Non-destructive rapid analysis of brominated flame retardants in electrical and electronic equipment using Raman spectroscopy.

Using Raman spectroscopy without any preparation, we analyzed the brominated flame retardant, polybromodiphenyl ethers (PBDEs), which has been prohibited by the European Union. The typical Raman bands of PBDEs, which are clearly different from those of other brominated flame retardants, are from 100 to 300 cm(-1). In our analysis, the detection limit was about 100 ppm, and the analysis took about 1 min, whereas the usual method of solvent extraction using gas chromatography/mass spectroscopy takes 50 h.     

Two-dimensional numerical calculation of the flow field about a scoop inlet by the piecewise linear method

The piecewise linear method (PLM) based on time operator splitting is used to solve the unsteady compressible Euler equations describing the two-dimensional flow around and through a straight wall inlet placed stationary in a rapidly rotating supersonic flow. The PLM scheme is formulated as a Lagrangian step followed by an Eulerian remap. The inhomogeneous terms in the Euler equations written in cylindrical coordinates are first removed by Sod's method and the resulting set of equations is further reduced to two sets of one-dimensional Lagrangian equations, using time operator splitting. The numerically generated flow fields are presented for different values of the back pressure imposed at the downstream exit of the inlet nozzle. An oblique shock wave is formed in front of the almost whole portion of the inlet entrance, the incoming streamlines being deflected towards the higher pressure side after passing through the oblique shock wave and then bending down to the lower pressure side. A reverse flow appears inside the inlet nozzle owing to the recovery pressure of the incoming streams being lower than the back pressure of the inlet nozzle.     

Effect of core-shell micelle formation on the redox properties of phenothiazine-labeled poly(ethyl glycidy ether)-block-poly(ethylene oxide)

Redox properties of phenothiazine-labeled poly(ethyl glycidy ether)-block-poly(ethylene oxide) (PT-EGE_n-b-EO_m) are reversibly changed by core-shell micelle formation. In the temperature range higher than the critical micellization temperature (cmt), the anodic potential of PT group positively shifts and concomitantly its anodic current decrease, or levels off compared to those of the reference polymer PT-EO_m without the thermo-responsive EGE_n segment. The former alteration is caused by incorporation of hydrophobic PT groups into a core of the micelle and the latter by the decrease in the diffusion coefficient of PT groups due to formation of the core-shell micelles. The cmt value and the temperature-dependent alteration in the redox properties strongly depend on the polymer structure, especially the length of thermo-responsive EGE_n segment. The electrochemically determined hydrodynamic radii of the polymer aggregates seem to be overestimated, compared to the values reported for the aggregates of other thermo-responsive polymers with similar molecular weights, implying the presence of electrochemically inactive PT groups in the copolymers having longer thermo-responsive segments.     

Structural and electrical properties of crystalline (1−x)Ta2O5−xTiO2 thin films fabricated by metalorganic decomposition

Polycrystalline (1−x)Ta₂O₅−xTiO₂ thin films were formed on Si by metalorganic decomposition (MOD) and annealed at various temperatures. As-deposited films were in the amorphous state and were completely transformed to crystalline after annealing above 600 °C. During crystallization, a thin interfacial SiO₂ layer was formed at the (1−x)Ta₂O₅−xTiO₂/Si interface. Thin films with 0.92Ta₂O₅–0.08TiO₂ composition exhibited superior insulating properties. The measured dielectric constant and dissipation factor at 1 MHz were 9 and 0.015, respectively, for films annealed at 900 °C. The interface trap density was 2.5×10¹¹ cm⁻² eV⁻¹, and flatband voltage was −0.38 V. A charge storage density of 22.8 fC/μm² was obtained at an applied electric field of 3 MV/cm. The leakage current density was lower than 4×10⁻⁹ A/cm² up to an applied electric field of 6 MV/cm.     

A conducting crystal based on a single-component paramagnetic molecule, [Cu(dmdt)(2)] (dmdt = dimethyltetrathiafulvalenedithiolate)

A single-component conducting molecular crystal composed of paramagnetic copper complexes, [Cu(dmdt)2]0+, was prepared. The crystal has an unprecedented three-dimensionally packed molecular arrangement and exhibits a fairly high conductivity (1 S cm-1 at room temperature). The magnetic susceptibility measurements revealed that [Cu(dmdt)2]0+ molecule keeps most of S = 1/2 spin moments. The difference of the bond lengths between [Cu(dmdt)2]0+ and [Cu(dmdt)2]2- is consistent with the result of the molecular orbital calculation.     

Lewis acid-mediated selective chlorinations of silyl enolate

A new method involving efficient, widely applicable, and highly selective alpha-chlorination of simple silyl enolate with Lewis acid and an alpha,alpha-dichloro-1,3-dicarbonyl controller unit was reported. Diastereoselectivity and enantioselectivity of the reaction were investigated. High reactivity and selectivity were achieved by using alpha,alpha-dichlorinated malonic ester.     

Catalytic, highly enantio- and diastereoselective pinacol coupling reaction with a new tethered bis(8-quinolinolato) ligand

A new class of chiral ligand, tethered bis(8-quinolinol) (TBOxH), is developed. Its chromium complex, TBOxCrCl (3 mol %), effectively catalyzes the pinacol coupling reaction of aromatic aldehydes at room temperature with high yield (up to 94%), high diastereoselectivity (up to dl:meso = 98:2), and high enantioselectivity (up to 98%). The scope of the present method turns out not to be limited to aromatic aldehyde derivatives, as cyclohexanecarboxaldehyde undergoes pinacolization as well (44% yield, dl:meso = 93:7, 84% ee). The method provides an efficient access to enantioenriched 1,2-diols.     

Bounds to average interelectronic angles in Hartree-Fock theory of atoms

The average interelectronic is the expectation value of the angle thetaij (0 < or = thetaij < or = pi) subtended by the position vectors ri and rj of a pair of electrons i and j. In the Hartree-Fock theory of atoms, we point out that the angle and its subshell-pair components nl,n'l' are bounded from above and below, where n and l are the principal and azimuthal quantum numbers. The upper bounds for nl,n'l' with 0 < or = l, l' < or = 3 are 9pi/16 (=101.25 degrees), 135pi/256 (approximately 94.922 degrees), 265pi/512 (approximately 93.164 degrees), and 129pi/256 (approximately 90.703 degrees) for sp, pd, df, and sf pairs, respectively, while they are pi/2 (=90 degrees ) for the other ll' pairs, independent of n and n'. A weighted sum of these subshell-pair bounds gives an upper bound to . The lower bounds are pi/2 in all the cases.