A novel example of chiral counteranion induced enantioselective metal catalysis: the importance of ion-pairing in copper-catalyzed olefin aziridination and cyclopropanation

A new ion-pairing route to achieve asymmetric catalysis has been observed in the copper-catalyzed aziridination of styrene with a chiral counteranion. Structural studies suggest that enantioinduction occurs via ion-pairing of the cationic copper catalyst in the chiral pocket created by the anion. The degree of asymmetric induction can be tuned with features that affect ion-pairing, such as achiral and chiral ligands, temperature, and solvent polarity.     

The influence of a multilayer system of inhomogeneous ultrathin films on reflection of light from dielectric materials

Optics and Spectroscopy - The influence of surface layers on reflection of light in the absence of absorption is studied. The contribution of an ultrathin N-layer film system to the light...     

Laser stimulation of low-temperature dissociative recombination of electrons and oxygen molecular ions

A theory of dissociative recombination of slow electrons and molecular ions in a strong monochromatic light field is developed. The theory takes into account interference between various reaction channels and is constructed in a rigid basis adiabatic with respect to rotation (the approximation of a fixed molecular axis). The mathematical apparatus of the theory is based on the stationary formalism of the matrix of radiation collisions, whose poles correspond to “quasi-energy” states of a composite system. Along with transitions into dissociative configurations, field-induced nonadiabatic transitions into bound intermediate states of valence (non-Rydberg) configurations are considered. As a particular application of the theory, the e^? + O ₂ ⁺ (²Π _g ) → $ O(^{2s_1 + 1} l_1 ) + O(^{2s_2 + 1} l_2 ) A theory of dissociative recombination of slow electrons and molecular ions in a strong monochromatic light field is developed. The theory takes into account interference between various reaction channels and is constructed in a rigid basis adiabatic with respect to rotation (the approximation of a fixed molecular axis). The mathematical apparatus of the theory is based on the stationary formalism of the matrix of radiation collisions, whose poles correspond to “quasi-energy” states of a composite system. Along with transitions into dissociative configurations, field-induced nonadiabatic transitions into bound intermediate states of valence (non-Rydberg) configurations are considered. As a particular application of the theory, the e⁻ + O₂⁺(²Π _g ) → reaction is analyzed. A study of this reaction requires detailed information about the potential curves of the states participating in it with taking into account the external electromagnetic field (l and s are the electronic angular momenta and reaction product spins). For this purpose, the general problem is divided into three stages. At the first stage, the theoretical approach is formulated, and at the second stage, the corresponding potential curves are calculated and the main reaction mechanisms are determined. The third stage should include calculations of the total and differential cross sections. This work is concerned with the first two stages; that is, the adiabatic potential curves of the singlet and triplet dissociative states of the O₂^** oxygen molecule are calculated, a classification of all possible transition types is given, and reaction mechanisms in the presence of monochromatic laser radiation are determined. The frequency regions of external radiation in which these mechanisms are most effective are found. Original Russian Text ? S.O. Adamson, R.J. Buenker, G.V. Golubkov, M.G. Golubkov, A.I. Dement’ev, 2009, published in Khimicheskaya Fizika, 2009, Vol. 28, No. 4, pp. 26–42.     

Potential Energies of the Orbitally Degenerate Atmospheric Rydberg Complexes

A method was developed for calculating the vibronic potential energy surfaces (PESs) of atmospheric complexes consisting of orbitally degenerate Rydberg nitrogen and oxygen molecules and the molecules of a neutral medium in the ground electronic state. The degenerate states are formed as a result of l-mixing in the D and E layers of the atmosphere during the periods of increased solar activity. The complexes are populated in the nonequilibrium two-temperature plasma and are responsible for the incoherent additional background radiation in the decimeter (microwave) and terahertz (IR) bands at an altitude of 80–110 km from the Earth’s surface. To describe the interaction of a weakly bound electron with a singly charged molecular ion and a neutral molecule of a gas medium, the formalism of the multichannel quantum defect (MCD) theory was used. Quantum-chemical calculations of the dependences of the scattering lengths, polarizabilities, and quadrupole moments of the main atmospheric molecules N₂ and O₂ on the interatomic distance were performed. The specific features of the behavior of vibronic PESs of Rydberg complexes for large values of the principal quantum number (n ? 1) were analyzed. The vibronic PESs of orbitally degenerate states were constructed. They are necessary for determining the positions and shape of the vibronic minima of the l-mixing cross sections of the N₂ and O₂ Rydberg molecules in the D and E layers of the Earth’s atmosphere, where the delay times of satellite positioning signals should be minimum. The possibility of “quantum chaos” appearing in the Rydberg complexes at sufficiently large n values and angular momenta of the weakly bound electron was noted.     

Chemical carcinogenesis studies in nonhuman primates

This review covers chemical carcinogenesis studies in nonhuman primates performed by the National Cancer Institute, USA, to provide hitherto unavailable information on their susceptibility to compounds producing carcinogenic effects in rodents. From autopsy records of 401 breeders and untreated controls, incidences of spontaneous malignant tumors were found to be relatively low in cynomolgus (1.9%) and rhesus monkeys (3.8%), but higher in African green monkeys (8%). Various chemical compounds, and in particular 6 antineoplastic agents, 13 food-related compounds including additives and contaminants, 1 pesticide, 5 N-nitroso compounds, 3 heterocyclic amines, and 7 "classical" rodent carcinogens, were tested during the 34 years period, generally at doses 10 approximately 40 times the estimated human exposure. Results were inconclusive in many cases but unequivocal carcinogenicity was demonstrated for IQ, procarbazine, methylnitrosourea and diethylnitrosamine. Furthermore, negative findings for saccharine and cyclamate were in line with results in other species. Thus susceptibility to carcinogens is at least partly shared by nonhuman primates and rodents.     

Measurement Instruction in the Context of Scientific Investigations With Diverse Student Populations

The purpose of this study was to investigate the impact of a hands‐on science curriculum, which integrates mathematics and supports English language development, on third‐grade students' mathematics achievement—specifically the measurement subscale of the statewide assessment. The data drew from a larger five‐year research and development project consisting of reform‐based science curriculum units and teacher workshops designed to promote effective science instruction while integrating mathematics and supporting English language development. The third‐grade curriculum places a strong emphasis on measurement skills in the context of science inquiry. The third‐grade students' performance on the measurement subscale of the statewide mathematics assessment in the treatment schools was compared with that of comparison schools using a hierarchical linear model. Students at the treatment schools performed significantly higher than students at the comparison schools. The results provide evidence that an integrated approach to mathematics and science instruction can benefit diverse student groups.     

Adsorptions- und Kontaktwinkel-Studien. II. Wasser und organische Substanzen an poliertem Polytetrafluoräthylen

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