Temperature and solvent control of the stereoselectivity in the reactions of singlet oxygen with oxazolidinone-substituted enecarbamates

Oxazolidinone-functionalized enecarbamates react stereoselectively with singlet oxygen to give methyldesoxybenzoin (MDB) in moderate to high enantiomeric excess. The stereochemical outcome depends on the E/Z substrate geometry, temperature, and solvent variables. The analysis of the differential activation parameters suggests a large contribution from the entropy term in determining the enantioselectivity. We demonstrate the utility of the temperature and solvent variables in determining the degree of the photochemical kinetic resolution of the enecarbamates; for example, in the photooxygenation at -70 degrees C in methanol, MDB may be obtained in methanol.     

Self-consistent electronic structure of quantum wells by invariant embedding method

A new approach based on the invariant embedding method for the self-consistent calculation of electronic structure of quantum wells is presented and is applied to both neutral quantum well and parabolic quantum well. Numerical results obtained for these structures agree very well with those of previous theoretical and experiment studies. The present approach is expected to lead to a more efficient and stable scheme for the calculation of electronic band structure of quantum structures. Realistic boundary conditions are naturally taken into account in the present calculation which provides a convenient way for studying boundary effects. Received 21 September     

Fate of Petroleum Hydrocarbons in the Sediment of Coastal Water

Assessment of the concentrations of petroleum hydrocarbons and their fate in marine environment is very important and necessary for marine environment scientists. In order to study the ecotoxicological effects of this kind of pollutants on marine ecological system, the fate of petroleum hydrocarbons in sediment of coastal water has been studied under natural conditions by Chromatography-FID.     

SYNTHESIS AND OPTICAL PROPERTIES OF POLY (THIENYLACETYLENES)*

3 -Ethynyl-4-(trimethylsilyl)thiophene (1a) and 3 -ethynyl-4-bromothiophene (1 b ) selectivelyundergo acetylene polymerizations in the presence of the MoCl_5- and WCl_6-Ph_3SiH catalysts to give soluble,high-molecular-weight poly(thienylacetylenes) (2) (M_w up to 602000) in high yields (up to 100%). Lighttransmission spectra of THF solutions of 2 continuously red-shift with increasing concentration. Theconcentratochromism shows a logarithmic concentration dependence; that is, the optical transitions of 2 arepredictably tunable by simply changing their concentrations.     

Formation of self-supporting reversible cellular networks in suspensions of colloids and liquid crystals

In mixtures of thermotropic liquid crystals with spherical poly (methyl methacrylate) particles, self-supporting networklike structures are formed during slow cooling past the isotropic-to-nematic phase transformation. To characterize the process of network formation in terms of morphology, phase transformation kinetics, and mechanical properties, we have combined data from polarization and laser scanning confocal microscopy with calorimetric, NMR, and rheological results. Our data suggest that the mechanism of network formation is dominated by a broadened temperature and time interval of phase transformation rather than by particle size or concentration. The observation that the width of the transformation interval strongly depends on sample preparation supports the hypothesis that a third component, most likely alkane remnants slowly liberated from the particles, plays a crucial role. In addition, calorimetric findings for liquid crystal/colloid mixtures, heated and cooled up to 13 times, point to separation of the liquid crystal into two compartments with different phase transformation kinetics. This could be explained by redistribution and enrichment of alkane in the particle-composed network walls. A further increase of the storage modulus, G', and incomplete dissolution of the networks in the isotropic state indicate that the formation of two compartments during repeated temperature cycles stabilizes the network and confers strong memory effects.     

Layer spacings in coherently strained epitaxial metal films

Laterally resolved measurements of the quantum size effect (QSE) in electron reflectivity are made with low energy electron microscopy on coherently strained Ag films on a W(110) surface. The evolution of the total film thickness with increasing number of atomic layers is determined accurately by dynamical theory analysis of the QSE features. Combined with a model of layer spacings obtained from first-principles calculations, this provides for a novel approach to determine the buried interface layer spacing, which is inaccessible to other methods.     

Measurement of neutrino oscillation with KamLAND: evidence of spectral distortion

We present results of a study of neutrino oscillation based on a 766 ton/year exposure of KamLAND to reactor antineutrinos. We observe 258 nu (e) candidate events with energies above 3.4 MeV compared to 365.2+/-23.7 events expected in the absence of neutrino oscillation. Accounting for 17.8+/-7.3 expected background events, the statistical significance for reactor nu (e) disappearance is 99.998%. The observed energy spectrum disagrees with the expected spectral shape in the absence of neutrino oscillation at 99.6% significance and prefers the distortion expected from nu (e) oscillation effects. A two-neutrino oscillation analysis of the KamLAND data gives Deltam(2)=7.9(+0.6)(-0.5)x10(-5) eV(2). A global analysis of data from KamLAND and solar-neutrino experiments yields Deltam(2)=7.9(+0.6)(-0.5)x10(-5) eV(2) and tan((2)theta=0.40(+0.10)(-0.07), the most precise determination to date.     

Experimental demonstration of waveguide-coupled round-cornered octagonal microresonators in silicon nitride

We report laterally waveguide-coupled octagonal microresonators with designed round resonator corners in silicon nitride. We demonstrate nearly single-mode add-drop filter characteristics, when 50-microm-size round-cornered octagonal microresonators are used, with an optimum coupling efficiency exceeding 96%, a finesse of approximately 30, and a Q of approximately 6400. Our experiments also reveal two unforeseen phenomena in certain microresonator shapes: a pronounced drop in coupling efficiency and resonance notches in the drop spectrum. These device characteristics hint at the recently postulated multiple orbit interference in waveguide-coupled polygonal microresonators.     

Stereoselective photooxidation of enecarbamates: reactivity of ozone vs singlet oxygen

[reaction: see text]. Oxazolidinone-functionalized enecarbamates show contrasting behavior upon oxidation by singlet oxygen and by ozone. The observed stereoselectivity difference indicates that the oxidation with ozone is subject to classic steric effects, whereas the very high selectivity in the photooxidation with singlet oxygen is derived from vibrational deactivation.