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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
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Photocatalytic Systems. XLIV. On the Intervalence Charge Transfer Behaviour of Ion Pairs of Octacyanomolybdate [Mo(CN)8]4? ions are forming coloured ion pairs with FeIII, CuII, UVIO2, and VIVO, the long-wavelength absorption band of which could be assigned to an intervalence charge-transfer transition. From the solvent dependence of the IT band, interionic distances could be estimated. 相似文献
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U. Steinike L. I. Barsova T. K. Jurik U. Kretchmar H. -P. Hennig U. Bol'mann 《Russian Chemical Bulletin》1990,39(7):1321-1324
Mechanical treatment of hydrargillite Al(OH)3 in a vibrational grinder and in a ball-mill grinder increases the dispersion, the specific surface area, and the unit-cell constants. An x-ray amorphous phase forms. Differences in the nature and in the concentration of paramagnetic centers arise on irradiation (77 K) of the mechanically treated samples. Anion vacancies and oxygen ions with disrupted short-range order appear in the mechanically treated samples. Their concentration increases with increased time of mechanical treatment. Pulsed thermal treatment of hydrargillite forms the Al2O3-Al(OH)3 system and anneals the mechanically induced defects.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1463–1467, July, 1990. 相似文献
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Philippe Hennig Eric Raimbaud Christophe Thurieau Jean-Paul Volland André Michel Jean-Luc Fauchère 《Journal of computer-aided molecular design》1996,10(1):83-86
Summary The conformation in dimethylsulfoxide of the somatostatin derivative angiopeptin and of three disulfide-free analogs was estimated by two-dimensional nuclear magnetic resonance spectroscopy at room temperature. The resulting 3D molecular graphics were compared and shown to reflect the observed differences in the inhibition of restenosis after rat aorta balloon injury by these octapeptide inhibitors. Angiopeptin and its active analog 2 displayed a relatively rigid conformation of the cyclic hexapeptide backbone due to the presence of two well-defined hydrogen bonds, further stabilized by a third hydrogen bond outside the ring. No such constraints were detected for the two biologically inactive analogs, which, compared to 2, had a two-atom longer or shorter hexapeptide ring. The well-defined structure of compound 2 may serve as an improved pharmacophore for this new class of drugs. 相似文献
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Summary Retention indices of 6 selected hydroxy compounds (aliphatic and bicyclic alcohols, phenols) were determined on 2 HP-5 fused-silica, capillary columns with different film thicknesses (0.11 m and 0.33 m) at 8 different oven temperatures between 80 and 150°C. For some substances the I-T plot was found to show a minimum which cannot be explained by the common retention-index temperature-dependence in gas-liquid chromatography. This result is discussed in terms of adsorption at the liquid-solid interface of the capillary column. 相似文献
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Lothar Hennig Mario Alva-Astudillo Gerhard Mann Thomas Kappe 《Monatshefte für Chemie / Chemical Monthly》1992,123(6-7):571-579
Summary Treatment of substituted benzylidene anilines1 a – df with cyclic CH-acidic compounds2a–m in ethanol at room temperature yields in additon/elimination reactions the corresponding arylidene derivatives4 and the 2:1 adducts5. The addition products3, which are formed as intermediates, could not be isolated in any case. The donor/acceptor effect of the substituents on the benzylidene moiety influences to a significant extent the reactivity towards the azomethine carbon.
Neue Aspekte der Reaktion von Azomethinen mit cyclischen CH-aciden Verbindungen
Zusammenfassung Bei der Umsetzung der substituierten Benzylidenaniline1 a – f mit den cyclischen CH-aciden Verbindungen2 a – m in Ethanol bei Raumtemperatur erhält man in Additions/Eliminierungsreaktionen die Arylidenderivate4 und die 2:1-Addukte5. Die als Intermediat gebildeten Additionsprodukte3 konnten in keinem Fall isoliert werden. Die Donor-bzw. Acceptorwirkung der Substituenten am Benzylidenrest beeinflußt maßgebend die Reaktivität am Azomethinkohlenstoff.相似文献