Efficient oxidation of alcohols electrochemically mediated by azabicyclo-N-oxyls

Preparation of azabicyclo-N-oxyls and the electrochemical oxidation of alcohols using them as mediators have been exploited. This oxidation was applicable to a transformation of sterically hindered secondary alcohols into the corresponding ketones in high yields.     

Initial stage of fiber structure development in the continuous drawing of poly(ethylene terephthalate)

The initial stage of fiber structure development in the continuous neck‐drawing of amorphous poly(ethylene terephthalate) fibers was analyzed by in situ wide‐angle X‐ray diffraction, small‐angle X‐ray scattering, and fiber temperature measurements. The time error of the measurements (<600 μs) was obtained by synchrotron X‐ray source and laser irradiation heating. A highly ordered fibrillar‐shaped two‐dimensional (smectic‐like) structure was found to be formed less than 1 ms after necking. By analyzing its (001′) and (002′) diffractions, the length of the structure 60–70 nm were obtained. A three‐dimensionally ordered triclinic crystal began to form with the vanishing of the structure around 1 ms after necking. The amount and size of the crystal were almost saturated within several milliseconds of necking, during which time a mainly exothermic heat of crystallization was also observed. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2126–2142, 2008     

Challenge to detect 1,4-zwitterions spectroscopically in a ketene-alkene reaction

The first example of direct spectroscopic detection of transient species, 1,4-zwitterions, generated in a ketene-alkene reaction is reported. Also, a striking result of the intervention of an unprecedented "1,4-zwitterion neutral dimer" is presented in a new mechanistic pathway; the ketene-alkene reaction gives the product cyclobutanone from the initial cycloadduct alpha-methyleneoxetane.     

Grain-boundary faceting at a = 3, [110]/{112} grain boundary in a cubic zirconia bicrystal

The atomic structure of a = 3, [110]/{112} grain boundary in a yttria-stabilized cubic zirconia bicrystal has been investigated by high-resolution transmission electron microscopy (HRTEM). It was found that the grain boundary migrated to form periodic facets, although the bicrystal was initially joined so as to have the symmetric boundary plane of {112}. The faceted boundary planes were indexed as {111}/{115}. The structure of the {111}/{115} grain boundary was composed of an alternate array of two types of structure unit: {112}- and {111}-type structure units. HRTEM observations combined with lattice statics calculations verified that both crystals were relatively shifted by (α/4)[110] along the rotation axis to form a stable grain-boundary structure. A weak-beam dark-field image revealed that there was a periodic array of dislocations along the grain boundary. The grain-boundary dislocations were considered to be introduced by the slight misorientation from the perfect = 3 orientation. The fact that the periodicity of the facets corresponded to that of the grain-boundary dislocations must indicate that the introduction of the grain-boundary dislocations is closely related to the periodicity of the facets. An atomic flipping model has been proposed for the facet growth from the initial = 3, {112} grain boundary.     

CDW-induced negative thermal expansion in two-dimensional conductor η-Mo4O11

Two-dimensional oxide η-Mo₄O₁₁ exhibits almost isotropic thermal expansion in the normal phase, while anisotropic negative thermal expansion (NTE) in the charge density wave (CDW) phase below T_c1=105 K, where a remarkable anomalous expansion occurs along the a-axis. The incommensurate nesting vector along the b-axis is independent of temperature, q₁=(0.000(1) 0.2335(1) 0.0000(5)). We propose that the CDW-induced NTE occurs as a result of the structural relaxation of the MoO₆ octahedra layers along the stacking direction with the aid of the open spaces around the MoO₄ tetrahedra.     

Single Telephoto Lens for Focus Error Detection with Astigmatic Method

An astigmatic method for focus error detection has been integrated into a singlet. The first convex and the second concave surfaces compose a telephoto system with a telephoto ratio of about 0.4. The first surface of the lens is rotationally symmetrical asphere and the second surface is a toric shape whose aspherical profiles correct spherical aberration. We implemented our optical design using a molded glass process. Its performance was confirmed using the optical head of a magneto-optical disk system.     

Soft dipole resonance in the neutron-skin nucleus 6He

We consider a billiard model of a self-bound, interacting three-body system in two spatial dimensions. Numerical studies show that the classical dynamics is chaotic. The corresponding quantum system displays spectral fluctuations that exhibit small deviations from random matrix theory predictions. These can be understood in terms of a new type of scarring caused by a one-parameter family of orbits inside the collinear manifold.     

Role of Pr segregation in acceptor-state formation at ZnO grain boundaries

The role of Pr doping on double Schottky barrier formations at ZnO single grain boundaries was investigated by the combination of current-voltage measurements, atomic-resolution Z-contrast scanning transmission electron microscopy, and first-principles calculations. Although Pr segregated to the specific atomic site along the boundaries, it was found not to be the direct cause of nonlinear current-voltage properties. Instead, under appropriate annealing conditions, Pr enhances formations of acceptor-type native defects that are essential for the creation of double Schottky barriers in ZnO.     

Mitigation of Diffraction Fringe in Quasi-Far Field Pattern Using an Edge-Shaped Plate

A new concept is developed for improving the laser intensity distribution in quasi-far field using geometrical optics of a continuous phase (so-called edge-shaped plate). The diffraction fringe on a quasi-far field beam pattern of a well collimated He-Ne laser beam 5 cm in diameter is mitigated by the insertion of an edge-shaped plate with a super-Gaussian (n=40) surface profile. A diffraction code using Fresnel-Kirchhoff diffraction integration was developed to calculate diffraction patterns of aspherical optical elements. The measured beam profile is in good agreement with the calculated beam pattern.     

Point spread function measurement of an X‐ray beam focused by a multilayer zone plate with narrow annular aperture

The experimental procedure for obtaining the point spread function (PSF) of a focusing beam generated using an X‐ray multilayer zone plate (MZP) with a narrow annular aperture has been developed. It was possible to reconstruct the PSF by applying the tomographic process to the measured dataset consisting of line spread functions (LSFs) in every radial direction on the focal plane. The LSFs were measured by a knife‐edge scanning method of detecting scattered intensity. In the experimental work, quasi‐monochromatic undulator radiation with a first harmonic energy of 20 keV was directly focused without a monochromator by the MZP, and the PSF was measured using this procedure. As a result, a near diffraction‐limited focused beam size of 46 nm full width at half‐maximum was obtained.