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The behavior of (Z)-3-p-tolylsulfinylacrylonitrile (1) as a chiral dienophile has been evaluated from its reactions with furan and acyclic dienes. Electrostatic interactions of the cyano group with the sulfinyl one restrict the conformational mobility around the C-S bond, thus controlling the pi-facial selectivity, which is almost complete in all cases, the approach of the diene from the less-hindered face of the dienophile (that bearing the lone electron pair) in the predominant rotamer being the favored one. The regioselectivity is also completely controlled by the cyano group. Additionally, the reactivity of compound 1 as well as its endo-selectivity are both higher than those observed for the corresponding (Z)-3-sulfinylacrylates, thus proving the potential of sulfinylnitriles as chiral dienophiles.  相似文献   
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ABSTRACT: BACKGROUND: The peri-adolescent period is a crucial developmental moment of transition from childhood to emergent adulthood. The present report analyses the differences in Power Spectrum (PS) of the Electroencephalogram (EEG) between late childhood (24 children between 8 and 13 years old) and young adulthood (24 young adults between 18 and 23 years old). RESULTS: The narrow band analysis of the Electroencephalogram was computed in the frequency range of 0--20 Hz. The analysis of mean and variance suggested that six frequency ranges presented a different rate of maturation at these ages, namely: low delta, delta-theta, low alpha, high alpha, low beta and high beta. For most of these bands the maturation seems to occur later in anterior sites than posterior sites. Correlational analysis showed a lower pattern of correlation between different frequencies in children than in young adults, suggesting a certain asynchrony in the maturation of different rhythms. The topographical analysis revealed similar topographies of the different rhythms in children and young adults. Principal Component Analysis (PCA) demonstrated the same internal structure for the Electroencephalogram of both age groups. Principal Component Analysis allowed to separate four subcomponents in the alpha range. All these subcomponents peaked at a lower frequency in children than in young adults. CONCLUSIONS: The present approaches complement and solve some of the incertitudes when the classical brain broad rhythm analysis is applied. Children have a higher absolute power than young adults for frequency ranges between 0-20 Hz, the correlation of Power Spectrum (PS) with age and the variance age comparison showed that there are six ranges of frequencies that can distinguish the level of EEG maturation in children and adults. The establishment of maturational order of different frequencies and its possible maturational interdependence would require a complete series including all the different ages.  相似文献   
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Using a local technique, we study the microwave radiation power P3(T,P,Hdc) at the triple frequency of the main signal as a function of the temperature T, the input power P, and the external magnetic field Hdc perpendicular to the superconductor surface for YBa2Cu3O7 (YBCO) films, monocrystals, and polycrystals and for Nb films. The most distinctive feature of the temperature dependence P3(T) of nonlinear response of superconductors is a maximum of the nonlinearity near the critical temperature Tc. Spatial distributions of the third-harmonic power are obtained for YBCO films at various temperatures. These distributions are indicative of a nonuniform distribution of Tc over the superconductor surface. Additional nonlinearity maxima are discovered in the dependence P3(T) for YBCO films and monocrystals at temperatures about 2Tc/3. These maxima are probably related to the existence of several superconducting phases with different critical temperatures. For Nb films, the second nonlinearity maximum in the dependence P3(T) appears only in the presence of an external magnetic field. The experimental data are interpreted within the framework of a two-fluid model of a superconductor, which takes into account the phenomenological nonlinear relationship between the vector potential A and the supercurrent js(A). The origin of nonlinearity in the studied superconductors is discussed.  相似文献   
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We propose a picture of Wigner function scars as a sequence of concentric rings along a two-dimensional surface inside a periodic orbit. This is verified for a two-dimensional plane that contains a classical hyperbolic orbit of a Hamiltonian system with 2 degrees of freedom. The stationary wave functions are the familiar mixture of scarred and random waves, but the spectral average of the Wigner functions in part of the plane is nearly that of a harmonic oscillator and individual states are also remarkably regular. These results are interpreted in terms of the semiclassical picture of chords and centers.  相似文献   
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