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121.
Summary The capillary gas chromatographic retention behavior of -pinene and tricyclene has been investigated on stationary phases of different polarities. On all but one of the columns employed, tricyclene eluted before -pinene; only permethylated -cyclodextrins dissolved in moderately polar polisiloxanes gave a reversed elution order. The intermolecular interactions which caused the unexpected retention behavior were investigated in detail, applying methods of computer simulation. To achieve this, we have developed a calculation algorithm on the basis of molecular mechanical optimizations and programmed it in a macro. This makes it possible to systematically investigate a given configuration space in which all the possible interactions can take place. It was shown that permethylated -cyclodextrin as host molecule for both guest molecules offers an optimum cavity size. As a result the number of energetically favorable contacts between host and guest molecules as well as the strength of the interactions in this stationary phase were larger. As a consequence the elution order, normally only influenced by the vapor pressure of the compounds at a given temperature, was changed. Nonspecific interactions played an especially important role for these kinds of substances. 相似文献
122.
The reaction of B2H4 with acetylene has been studied by the MNDO method. It is shown that the reaction is exothermic and proceeds in two steps. The first step is the formation of a three-center -complex and this is the rate-determining step of the reaction. The second step is the rearrangement of the -complex to the product and this step requires a very small amount of activation energy. The activation barrier for the diboration reaction is 12.8 kcal/mol.The proposed mechanism is significantly different from those proposed earlier and explains all experimental data relating to this reaction. 相似文献
123.
Summary The -carbonyl substituted vinylphosphonates6–9 were synthesized from the -dicarbonyl compounds2–5 and the methylenbisphosphonate1 by a Horner-Emmons reaction in different yields.
Synthese von Phosphonocarbonylverbindungen durch Horner-Emmons-Reaktion von Methylenbisphosphonsäuretetraethylester
Zusammenfassung Es wurden die -carbonylsubstituierten Vinylphosphonate6–9 mittels Horner-Emmons-Reaktion aus den -Dicarbonylverbindungen2–5 und Methylenbisphosphonat1 in verschiedenen Ausbeuten hergestellt.相似文献
124.
M. M. Krayushkin M. A. Kalik L. G. Vorontsova E. Yu. Zvezdina M. G. Kurella 《Russian Chemical Bulletin》1993,42(7):1204-1208
9-Methyl-3,3a,4,5-tetrahydro-6H-thieno[2,3-b]thiocino[4,5-c]isoxazole and 9-hydroxyimino-2-methyl-7-methylene-6, 7,8,9-tetrahydro-5H-thieno[2,3-b]thiocine have been prepared for the first time by the oxidation of 2--alkenylthio-3-thiophenecarbaldoximes with NaOCl. X-ray structural investigations of thieno[2,3-b]thiocine and 2-homomethallylthio-5-methyl-3-thiophenecarbaldoxime have been carried out.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1262–1266, July, 1993. 相似文献
125.
Suzdalev I. P. Buravtsev V. N. Maksimov Yu. V. Zharov A. A. Imshennik V. K. Novichikhin S. V. Matveev V. V. 《Russian Chemical Bulletin》2003,52(9):1950-1958
Magnetic phase transitions of the first and second order were revealed by Mössbauer spectroscopy in nanosystems of - and -ferric oxides and metallic europium subjected to shear stress (240°) under high pressure (20 kbar). For - and -ferric oxide nanoclusters, the Curie (Neel) points decreased to 300 K, whereas for nanostructured europium the Neel point increased from 90 to 100 K. The thermodynamic model of magnetic phase transitions predicting a change in the character of magnetic phase transitions and a decrease (increase) in the critical Neel (Curie) points in nanoclusters was developed. The type of magnetic phase transitions and the change in the critical points were caused by defects in nanoclusters, whose maximum concentration was observed for the clusters with the 20—50 nm size range. 相似文献
126.
127.
建立了反相高效液相色谱法监测人口服地尔硫艹卓缓释片后血药浓度。血样用正己烷-氯仿-异丙醇混合溶剂(60405)提取后,以C18化学键合硅胶为固定相,甲醇-水-三乙胺为流动相,安定为内标,在239nm波长处定量检测。血药浓度在15~300μg/L范围内线性关系良好,最低检测浓度为3μg/L。批内(n=7)及批间(n=5)测定相对标准偏差分别小于6.8%和8.4%,回收率为91%~104%。监测了8名健康人口服盐酸地尔硫艹卓缓释片后的不同时间的血药浓度变化,计算了有关的药代动力学参数。 相似文献
128.
R. M. Zolotar' A. I. Bykhovets S. N. Sokolov N. V. Kovganko 《Chemistry of Natural Compounds》2002,38(1):66-69
The toxicity of steroids 1-11 for colorado beetle (Leptinotarsa decemlineata Say.) larvae was studied by contact-intestinal treatment. Active insect-growth regulators were found among the studied compounds. 相似文献
129.
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
130.