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191.
García-Herrero A Montero E Muñoz JL Espinosa JF Vián A García JL Asensio JL Cañada FJ Jiménez-Barbero J 《Journal of the American Chemical Society》2002,124(17):4804-4810
We show that the conformational features of the molecular complexes of E. coli beta-galactosidase and O-glycosides may differ from those formed with closely related compounds in their chemical nature, such as C- and S-glycosyl analogues. In the particular case presented here, NMR and ab initio quantum mechanical results show that the 3D-shapes of the ligand/inhibitor within the enzyme binding site depend on the chemical nature of the compounds. In fact, they depend on the relative size of the stereoelectronic barriers for chair deformation or for rotation around Phi glycosidic linkage. 相似文献
192.
Insight is gained into about the processes governing cavitational activity and acoustic streaming induced by high frequency (500 kHz) ultrasound by the use of microelectrodes with short time resolution electrochemical equipment to allow monitoring of the activity of single cavitating bubbles. Current transients are interpreted as showing the flux of solution towards the electrode surface due to microstreaming. In order to explain the current amplitude, a simplified model is produced. Important parameters such as bubble size and shape on the surface as well as the boundary layer thickness for microstreaming are taken into account. This model leads to the amplitude of the oscillations of the cavitating bubble. Introducing realistic bubble sizes, this amplitude is found to be in the order of 1 micron. The conclusions arising from this work allow a further interpretation of previous observations at millimeter scale electrodes. 相似文献
193.
Hernandez J Solla-Gullón J Herrero E Aldaz A Feliu JM 《The journal of physical chemistry. B》2005,109(26):12651-12654
The surface structure of gold nanorods has been determined by studying the behavior of electrochemical reactions sensitive to the structure and compared to that obtained by other structure characterization techniques. Lead underpotential deposition (UPD) reveals that the surface of the nanorods is composed by (111) and (110) domains, while (100) domains are practically absent from the surface. In the case of the oxygen reduction reaction, the formation of hydrogen peroxide as a final product of the reaction in the whole potential range also indicates that (100) domains are absent on the surface of the nanoparticles, corroborating the previous result. These results are compared with other surface structure information provided by other techniques. 相似文献
194.
We provide numerically exact photoexcitation cross sections of rubidium Rydberg states in crossed, static electric, and magnetic fields, in quantitative agreement with recent experimental results. Their spectral backbone underpins a clear transition towards the Ericson regime, associated with a universal, fluctuating behavior of the cross section of strongly coupled, fragmenting quantum systems. 相似文献
195.
Intermodal dispersion between the supermodes of a directional coupler may induce undesirable pulse breakup in a sufficiently large device. When this happens the device will no longer exchange power between its arms, and the extinction ratio is completely canceled. It is shown that, by carefully designing the coupling area of the directional coupler, one may compensate for intermodal dispersion. The compensating device should accomplish three basic requirements: inverse intermodal dispersion, balanced coupling of each supermode, and maximum power transfer while preserving the sign of the slope of the coupling coefficient with frequency for multiplexing-demultiplexing applications. This structure is designed and optimized with a genetic algorithm. 相似文献
196.
We introduce the concept of topological finite-determinacy for
germs of analytic functions within a fixed ideal
I, which provides a notion of topological finite-determinacy
of functions with non-isolated singularities. We prove the following statement
which generalizes classical results of Thom and Varchenko: let
A be the complement in the ideal I of the space
of germs whose topological type remains unchanged under a
deformation within the ideal that only modifies sufficiently
large order terms of the Taylor expansion. Then A has infinite
codimension in I in a suitable sense. We also prove the
existence of generic topological types of families of germs of
I parametrized by an irreducible analytic set. 相似文献
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Fernández I González J López-Ortiz F 《Journal of the American Chemical Society》2004,126(39):12551-12564
The mechanism of the anionic cyclization dearomatizing reaction of N-benzyl-N-methyldiphenylphosphinamide (1) upon treatment with s-BuLi in tetrahydrofuran (THF) at -90 degrees C has been analyzed by deuterium-labeling and natural abundance multinuclear magnetic resonance ((1)H, (2)H, (7)Li, (13)C, (31)P) studies. In the absence of coordinating cosolvents such as hexamethylphosphoramide (HMPA), eight major anionic species were identified, which allowed us to unravel the pathway of the metalation reaction. In agreement with the complex-induced proximity effect (CIPE) mechanism, the sequence of transformations emerging from this study involves the coordination of the lithium base to the P=O group of 1 to give four dimeric precomplexes whose NMR data are consistent with structures Va/Vb and VIIIa/VIIIb. The diastereomers Va/Vb are the precursors of the monomeric benzylic anion II, whereas the VIIIa/VIIIb diastereomers are assumed to undergo ortho deprotonation leading to anions I. Translocation from the ortho anion to the benzylic one is not observed. Intramolecular conjugate addition of anion II to the P-phenyl rings happens in a reversible way, affording the monomeric dearomatized anions III, IV, VI, and VII. The reaction progresses to yield a mixture containing only the species I, III, and IV. HMPA acts as a catalyst for the ortho-to-benzylic translocation and anionic cyclization reactions. Two-dimensional (2D) (7)Li,(31)P[(1)H] shift correlations and (7)Li[(31)P] NMR spectra proved to be crucial for the structural assignment of the anionic species. These techniques also demonstrated the diastereotopicity of the two achiral ligands involved in a dimer with s-BuLi (Vb) owing to the slow configuration inversion of the carbanion center. 相似文献