(Z)-3-p-tolylsulfinylacrylonitrile as a chiral dienophile: diels-alder reactions with furan and acyclic dienes

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.     

Crown compounds for anions. Sandwich complex of cyclic trimeric perfluoro-o-phenylenemercury with [B12H11SCN]2– anion

The reaction of cyclic trimeric perfluoro-o-phenylenemercury (o-C₆F₄Hg)₃ (1) with the polyhedral [B₁₂H₁₁SCN]^2– anion in THF at 20 °C affords the {[(o-C₆F₄Hg)₃](B₁₂H₁₁SCN)}^2– (4) and {[(o-C₆F₄Hg)₃]₂(B₁₂H₁₁SCN)}^2– (5) complexes. Complex 5 was isolated as the tetrabutylammonium salt. X-ray diffraction analysis showed that this complex has a bent-sandwich structure in which the [B₁₂H₁₁SCN]^2– anion is located between the planes of two molecules 1 and is coordinated to both these molecules through B—H—Hg bridges and S—Hg bonds. The stability constants of complexes 4 and 5 in THF (20 °C), which were determined from the IR spectroscopic data, are 16 L mol^–1 and 992 L² mol^–2, respectively.     

Mössbauer spectroscopy of237Np in solid solutions of actinide dioxides

Emission Mössbauer (nuclear gamma-resonance) spectra of²³⁷Np resulting from the alpha-decay of²⁴¹Am in solid solutions AmO₂–ThO₂ and AmO₂–UO₂ prepared by precipitation from LiF–NaF eutectic melts under fluorine-oxygen exchange were first investigated in the temperature range from 77 to 296 K. The resonant absorbers are NpO₂ and NpAl₂. The possibility is stated of managing the form of the emission Mössbauer spectra of²³⁷Np in dioxides by the directed change of the matrix stoichiometry or by its irradiation by visible light. At temperatures from 77 to 230 K the authors measured for the first time the NGR absorption spectra of²³⁷Np in solid solution NpO₂–ThO₂ with various concentrations of neptunium dioxide. An increase of the absorption line width (approximately by a factor of 4) with a decrease in the NpO₂ contents (to 10 mol.%) was explained by the influence of fast electron exchange between Np⁴⁺ and Np⁵⁺ states observed in the NpO₂–ThO₂ solid solution at low concentrations of neptunium dioxide.     

Narrow band quantitative and multivariate electroencephalogram analysis of peri-adolescent period

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.     

Dependence of growth of the phases of multiphase binary systems on the diffusion parameters

A mathematical model of the diffusion interaction of a binary system with several phases on the equilibrium phase diagram is presented. The theoretical and calculated dependences of the layer thickness of each phase in the multiphase diffusion zone on the isothermal annealing time and the ratio of the diffusion parameters in the neighboring phases with an unlimited supply of both components were constructed. The phase formation and growth in the diffusion zone during “reactive” diffusion corresponds to the equilibrium state diagram for two components, and the order of their appearance in the diffusion zone depends only on the ratio of the diffusion parameters in the phases themselves and on the duration of the incubation periods. The dependence of phase appearance on the incubation periods, annealing time, and difference in the movement rates of the components across the interface boundaries was obtained. An example of the application of the model for processing the experimental data on phase growth in a two-component three-phase system was given.     

Study of K^ - \to \pi ^0 e^ - \overline \nu _e \gamma decay with ISTRA+ setup

Results of study of the $K^ - \to \pi ^0 e^ - \overline \nu \gamma $ decay at the ISTRA+ setup are presented. We observed 4476 events of this decay. The branching ratio is found to be $R = \frac{{Br(K^ - \to \pi ^0 e^ - \overline \nu _e \gamma )}}{{Br(K^ - \to \pi ^0 e^ - \overline \nu _e )}}$ = (1.81±0.03(stat.)±0.07(syst.)) × 10^?2 for E*_γ > 10 MeV and θ*_eγ > 10°. For comparison with the previous experiment the branching ratio with cuts E*_γ > 10 MeV, 0.6 < cos θ*_eγ < 0.9 is calculated: R = $\frac{{Br(K^ - \to \pi ^0 e^ - \overline \nu _e \gamma )}}{{Br(K^ - \to \pi ^0 e^ - \overline \nu _e )}}$ = (0.47±0.02(stat.) ± 0.03(syst.)) × 10^?2. For the cuts E*_γ > 30 MeV and θ*_eγ > 20°, used in most theoretical papers, Br = (3.06 ± 0.09(stat.) ± 0.14(syst.)) × 10^?4. For the asymmetry we get A _ξ = ?0.015 ± 0.021. At present it is the best estimate of this asymmetry.     

Scars of the Wigner Function

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.