B. Reindl 《Journal of solution chemistry》1991,20(9):875-891
A variety of methods has been used for the study of lithium bromide solutions in acetonitrile yielding by their combination reliable information on different levels of approximation. Osmotic coefficients based on precise vapor pressure measurements are reproduced by CM (chemical model) and HNC (hypernetted chain) calculations and by BD (brownian dynamics) simulations. The results of neutron scattering experiments are treated with the help of HNC and BD methods. Hartree-Fock calculations on isolated LiBr pairs and solvated lithium ions yield reliable particle distances and reveal the geometry of the lithium solvation sphere. 相似文献
138.
对130℃下1,3 二烯基 1,1,3,3 四甲基二硅氧烷(DVDS)/苯乙烯(St)的溶液环化共聚合动力学进行了研究.根据低转化率(<10%)的共聚物组成及环状结构比例,通过参数估计方法,求得环化率与竞聚率,分别为r1=0102、r2=348、rc=00210、Kc=381mol/L、K′c=0389mol/L,同时得到它们95%置信概率的联合置信区间及其交互影响的联合置信区间.表明DVDS的反应活性较St低,其非环状结构自由基具有较强的分子内环化反应能力;环的位阻效应使环状结构DVDS自由基的活性低于其非环状结构自由基. 相似文献
139.
The surface wave produced plasma belongs to a class of RF and microwave induced plasmas. It results from the propagation of an electromagnetic wave which uses the plasma column it sustains and the plasma tube as its sole propagating media. This type of plasma offers several advantages compared to the positive column plasma of dc discharges or to other RF and microwave produced plasmas. Surface wave plasmas require no internal electrodes, and they can be applied over an extremely broad range of wave frequencies (27 MHz to 10 GHz demonstrated) and gas pressures (about 10–4 Torr to a few times the atmospheric pressures). Using the surface wave plasma technique, a large variety of plasma column diameters have been created (0.5–150 mm demonstrated) and no limitation on plasma column length (column up to 6 m long demonstrated) has been found. The surface wave produced plasma is used in elemental analysis and to sustain emission in lasing media. This article is intended as a guide for potential users of surface wave plasmas in the field of plasma processing and plasma chemistry. 相似文献
140.
I. M. Krukovskii M. S. Molchanova A. V. Evtushenko V. A. Shlyapochnikov 《Russian Chemical Bulletin》1998,47(7):1266-1273
The ratio between the numbers of structural formulas of C,H,N,O-containing energetic compounds belonging to the classes of
fuels (low values of the oxygen coefficientA), explosives (mediumA), and oxidants (highA values) was studied by a computer generation procedure. The number of the theoretically possible structural formulas was
found to decrease rapidly on going from fuels to explosives and then to oxidants; this observation agrees with the data on
the numbers of various energetic compounds currently used and proposed. The strategy of the search for new compounds with
the specified properties is described in brief, and its applicability to the search for explosives and oxidants with a small
(up to 12) number of atoms in a molecule is evaluated.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1304–1310, July, 1998. 相似文献