Synthesis and oxidation of 1,1,2,2-tetramethyl-3,4,5,6-tetraphenyl-1,2-disila-3,4-cyclohexadiene

The synthesis of 1,1,2,2-tetramethyl-3,4,5,6-tetraphenyl-1,2-disila-3,4-cyclohexadiene, (I), from 1,4-dilithiotetrapheynylbutadiene and 1,2-dichlorotetramethyldisilane is described. (I) is reluctant to react with singlet oxygen, in contrast to its carbon analogue, but the SiSi bond of(I) is readily oxidized to give 2,2,7,7-tetramethyl- 3,4,5,6-tetrapheynyl-1-oxo-2,7-disila-3,5-cycloheptadiene. The mechanism of the formation of this siloxane is discussed, and a peroxy radical shown to act as an important intermediate in the oxidation.     

Carbon-13 NMR spectra of some epoxides derived from dicyclopentadiene

The ¹³C NMR spectra of a series of epoxides derived from endo- and exo-dicyclopentadiene and their partially hydrogenated compounds were determined to examine the substituent effects arising from the introduction of the oxirane ring in comparison with those found in other ring systems. The ¹³C signals of some epoxides were assigned by using lanthanide shift reagents. Characteristic substituent effects exerted by an oxirane ring were demonstrated. Marked steric γ-effects of ?8—13 ppm were observed at the bridge carbon signal in the bicyclo[2.2.1]heptane skeleton. Differences were found in the substituent effects between endo- and exo-dicyclopentadiene epoxides, and have been discussed in relation to the molecular geometry.     

Broadly tunable UV-blue picosecond pulsed laser and its application for biological imaging

We have achieved a rapid and random wavelength tuned picosecond pulsed laser and a widely tunable UV-blue picosecond pulsed laser by using the intracavity second harmonic generation of the laser. The tuning range was from 384 to 434 nm with picosecond pulse oscillation. In addition, we demonstrated biological imaging using a fluorescent protein excited by the widely tunable UV-blue picosecond pulsed laser. We found that the laser is suitable for biological imaging using the fluorescent protein as an excitation light source without damages.     

Measurement of temporal changes in vocal tract area function from 3D cine-MRI data

A 3D cine-MRI technique was developed based on a synchronized sampling method [Masaki et al., J. Acoust. Soc. Jpn. E 20, 375-379 (1999)] to measure the temporal changes in the vocal tract area function during a short utterance /aiueo/ in Japanese. A time series of head-neck volumes was obtained after 640 repetitions of the utterance produced by a male speaker, from which area functions were extracted frame-by-frame. A region-based analysis showed that the volumes of the front and back cavities tend to change reciprocally and that the areas near the larynx and posterior edge of the hard palate were almost constant throughout the utterance. The lower four formants were calculated from all the area functions and compared with those of natural speech sounds. The mean absolute percent error between calculated and measured formants among all the frames was 4.5%. The comparison of vocal tract shapes for the five vowels with those from the static MRI method suggested a problem of MRI observation of the vocal tract: data from static MRI tend to result in a deviation from natural vocal tract geometry because of the gravity effect.     

Structures of 17,19-hexatriacontadiyne monolayers on Au(111) studied by infrared reflection absorption spectroscopy and scanning tunneling microscopy

The aggregation and reaction of 17,19-hexatriacontadiyne molecules are studied on a Au(111) surface. The molecular orientation and arrangement are elucidated by infrared reflection absorption spectroscopy (IRAS) and scanning tunneling microscopy (STM). A vapor-deposited monolayer and a multilayered film formed by adsorption from the solution provide IRA spectra with bands due to the antisymmetric and symmetric stretching of methylenes in the gauche conformation. After the adsorbed film is rinsed with the solvent, however, the spectrum loses the gauche bands and is characterized by the enhanced C-H(distal) and C-H(proximal) stretching bands, which means that all-trans molecules are laid flat. Only STM images for the rinsed film display columnar structures on the herringbones of the reconstructed Au(111) surface; the alkyl chain direction is found to be parallel to the Au atom row. The results indicate that an ordered monolayer is formed first at the liquid-solid interface, and then, disordered overlayers with the gauche conformation are grown but removed by a rinse. Upon exposure to UV light, thus obtained monomer columns are converted into oligomers with flexible backbones and an increased gauche population in the alkyl chains, which resemble red phase polydiacetylenes in LB films.     

Full counting statistics for a single-electron transistor: nonequilibrium effects at intermediate conductance

We evaluate the current distribution for a single-electron transistor with intermediate strength tunnel conductance. Using the Schwinger-Keldysh approach and the drone (Majorana) fermion representation, we account for the renormalization of system parameters. Nonequilibrium effects induce a lifetime broadening of the charge-state levels, which suppress large current fluctuations.     

Saturated ferromagnetism from statistical transmutation in two dimensions

The total spin of the ground state is calculated in the U-->infinity Hubbard model with uniform magnetic flux perpendicular to a square lattice, in the absence of Zeeman coupling. It is found that the saturated ferromagnetism emerges in a rather wide region in the space of the flux density phi and the electron density ne. In particular, the saturated ferromagnetism at phi=ne is induced by the formation of a spin-1/2 boson, which is a composite of an electron and the unit flux quantum.     

Infrared vibrational autodetachment spectroscopy of microsolvated benzonitrile radical anions

Vibrational spectra of microsolvated benzonitrile radical anions (C6H5CN- -S; S = H2O and CH3OH) were measured by probing the electron detachment efficiency in the 3 microm region, representing resonance bands of autodetachment via OH stretching vibrations of the solvent molecules. The hydrogen-bonded OH band for both the cluster anions exhibited a large shift to the lower energy side with approximately 300 cm-1 compared to those for the corresponding neutral clusters. The solvent molecules are bound collinearly to the edge of the CN group of the benzonitrile anion in the cluster structures optimized with the density functional theory, in which the simulated vibrational energies are in good agreement with the observed band positions. Natural population analyses were performed for a qualitative implication in changes of solvent orientation upon electron attachment. Asymmetric band shapes depending on the vibrational modes are discussed with respect to dynamics of the autodetachment process from a theoretical aspect incorporated with density functional calculations.     

Negative viscosity due to magnetic properties of a non-dilute suspension composed of ferromagnetic rod-like particles with magnetic moment normal to the particle axis

The negative viscosity of a colloidal dispersion composed of ferromagnetic rod-like particles, which have a magnetic moment normal to the particle axis, have been investigated. A simple shear flow problem has been treated to clarify the particle orientational distribution and rheological properties of such a semi-dense dispersion, under circumstances of an external magnetic field applied in the direction normal to the shear plane of a simple shear flow. The results obtained here are summarized as follows. For the cases of a very strong magnetic field and magnetic interactions between particles, the magnetic moment of the rod-like particles is significantly restricted in the magnetic field direction, so that the particle approximately aligns in the shear flow direction. Also, the particle can easily rotate around the axis of the cluster almost freely even in a simple shear flow. Characteristic orientational properties of the particle cause negative viscosity, as in the previous study for a dilute dispersion. However, magnetic particle-particle interactions have a function to make such negative viscosity decrease.