Stability of lithium in α-rhombohedral boron

The stability of lithium atoms in α-rhombohedral boron was studied by the density functional theory and Car-Parrinello molecular dynamics (MD) simulations. At a low Li concentration (1.03 at%), a Li atom at the center of the icosahedral B₁₂ site (the I-site) was found to be metastable, and the potential barrier was estimated at 775±25 K (=67±25 meV). Over 800 K, Li atoms began to escape from the B₁₂ cage and settled at the tetrahedral site (the T-site) or at the octahedral site (the O-site). Li at the T-site was also metastable below 1400 K, and Li at the O-site was energetically the most favorable. At a high Li concentration (7.69 at%), the I-site changed to an unstable saddle point. The T-site was still metastable, and the O-site was the most stable. Regardless of concentration, MD simulations showed that Li atoms at the O-site never jumped to other sites below 1400 K. The migration of Li would be very slow below this temperature.     

Ethylene hydroformylation over a nafion-supported rhodium catalyst

Ethylene hydroformylation over a Nafion-supported rhodium catalyst has been studied under atmospheric pressure in the temperature range of 100–135 °C, using the transient response method.

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Analysis of detected signal performance in multi-tracks of optical disk memory using convex-shaped recording mark

The possibility of multi-valued optical disk memory by using a convex-shaped recording mark fabricated by two-photon absorption is investigated. We fabricate a numerical model for convex-shaped recording marks and evaluate the signal characteristics in terms of the signal-to-noise ratio (SNR). The numerical results show that 6 bit data can be realized when the acceptable average SNR is 2 and a length of the mark is 4T.     

Optical Coherence Tomographic Features of Macular Diseases

Optical coherence tomography (OCT) is a new diagnostic technology which allows visualization of a cross-sectional image of the anterior eye and the retina in vivo with a high resolution similar to a histological section by light microscopy. Although the fundus can be examined at the semihistologic level by a biomicroscope, histopathologic study has been difficult because of the rare opportunity for retinal biopsy or enucleation. OCT reveals the intraretinal structure of macular diseases on the histopathologic level. In this article, we review the research on various macular diseases using OCT at Gunma University School of Medicine.     

Terahertz surface-wave resonant sensor with a metal hole array

A surface-wave sensor based on the resonant transmission characteristics of metal hole arrays is demonstrated in the terahertz (THz) region. Since the frequency of the transmission peak of a metal hole array, which corresponds to the resonant frequency of the surface waves, is particularly sensitive to the refractive index in the vicinity of the metal surface, a very small change in the substances attached to the surface can be detected by monitoring the transmission spectrum. By attaching a layer of substance (thickness t < 5 microm) much thinner than the wavelength of the THz wave (lambda(THz) = 1 mm at 0.3 THz) to the surface of a metal hole array, we demonstrated that the existence of such a small amount of substance can be detected more easily than without the metal hole array. This demonstration of THz sensing with metal hole arrays indicates the possibility of realizing THz surface-wave sensors for biochemical molecules in the THz region.     

Water-stable helical structure of tertiary amides of bicyclic β-amino acid bearing 7-azabicyclo[2.2.1]heptane. Full control of amide cis-trans equilibrium by bridgehead substitution

Helical structures of oligomers of non-natural β-amino acids are significantly stabilized by intramolecular hydrogen bonding between main-chain amide moieties in many cases, but the structures are generally susceptible to the environment; that is, helices may unfold in protic solvents such as water. For the generation of non-hydrogen-bonded ordered structures of amides (tertiary amides in most cases), control of cis-trans isomerization is crucial, even though there is only a small sterical difference with respect to cis and trans orientations. We have established methods for synthesis of conformationally constrained β-proline mimics, that is, bridgehead-substituted 7-azabicyclo[2.2.1]heptane-2-endo-carboxylic acids. Our crystallographic, 1D- and 2D-NMR, and CD spectroscopic studies in solution revealed that a bridgehead methoxymethyl substituent completely biased the cis-trans equilibrium to the cis-amide structure along the main chain, and helical structures based on the cis-amide linkage were generated independently of the number of residues, from the minimalist dimer through the tetramer, hexamer, and up to the octamer, and irrespective of the solvent (e.g., water, alcohol, halogenated solvents, and cyclohexane). Generality of the control of the amide equilibrium by bridgehead substitution was also examined.     

Coupling of Alkynes on a Pd-Pd Bond to Generate an Electrophilic µ-Butenediylidene Moiety

The first dipalladium μ-PPh(3) complex (1) was obtained by the facile loss of two CH(3)CN ligands from [Pd(2)(PPh(3))(2)(CH(3)CN)(4)](PF(6))(2) in CH(2)Cl(2). Coupling of p-tolylacetylene (p-TolC identical withCH) with 1 or its precusor afforded the μ-butenediylidene complex 2, treatment of which with CH(3)CN resulted in PPh(3) migration to give 3.     

Surface phonons of LaB6(100): deformation of boron octahedra at the surface

The surface phonon dispersion of clean LaB₆(100) surface has been measured by means of high resolution electron energy loss spectroscopy. Eight vibrational modes, of which most are located in the energy gaps between the bulk phonon bands, have been detected. The lattice dynamical calculation of a slab-shaped crystal based on a force constant model has reproduced these experimental dispersion curves, which indicates the large increase in the force constant of interoctahedral boron-boron bond at the surface by 25%, and the large decrease in the force constants of intraoctahedral boron-boron bonds at the surface by 25–50%. These changes together with the analysis of the bulk phonon structure of metal hexaborides strongly suggest that the boron octahedra at the surface are expanded by about 0.004 nm parallel to the surface.