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81.
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
82.
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
83.
The high pressure behaviour of InI is studied by DFT‐calculations and compared with experimental data. The existence of a 5s2 electron pair in In+ represents an unfavourable bonding situation for high symmetry structures because of effective closed shell repulsion. Since cations with a ns2 electron pair are highly polarizable and the electronic situation is more favourable in the low symmetry structure InI prefers a TlI‐type structure at ambient pressure. A pressure induced transition to the more densely packed high symmetry CsCl‐type structure takes place at about 19 GPa according to our calculations. At ambient pressure the interactions are predominantly ionic. However with increasing pressure the distances between In+ cations in the TlI‐type structure diminish drastically, mainly due to the changing space requirement of the lone electron pair. Apart from ionic interactions further bonding interactions between the In+ cations occur. At elevated pressure the electron localization function (ELF) as well as the band structure diagrams suggest metallic bonding between the In+ within the zigzag chain, i. e. increasing bonding interactions between the In+ cations due to the electron pair and its s‐p‐mixing. At ambient pressure In‐In interactions are rather weak and the space requirement of the lone electron pair mainly determines the characteristic arrangement of the ions. At elevated pressure the In‐In interactions become stronger and stabilise themselves additionally the specific structural arrangement. 相似文献
84.
Electrical conductance measurements are reported for aqueous NaCl solutions at 25°C as a function of concentration up to 0.02M and pressures up to 2000 atm. The data were analyzed with the Fuoss-Hsia-Fernandez-Prini (FHFP) equation. The standard error of fit, , varies from 0.04 at 1 atm to 0.10 at 2000 atm. The increase of with pressure arises from increasing non-randomness in the distribution of errors about the FHFP equation suggesting that modifications in the theory are necessary. The pressure dependence of O for NaCl and KCl is nearly identical.Contribution of the Scripps Institution of Oceanography, New Series 相似文献
85.
Takeshi SasakiHirotsugu Takizawa Kyota UhedaTakahiro Yamashita Tadashi Endo 《Journal of solid state chemistry》2002,166(1):164-170
Two new high-pressure phases of binary boron-sulfur compounds, B2S3-II and B2S3-III, were synthesized at 3-6.2 GPa. A single crystal of B2S3-III was grown and the structure was determined (tetragonal, space group I41/a, a=16.086(2) Å, c=30.488(4) Å; V=7888(1) Å3, Z=100, R=3.0% and Rw=2.8% for 3047 observed data [I>3.00σ(I)]. The structure of B2S3-III consists of two kinds of macrotetrahedra built up from 20 and 34 BS4-tetrahedra. These macrotetrahedra connect each other to form an interpenetrating zincblende-type structure by sharing BS4-tetrahedra at the corners of those. B2S3-III is anticipated having a rather disordered structure. From the UV-Vis diffuse reflectance spectrum, the optical band gap of B2S3-III was estimated to be 3.7 eV. 相似文献
86.
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
87.
Dielectric studies have been performed at elevated pressures on two compounds of a homologous series possessing a strongly polar terminal group and three phenyl rings in their molecular structure. This is the first high pressure dielectric study on such systems that exhibit a monolayer smectic A phase. Also notable is the fact that these compounds show a dual frequency response, a promising feature for fast liquid crystal display devices. The low frequency relaxation recorded in the nematic and smectic A phases is attributed to the reorientation of the molecules about the short axis. The temperature and pressure dependence of the relaxation frequency of this mode as well as the involved activation parameters are discussed. At a given relative temperature the relaxation frequency decreases as the pressure is increased. However, the parameter that characterizes the temperature dependences of the relaxation frequency, viz., the activation enthalpy, has a very weak dependence on pressure. In contrast, the activation volume shows a linear decrease with temperature. 相似文献
88.
Charles S. Oakes John M. Simonson Robert J. Bodnar 《Journal of solution chemistry》1995,24(9):897-916
Relative densities of CaCl
2
(aq) with 0.22ml(mol-kg–1)6.150 were measured with vibrating- tube densimeters between 25 and 250°C and near 70 and 400 bars. Apparent molar volumes V calculated from the measured density differences were represented with the Pitzer ioninteraction treatment, with appropriate expressions chosen for the temperature and pressure dependence of the virial coefficients of the model. It was found that the partial molar volume at infinite dilution V
o
, and the second and third virial coefficients B
V
and C
V
, were necessary to represent V near the estimated experimental uncertainty. The ionic-strength dependent (1)v term in the B
V
coefficient was included in the fit. The representation for V has been integrated with respect to pressure to establish the pressure dependence of excess free energies over the temperature range studied. The volumetric data indicate that the logarithm of the mean ionic activity coefficient, ln ±(CaCl
2
), increases by a maximum of 0.3 at 400 bars, 250°C, and 6 mol-kg–1 as compared with its value at saturation pressure. 相似文献
89.
Ju-Chun Huang Chien Hong Cheng Shyang Roeng Sheen Zhi Ling Lee Chien Ming Lei Maw Kuen Wu 《中国化学会会志》1996,43(2):139-143
The synthesis of bulk Y2Ba4Cu7O15-δ superconductor at atmospheric oxygen pressure via solid state sintering is reported. Temperature ranging from 860 to 890 °C as well as time interval over 2 to 15 days were used to investigate the formation of the Y2Ba4Cu7O15-δ phase. A time-temperature profile characterizing the conditions for the preparation of Y2Ba4Cu7O15-δ phase suggests the optimal condition to be sintering at 890 °C for over 10 days. Detailed results of X-ray diffraction, electrical resistivity, iodometric titration and magnetization measurements are described. 相似文献
90.
气相渗透法广泛用于测定齐聚物和低分子量聚合物的数均分子量(M_n)。分析文献数据和本文的实验证明,仪器常数K值随溶质的分子量而变化。本文提出了一种新的说明 VPO法 K值依赖于溶质分子量的模式,根据此模式,可清楚地说明这种依赖关系。 相似文献