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331.
Stanislaw Miertus Vladimir Frecer Emo Chiellini Federica Chiellini Roberto Solaro Jacopo Tomasi 《Journal of inclusion phenomena and macrocyclic chemistry》1998,32(1):23-46
Using a simple molecular mechanics approach interaction energy profiles of simple probes (C, CH4, C6H6, H2O, NH4
+, and HCOO-) passing through the center of the -CD ring cavity along the main molecular symmetry axis were first evaluated. Molecular Electrostatic Potential (MEP) values along the same path were also evaluated. The effect of the flexibility of the host -CD molecule together with solute-solvent (H2O) interactions have been represented by averaging structures of MD calculations for -CD alone and -CD surrounded by 133 H2O molecules. The effect of various substitutions of -CD has also been evaluated. Small symmetric hydrophobic probes (such as C, CH4, C6H6) are predicted to form stable inclusion complexes with non-substituted and substituted -CDs, the probe position typically being near the cavity center. The stability of the inclusion complexes will increase with increasing size and aliphatic character of the probe. Small polar and charged probes (such as H2O, NH4
+, HCOO-) are predicted to prefer the interaction with the solvent (water) in the bulk phase rather than the formation of inclusion complexes with non-substituted and substituted -CDs. Guest–host interactions in the stable inclusion complexes with hydrophobic probes are almost entirely dominated by dispersion interactions. The MEP reaches magnitudes close to zero in the center of the non-substituted -CD ring cavity and in most of the studied substituted -CDs and shows maximum positive or negative values outside of the cavity, near the ring faces. Substitution of -CD by neutral substituents leads to enhanced binding of hydrophobic probes and significant changes in the MEP profile along the -CD symmetry axis. 相似文献
332.
Stanislaw Zieliński Lechosław Łomozik Anna Wojciechowska 《Monatshefte für Chemie / Chemical Monthly》1982,113(3):323-330
The formation and the mode of coordination of rare earth (Y, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Lu) complexes with proline and hydroxyproline have been investigated by1H and13C NMR spectral techniques. It has been established that the nitrogen and the carboxyl group of the ligands are involved in complexation, and that the OH– group of hydroxyproline does not participate in coordination.
1H und13C NMR Untersuchungen an Lanthanid-Komplexen mit Prolin und Hydroxyprolin
Zusammenfassung Die Bildung und die Koordination von seltenen Erden (Y, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Lu) in Komplexen mit Prolin und Hydroxyprolin wurden mit Hilfe von1H- und13C-NMR-Spektroskopie untersucht. Es wurde festgestellt, daß in den Komplexen der Stickstoff und der Carboxylsauerstoff der Liganden koordinieren. Die OH–-Gruppe von Hydroxyprolin nimmt keinen Anteil an der Koordinierung.相似文献
333.
13C cross-polarization magic angle spinning (CP/MAS) NMR data for 2,2,5,7,8-pentamethylchroman-6-ol (2), 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (Trolox c) (3) and its acetate (4), 2-methoxy-2,2,5,7,8-pentamethylchroman-6-ol (5), 2-hydroxy-2,2,5,7,8-pentamethylchroman-6-ol (6) and 2,2,5,7,8-pentamethylchroman (7) are reported. A deshielding of 7.7 ppm for the carboxylic carbon was observed in solid Trolox due to formation of intermolecular hydrogen bonds within cyclic dimers. Such crystal packing permits effective cross-polarization and fast relaxation (short T1rho(H)). The impact of the proton concentration on the CP dynamics is reflected by the longer T(CP) and T1rhoH for Trolox-d2 (deuterated at mobile proton sites). The calculated GIAO RHF shielding constants are sensitive to intramolecular effects: rotation around the C-6-O bond (changes of sigma up to 8 ppm) and conformation at C-2. 相似文献
334.
Jamisz Jurczak Tomasz Kozluk Stanislaw Filipek Conrad Hans Eugster 《Helvetica chimica acta》1982,65(3):1021-1024
As an active diene (more active than furan itself), 3,4-dimethoxyfuran ( 1 ) affords with many dienophiles the respective cycloadducts in a high yield [2]. It has recently been found that under thermal conditions 1 easily reacts with maleic anhydride and its monomethyl derivative, but not with dimethylmaleic anhydride ( 2 ) [3]. This is probably due to steric hindrance resulting from the location of two methyl groups on the double bond of the dienophile. Since all Diels-Alder reactions in particular those with steric hindrance are pressure-sensitive [4]. we resolved to perform the title reaction under conditions of static high pressure. 相似文献
335.
γγγ-Trifluorocarbonyl compounds are easily obtained in a good yield by introduction of the 1,1,1-trifluoroethyl moiety (CF3-CH2-) on the -methylene group of a ketone. 相似文献
336.
Wieslaw Wiczk Leszek Łankiewicz Cezary Czaplewski Stanislaw Oldziej Krystyna Stachowiak Alicja Michniewicz Beata Micewicz Adam Liwo 《Journal of fluorescence》1997,7(4):257-266
Synthesis and photophysical studies of (O-methyl)--tyrosine (-tyrosine; an analogue of tyrosine, in which the amino group is moved from the - to the -carbon, closer to the phenol ring) and its derivatives with a blocked amino and/or carboxyl group were performed to explain the nature of the fluorescence of tyrosine derived analogues. All -tyrosine derivatives, except Ac-Tyr(Me), displayed the monoexponential fluorescence decay. The biexponential fluorescence decay observed for Ac-Tyr(Me) is assumed to be the result of the presence of two low-energy conformations (extended and with an intramolecular hydrogen bond). Higher quenching of the fluorescence of -tyrosine derivatives by the N-acetyl group than by the N-methylamide group moved farther was found, contrary to the data found for the respective derivatives of natural tyrosine. The obtained photophysical data are discussed with theoretical calculations (AMBER, AM1) on the basis of the rotamer model. 相似文献
337.
338.
339.
A negative chlorine ion source has been designed and constructed. The source utilizes direct surface ionization of chloromethane gas on a hot metal filament. Four different alloys for the filament material were tested: W99Th1, W75Re25, Hf97.5Zr2.5 and Mo52.5Re47.5. We conclude that the best filament material is the MoRe alloy, for which the signal‐to‐noise ratio is optimal. The ion source is used for chlorine isotope ratio measurements with higher precision and sensitivity than the positive ionization source used previously. Inasmuch as only negative ions of the two isotopes of interest are observed, no corrections to the measured isotope ratio are necessary, and less rigously purified samples may be analyzed. The negative ion currents are considerably larger than positive ion currents obtained with an electron ionization source. This implies higher analytical precision (typically 0.005 permil) and sensitivity. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
340.
Ró?a Sieniawska Pawel ?niady Stanislaw ?ukowski 《Journal of sound and vibration》2009,319(1-2):355-365
An approach to the flexural stiffness identification of a linear structure is proposed. The idea of the presented approach is to transform the dynamical problem into a static one by integrating the input and output signals. The output signal is the structure displacement due to different kinds of loads such as a pulse acting at a given point, moving a load of deterministic or random type. The obtained solution for the one-point force can be easily generalized to a set of point forces, which can be a model of the pressure of vehicle axes. The presented method can be applied to the identification of structure parameters of bridges. It allows also to take into account some stochastic disturbances following the movement of vehicles through the pavement roughness. 相似文献