Formation of cyclic organosilicon compounds via organopolysilyl anions starting from methoxymethyldisilanes. A mechanistic study

In the presence of a catalytic amount of sodium methoxide, sym-dimethoxytetramethyldisilane was converted into α,ω-dimethoxypermethylpolysilanes, MeO(SiMe₂)_nOMe where n ? 3, at room temperature. On the other hand, similar treatment of the disilane in THF solution gave cyclic polysilanes, (Me₂Si)_n where n = 5–7. Decomposition of the disilane in the presence of diphenylacetylene afforded a trisilacyclopentene derivative under similar conditions. This compound was obtained also by the reaction between α,ω-dimethoxypermethylpolysilanes and diphenylacetylene in the presence of sodium methoxide. These cyclic products most likely were formed via permethyl polysilyl anion intermediates derived from α,ω-dimethoxypermethylpolysilanes. Also, the formation of α,ω-dimethoxypermethylpolysilanes could be elucidated in terms of the mechanism involving the base-assisted, concerted nucleophilic substitution or stepwise substitution by silyl anions, rather than the successive dimethylsilylene (Me₂Si:) insertion reaction.     

Larmor precession in polarization spectroscopy with spatially separated beams

Sodium vapour in a sealed cell is irradiated by two counter-propagating but laterally displaced beams from the same laser, tuned to one of the hf components of the D₁ line. Atoms pumped by the stronger beam, circularly polarized, precess in a transverse magnetic field, < 300 mG, during their passage to the weaker beam where their orientation is monitored. The observed signals are interpreted quantitatively.     

X-ray absorption spectroscopic study on the electronic structure of Li(1)(-)(x)()CoPO(4) electrodes as 4.8 V positive electrodes for rechargeable lithium ion batteries

Changes in the electronic structure of olivine Li(1-x)CoPO(4), 4.8 V positive electrode material for lithium ion batteries, were investigated using the X-ray absorption spectroscopy (XAS) technique. The threshold energy in the Co K-edge increased with electrochemical Li removal, indicating the oxidation of cobalt ions due to charge compensation. Moreover, P and O K-edge XAS showed a slight shift in threshold energy with Li removal. Although it is generally believed that the electrons of PO(4) polyanion do not contribute to the oxidation process, present experimental results indicate changes in the electronic structure around PO(4) units. Such results would be interpreted by the idea of the hybridization effect between the Co 3d and O 2p orbitals and of the polarization effect introduced by Li ions.     

Investigation on the arrangement of lithium ions in LixLa(1/3)NbO3 with perovskite structure

The relationship between the Li arrangement and the electrochemical behavior has been examined as a function of composition x in electrochemically lithiated A-site deficient perovskite, Li(x)()La(1/3)NbO(3). The cell potential diagram and powder X-ray diffraction (XRD) study indicated that the Li ions are inserted into the vacant Perovskite A-site with an electrochemical reaction. In addition, the derivatives of the cell potential diagram showed three cathodic peaks, indicating a stepwise Li insertion mechanism takes place. Such a stepwise behavior would be ascribed to the changes in arrangement of inserted Li ions in the Perovskite lattice, since the XRD patterns of pristine La(1/3)NbO(3) showed that the La arrangement in La(1/3)NbO(3) was ordered along the c-axis, causing two kinds of A-site vacancies. To reveal the changes in the arrangement of Li ions, the entropy measurement of the reaction was performed by both the electrochemical and the calorimetric techniques. Moreover, the formation energy of the Perovskite structure with various Li arrangements was compared by using an ab initio calculation. The results of experiment and computation suggested that the electrochemical reaction proceeded via two kinds of superstructures of Li(1/6)La(1/3)NbO(3) and Li(1/2)La(1/3)NbO(3) due to the ordered arrangement of Li ions.     

Resonance effects on coherent phonon generation in lead phthalocyanine crystalline films

We report the first observation of coherent phonons in crystalline lead phthalocyanine (PbPc) films grown on a (0001) sapphire substrate by using a pump–probe technique. Coherent phonon oscillations corresponding to intermolecular (lattice) vibrations in the PbPc film are observed in the frequency region from 1 to 5 THz. It is found that the intensities of coherent phonons are resonantly enhanced at the exciton energies of the Q band observed in the absorption spectrum. PACS 78.47.+p; 78.66.-w; 82.53.Xa; 78.40.Me     

A direct electrochemical route to construct a polymer/manganese oxide layered structure

A layered nanocomposite with poly(diallyldimethylammonium), PDDA, intercalated between manganese oxide layers can be formed on a platinum electrode in a thin film form through a direct electrochemical route. The process involves a potentiostatic oxidation of aqueous Mn(2+) precursors in the presence of PDDA by applying a constant potential (+1.0 V vs Ag/AgCl).     

Photochemical regulation of the activity of an endonuclease BamHI using an azobenzene moiety incorporated site-selectively into the dimer interface

Endonuclease BamHI mutants having an azophenylalanine residue in the dimer interface (azoAla-BamHI) were synthesized; while the activity was almost suppressed using trans-azoAla-BamHI, the cis-isomer generated with photoirradiation recovered its intrinsic activity.     

Polarization-mode dispersion measurement by an optical time-domain reflectometer with polarimetry assuming backscattering by randomly oriented nonspherical particles

In previous work on polarization-mode dispersion (PMD) measurement with an optical time-domain reflectometer with polarimetry (p-OTDR), scatterers were assumed to be a cloud of small spherical particles in a fiber. We have found that the p-OTDR waveforms were fitted well by modified Mueller matrices, assuming scattering by a cloud of nonspherical particles. We realized a PMD measurement based on the p-OTDR Jones matrix eigenanalysis (JME) method. The measured PMD was consistent with that of JME standard measurement with transmission-type polarimetry.     

Measurement of Optical Constants of CVD-Diamond for Short-Wavelength Far-Infrared Lasers

A diagnostic system using short-wavelength far-infrared (FIR) lasers (40–70 m in wavelength) is now being developed for high density and large volume plasmas. In the wavelength region, a CVD-diamond is the excellent materials for optical windows of the laser and the plasma vessel and beam splitters of a multichannel interferometer. To design these optical elements, the optical constants (refractive index n, absorption coefficient and transmissivity T) of the CVD-diamond have been measured precisely by using FIR lasers of 48-, 57- and 71-m in wavelength. As an example, the result for 57.1511 m light is n = 2.383(1) ± 0.002, = 0.19 ± 0.05 cm^-1 and T = 97.5 ± 1.5% at 1.023 mm in thickness.