Imide-siloxane block copolymer/silica hybrid membranes: preparation, characterization and gas separation properties

Imide-siloxane block copolymer/silica hybrid membranes with covalent bonds were prepared via sol–gel reaction. The structural informations of these hybrid membranes were obtained by using Fourier transform-infrared spectrometry (FT-IR), ²⁹Si nuclear magnetic resonance (²⁹Si NMR), XPS and thermogravimetric analysis (TGA). The gas separation properties of the hybrid membranes were also investigated in terms of organosiloxane (PDMS) or silica content at various temperatures. In the hybrids, the addition of PDMS phase increased the permeabilities of gases such as He, CO₂, O₂, and N₂, indicating that the gas transport occurred mainly through rubbery organic matrix. Meanwhile, the PDMS phase contributed the decreased gas selectivities to nitrogen but the reduction in selectivities was very small in comparison with other siloxane containing polymeric membranes. This might be due to the restriction of chain mobility by the existence of inorganic component such as silica network in the hybrids. Additionally, the increase of silica content in these hybrid membranes considerably retarded the falling-off of gas selectivity at elevated temperature. The increase of silica content in hybrid membranes resulted in well-formed silica networks and hence these inorganic components restricted the plasticization of organic matrix by the thermal segmental motion of organic components, leading to preventing the large decrease of the gas selectivity.     

用DCC/DMAP合成N-苄氧羰基氨基酸薄荷酯

以乙腈为溶剂, 用DCC/DMAP偶合法合成了5个N-苄氧羰基氨基酸薄荷酯, 产率90%～94%. 起始原料氨基酸包括: 甘氨酸, DL-蛋氨酸, β-丙氨酸, L-缬氨酸和L-脯氨酸. 给出了目标产物的氢谱、碳谱、红外光谱、质谱、高分辨质谱和元素分析数据.     

Quantitative analysis of docetaxel in human plasma using liquid chromatography coupled with tandem mass spectrometry

An assay for the quantitative determination of docetaxel in human plasma is described. Docetaxel was extracted from the matrix using liquid-liquid extraction with ter-butylmethylether, followed by high-performance liquid chromatographic analysis using an alkaline eluent. Paclitaxel was used as internal standard. Positive ionization electrospray tandem mass spectrometry was performed for selective and sensitive detection. The method was validated according to the FDA guidelines on bioanalytical method validation. The validated range for docetaxel was from 0.25--1000 ng/mL using 200 microL plasma aliquots. The method requires only a limited volume (200 microL) of human plasma and the method can be applied in studies requiring a low lower limit of quantitation of 0.25 ng/mL. The assay was applied successfully in several clinical and pharmacological studies with docetaxel.     

New selective O-debenzylation of phenol with Mg/MeOH

Carboxylate-benzyl and nitro-benzyl groups used in phenols protection were selectively debenzylated with 3-25 equiv of Mg in methanol at room temperature. Good yields of the desired phenols were obtained within 3-10 h from a wide variety of O-(carboxylate-benzyl)- or O-(nitro-benzyl)-phenols. Selective O-debenzylation was possible in the presence of O-(carboxylate-benzyl)- or O-(nitro-benzyl)-phenols with Mg/MeOH.     

HIPS／PP熔融反应共混及其动态力学性质

研究了高抗冲聚苯乙烯（HIPS）／聚丙烯（PP）共混物在过氧化二异丙苯（DCP）存在下的熔融反应过程及其动态力学性质．HIPS在DCP存在下以聚苯乙烯（PS）的降解为主，伴随着聚丁二烯（PB）的交联和接枝，PP在DCP存在下以降解为主，HIPS／PP在DCP存在下以PP同HIPS的反应接枝为主，这种原位生成的增容剂显著地改善了HIPS／PP两组份间的相容性，其分子运动特征较前两者发生明显变化，PS的Tg下降，PB和PP的Tg升高．     

H2O−D2O solvent isotope effect in the volume behavior of some high-charge high-size electrolytes

The apparent molar volumes V of KCl, BaCl₂, K₂SO₄, LaCl₃, Co(en)₃Cl₃ [Tris(ethylenediamine)cobalt(III) chloride], K₃Co(CN)₆, K₃Fe(CN)₆, K₄Fe(CN)₆, and Ba₃[Co(CN)₆]₂ have been determined at 25°C in both light and heavy water. The V values in D₂O are systematically lower and increase more rapidly with salt concentration than the V in H₂O. The volume of transfer from H₂O to D₂O as well as the partial molar volume at infinite dilution in both solvents have also been calculated. These results together with literature values for other electrolytes were used to estimate both of these quantities for D₂O solutions of individual ions. The predictions of ion hydration models and ion-ion interactions are compared with experimental observations.     

Analysis of nitro-PAHs in diesel exhaust particulate extracts with multicolumn HPLC

Summary A method is described for the determination of nitrated polynuclear aromatic hydrocarbons (nitro-PAHs), in particular 1-nitropyrene, in diesel particulate extracts. The method employs a multidimensional HPLC (column switching) technique with final on-line peak identification by UV-VIS spectral comparison with standards. To achieve exceptional chromatographic selectivity for nitro-PAHs, a new pyrene butyric acid amide phase has been prepared which is capable of forming donor-acceptor complexes with them. With this technique it is possible to confirm the presence of 1-nitropyrene in the range 3–100 ng/mg on filter-collected diesel soot. Its utility was demonstrated with diesel exhaust extracts spiked with varying levels of 1-nitropyrene and proved to be highly selective.Parts of this work have been presented at the 15th International Symposium on Chromatography, Nürnberg, October 1984.Dedicated to Prof. J. F. K. Huber at the occasion of his 60th birthday.     

Peritektische Zersetzung von YBa2Cu3O7−x

During the heating of YBCO a peritectic reaction takes place at 1020C, which can be described by: 2YBa₂Cu₃O_7–xY₂BaCuO₅+L+(1-2x)/2O₂ (1) whereL = 3BaCuO₂ +2CuO is a fluid with limited amount of yttrium.It has been reported, that many parameters can influence the reaction. From one side not only the starting size of grains but also the heating rate have an influence on the resulting Y₂BaCuO₅-phase. From the other side, there is a change of the peritectical temperature caused by changing of the partial pressure of O₂ and the presence of parasitic phase.From general kinetic consideration one can draw the conclusion, that different mechanisms (nucleation, phase-boundary reaction and diffusion) can control the reaction.Using DTA/TG measurements, the peritectic reaction has been examined. Classical kinetic methods (Kissinger and Friedman) has been used. The Friedman method has given the dependence of the activation energy from reaction degree. This suggests many steps reactions. The dependence of the DTA-peaks from the heat rate suggest a parallel steps of reaction. This assumption can be motivated by evaluation of free O₂, one solid and liquid phase formation. Amount of this phases depends on the heating rate. Additionally X-ray and microscopic methods has been used. In this way was shown, that the perovskit structure is stable up to peritectical temperature and than is dramatically destroyed. From microscopic observations has been got information about shape and size of solid phase and it's creation as a function of temperature, time and starting grain size.

Die Arbeit wurde BMBF gefördert und durch Land NRW unterschtützt.     

Hydration behaviour of a lime-pozzolan cement containing MSW incinerator fly ash

A lime-pozzolan cement was used to make pastes containing different quantities of MSW fly ash. After setting, the pastes were cured in water at room temperature from 1 h to 260 days. The hydration characteristics and the nature of the hydration products of the various pastes were studied by simultaneous TG/DSC thermal analysis and X-ray diffractometry. The MSW fly ash was found to induce a slowing of the hydration process in lime-pozzolan pastes, and after some days an evident acceleration of hydration reactions occurred. Sulphate and chloride in the MSW fly ash yield hydration products forming a cementitious matrix.The author is grateful to D. Calabrese for assistance with the thermal and XRD analyses.     

Effect of cooperativity on the O-H stretching force constant in associated water species

CNDO/force calculations have been employed to calculate the O-H stretching force constants for various structures of associated water species such as water-dimethylether, water-acetonitrile, water-lithium fluoride, linear and cyclic water polymers. The variation in the O-H stretching force constant in A_m… O-H… D_n species where A_m and D_n represent, respectively,m number of electron-acceptor andn number of electron-donor molecules, is explained on the basis of the cooperativity effect. With increasing electron-acceptor power of A and electron-donor power of D, the hydrogen-bonded O-H stretching force constant is significantly reduced. The results obtained in these studies are in general agreement with experimental observations reported earlier.