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11.
Lewis acid-mediated Diels-Alder reactions of quinol lactone 2 gave regioselectivity opposite to that of the uncatalyzed reaction. Compound 12 is proposed as the reactive intermediate generated by the reaction of 2 with stannic chloride. 相似文献
12.
13.
The nonlinear integro-differential equation, obtained from the coupled Maxwell-Dirac equations by eliminating the potential A, is solved by iteration rather than perturbation. The energy shift is complex, the imaginary part giving the spontaneous emission. Both self-energy and vacuum polarization terms are obtained. All results, including renormalization terms, are finite. 相似文献
14.
Th Kraus 《Monatshefte für Chemie / Chemical Monthly》1964,95(3):733-738
Zusammenfassung Die Dampfdruckerniedrigung, die kondesierendes Argon bei 4,2° K auf Wasserstoff ausübt, wurde unter der Annahme, da die Stammfunktion desRaoultschen Gesetzes unter den herrschenden Bedingungen gültig ist, berechnet und mit Mewerten vonHengevoss undTrendelenburg verglichen. Aus der guten Übereinstimmung der Ergebnisse kann mit gro Wahrscheinlichkeit auf die Richtigkeit dieser Voraussetzungen geschlossen werden. 相似文献
15.
Kraus M Janek K Bienert M Krause E 《Rapid communications in mass spectrometry : RCM》2000,14(13):1094-1104
The self-assembly of beta-sheet peptide domains resulting in the formation of fibrillar aggregates (amyloids) is a feature of various neurodegenerative disorders. In order to evaluate mass spectrometric methods for the characterization of intermolecular beta-sheet structures the hydrogen/deuterium exchange behaviour of model peptides DPKGDPKG-(VT)(n)-GKGDPKPD-amide (n = 3,4,5,6,7,8), (VT)(n)-peptides, composed of a central beta-sheet-forming domain and N- and C-terminal nonstructured octapeptide sequences, was measured by electrospray ionization mass spectrometry (ESI-MS) and matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). The kinetic analysis of the hydrogen/deuterium exchange (HX) shows that intermolecular beta-sheet structures contain slowly exchanging protons (k =0.001 1/min). Localization of beta-sheet domains was achieved by monitoring the hydrogen exchange of peptide fragments generated via collision-induced dissociation (CID) or post source decay (PSD). The hydrogen exchange kinetics and the beta-sheet domains determined by ESI- and MALDI-MS were found to correlate with the length and stability of the beta-structure domain of the (VT)(n)-peptides. 相似文献
16.
Résumé Les auteurs montrent que le moment dipolaire d'une molécule peut, avec une bonne approximation, se réduire à la somme vectorielle des moments atomiques et d'un moment de charges ponctuelles centrées sur les atomes. Les charges ainsi définies sont indépendantes du système d'axes de coordonnées.
Equipe de Recherche Associée au C.N.R.S. n 22.
Remerciements. Ce travail a été en partie présenté au 2ème Colloque International des Chimistes Théoriciens d'expression latine (Paris, septembre 1970).Les auteurs remercient les participants à ce Colloque et en particulier Madame A. Pullman et Monsieur P. Claverie pour leurs remarques et leurs suggestions. Leur gratitude va également au Centre National de la Recherche Scientifique pour l'aide matérielle qu'il apporte à ces recherches. 相似文献
Population analysis by LCAO calculations: Charges and atomic moments
The authors show that the dipole moment of a molecule can be reduced to the vector sum of the atomic moments and of a moment due to point charges centred on atoms with a good accuracy. The so defined charges are independent of the coordinate system.
Zusammenfassung Die Autoren zeigen, daß das Dipolmoment von Molekülen als Vektorsumme der Atommomente und eines Moments, das von Punktladungen an den Atomen herrührt, dargestellt werden kann. Die dabei definierten Ladungen sind unabhängig vom Koordinatensystem.
Equipe de Recherche Associée au C.N.R.S. n 22.
Remerciements. Ce travail a été en partie présenté au 2ème Colloque International des Chimistes Théoriciens d'expression latine (Paris, septembre 1970).Les auteurs remercient les participants à ce Colloque et en particulier Madame A. Pullman et Monsieur P. Claverie pour leurs remarques et leurs suggestions. Leur gratitude va également au Centre National de la Recherche Scientifique pour l'aide matérielle qu'il apporte à ces recherches. 相似文献
17.
The study of the mass analysed ion kinetic energy spectra of deuterated derivatives of aniline, aminopyridines and 2-chloro-5-aminopyridine shows that prior to HCN loss, hydrogen scrambling does not occur for aminopyridines and is limited but noticeable for aniline. In the case of this last compound the extent of scrambling varies markedly for small variations in the energy of the ions studied, these variations being within the energy window corresponding to metastable ions. Furthermore, an examination of the mass analysed ion kinetic energy spectra of monodeuterated derivatives of aminopyridines leads to the rejection of the generally accepted mechanism for HCN loss from the molecular ions of these compounds. 相似文献
18.
Ganjehi L Marchiano R Coulouvrat F Thomas JL 《The Journal of the Acoustical Society of America》2008,124(1):57-71
The influence of the planetary boundary layer on the sonic boom received at the ground level is known since the 1960s to be of major importance. Sonic boom propagation in a turbulent medium is characterized by an increase of the mean rise time and a huge variability. An experiment is conducted at a 1:100,000 scale in water to investigate ultrasonic shock wave interaction with a single heterogeneity. The experiment shows a very good scaling with sonic boom, concerning the size of the heterogeneities, the wave amplitude, and the rise time of the incident wave. The wave front folding associated with local focusing, and its link to the increase of the rise time, are evidenced by the experiment. The observed amplification of the peak pressure (by a factor up to 2), and increase of the rise time (by up to about one magnitude order), are in qualitative agreement with sonic boom observations. A nonlinear parabolic model is compared favorably to the experiment on axis, though the paraxial approximation turns out less precise off axis. Simulations are finally used to discriminate between nonlinear and linear propagations, showing nonlinearities affect mostly the higher harmonics that are in the audible range for sonic booms. 相似文献
19.
We report on an innovative configuration of a supercontinuum laser based on an Yb-doped nonlinear microstructured fiber. Due to this particular fiber design combining amplification and nonlinear properties, a wideband output spectrum is generated in the fiber under the Q-switched regime. By exploiting stimulated Brillouin scattering, high peak power pulses are achieved and contribute to a spectral broadening due to a nonlinear wavelength conversion process. Both infrared (1000-1200 nm) and visible (650-750 nm) spectra are generated with an average power of 200 mW. 相似文献
20.
Grald Monard Michel Loos Vincent Thry Kristofor Baka Jean-Louis Rivail 《International journal of quantum chemistry》1996,58(2):153-159
A coherent computational scheme on a very large molecule in which the subsystem that undergoes the most important electronic changes is treated by a semiempirical quantum chemical method, though the rest of the molecule is described by a classical force field, has been proposed recently. The continuity between the two subsystems is obtained by a strictly localized bond orbital, which is assumed to have transferable properties determined on model molecules. The computation of the forces acting on the atoms is now operating, giving rise to a hybrid classical quantum force field (CQFF ) which allows full energy minimization and modeling chemical changes in large biomolecules. As an illustrative example, we study the short hydrogen bonds and the proton-exchange process in the histidine-aspartic acid system of the catalytic triad of human neutrophil elastase. The CQFF approach reproduces the crystallographic data quite well, in opposition to a classical force field. The method also offers the possibility of switching off the electrostatic interaction between the quantum and the classical subsystems, allowing us to analyze the various components of the perturbation exerted by the macromolecule in the reactive part. Molecular dynamics confirm a fast proton exchange between the three possible energy wells. The method appears to be quite powerful and applicable to other cases of chemical interest such as surface reactivity of nonmetallic solids. © 1996 John Wiley & Sons, Inc. 相似文献