Novel high‐temperature reactors for in situ studies of three‐way catalysts using turbo‐XAS

Two novel high‐temperature reactors for in situ X‐ray absorption spectroscopy (XAS) measurements in fluorescence are presented, each of them being optimized for a particular purpose. The powerful combination of these reactors with the turbo‐XAS technique used in a dispersive‐XAS beamline permits the study of commercial three‐way catalysts under realistic gas composition and temporal conditions.     

Alkaline metal ion-enhanced chemiluminescence of bicyclic dioxetanes bearing a hydroxyaryl group with an ‘even’ substitution pattern

Bicyclic dioxetane 5 bearing a 3-hydroxynaphthalen-2-yl group and its analogs 14 and 15 decomposed to give light with efficiencies of only 0.002-0.005% in a tetrabutylammonium fluoride (TBAF)/THF system, which was as expected for dioxetanes with a so-called ‘even’ substitution pattern. However, the chemiluminescence efficiencies (Φ^CL) markedly increased when these dioxetanes were decomposed with alkaline metal t-butoxide in THF. This enhancement of Φ^CL by alkaline metal ion was most likely due to the highly ordered conformation of an aromatic ring by chelate formation of the metal ion with both an oxido anion and oxygen atom of a tetrahydrofuran ring in an intermediary dioxetane like 12. Alkaline metal ion-enhanced chemiluminescence was similarly observed for dioxetane 6 bearing a 2-hydroxyphenyl group.     

TeV-scale seesaw from a multi-Higgs model

We suggest new simple model of generating tiny neutrino masses through a TeV-scale seesaw mechanism without requiring tiny Yukawa couplings. This model is a simple extension of the standard model by introducing extra one Higgs singlet, and one Higgs doublet with a tiny vacuum expectation value. Experimental constraints, electroweak precision data and no large flavor changing neutral currents, are satisfied since the extra doublet only has a Yukawa interaction with lepton doublets and right-handed neutrinos, and their masses are heavy of order a TeV-scale. Since active light neutrinos are Majorana particles, this model predicts a neutrinoless double beta decay.     

Effect of hydroxyl impurity on temperature coefficient of refractive index of synthetic silica glasses

We have studied the temperature coefficient of the refractive index of synthetic silica glasses with various hydroxyl impurities. The refractive index was measured at 15 °C and 35 °C at 1.707–0.238 μm wavelengths. The temperature coefficient of a low-OH group (110 wt. ppm) containing glass increased from 8.0 ± 0.2 × 10^?6/°C (at 1.707 μm) to 14.0 ± 0.2 × 10^?6/°C (at 0.238 μm), although it increased respectively from 7.0 ± 0.2/°C to 12.0 ± 0.2 × 10^?6/°C for a high-OH group (1300 wt. ppm) containing glass. The three-term Sellmeier equation, having two terms with resonance photon energies in the vacuum ultraviolet region and one term in the infrared region, was used to analyze the wavelength dispersion of the refractive index. Increasing temperatures shifted the resonance energy in the second term by ?4.14 ± 0.4 × 10^?4 eV/°C for low-OH (110 wt. ppm) glass and ?2.64 ± 0.4 × 10^?4 eV/°C for high-OH (1300 wt. ppm) glass. The fundamental absorption edge in the vacuum ultraviolet region shifted by ?8.8 ± 0.7 × 10^?4 eV/°C for the low-OH glass and ?6.3 ± 0.7 × 10^?4 eV/°C for the high-OH glass in a region of 25–100 °C. Both high-OH glass shift rates were lower than low-OH glass shift rates. The lower temperature coefficient for the Si–OH-related band probably explains the smaller temperature coefficient for high-OH glass: the absorption band of Si–O–H structure is located at lower energy side close to the fundamental absorption band associated with the Si–O–Si structure.     

Contributions to osteoclast biology from Japan

Bone is a dynamic tissue, in which bone formation by osteoblasts and bone resorption by osteoclasts continue throughout life. In 1998, we molecularly cloned osteoclast differentiation factor (ODF), a long-thought factor responsible for osteoclast formation. This review article describes how Japanese scientists contributed to osteoclast biology before and after the discovery of ODF. This review article is based on the Louis V. Avioli Memorial Lecture of the American Society for Bone and Mineral Research (ASBMR) held in Honolulu in September, 2007.     

Thermal and ionic‐conductive behaviors of liquid crystalline polymers with alkali metal salt

In order to investigate the relationship between ionic conductivity and liquid crystallinity, we prepared the main‐chain type polyester having 1,4‐bisstyrylbenzene units and ethyleneoxide chain in the repeating unit. The main‐chain type polyester with lithium salt at the ratio of 0.04 per polymer repeating unit exhibited a smectic phase. However, the polyester with lithium salt (0.11) showed a nematic phase. The ionic conductivity of the polyester with lithium salt increased with increasing lithium salt concentration. The trans‐type polyester exhibited a liquid crystalline phase, while the cis‐type polyester did not show any mesophase. We found that the ionic conductivity of the trans‐type polyester with lithium salt (0.11) was larger than that of the cis‐type polyester with lithium salt (0.11). However, a liquid crystalline phase was found in the side‐chain type polyether with alkoxy chain length of below 12. A smectic phase was induced for the non‐mesomorphic polyethers with lithium salt. The layer spacing of the smectic A phase for the non‐mesomorphic polyether with lithium salt decreased from 55 to 41 Å with increasing temperature. The ionic conductivity of the polyether with lithium salt increased with decreasing the layer spacing. Copyright © 2001 John Wiley & Sons, Ltd.     

Multidimensional umbrella sampling and replica‐exchange molecular dynamics simulations for structure prediction of transmembrane helix dimers

Structural information of a transmembrane (TM) helix dimer is useful in understanding molecular mechanisms of important biological phenomena such as signal transduction across the cell membrane. Here, we describe an umbrella sampling (US) scheme for predicting the structure of a TM helix dimer in implicit membrane using the interhelical crossing angle and the TM–TM relative rotation angles as the reaction coordinates. This scheme conducts an efficient conformational search on TM–TM contact interfaces, and its robustness is tested by predicting the structures of glycophorin A (GpA) and receptor tyrosine kinase EphA1 (EphA1) TM dimers. The nuclear magnetic resonance (NMR) structures of both proteins correspond to the global free‐energy minimum states in their free‐energy landscapes. In addition, using the landscape of GpA as a reference, we also examine the protocols of temperature replica‐exchange molecular dynamics (REMD) simulations for structure prediction of TM helix dimers in implicit membrane. A wide temperature range in REMD simulations, for example, 250–1000 K, is required to efficiently obtain a free‐energy landscape consistent with the US simulations. The interhelical crossing angle and the TM–TM relative rotation angles can be used as reaction coordinates in multidimensional US and be good measures for conformational sampling of REMD simulations. © 2013 Wiley Periodicals, Inc.     

Electronic and infrared spectroscopy of [benzene-(methanol)(n)](+) (n = 1-6)

The microsolvation structure of the [benzene-(methanol)(n)](+) (n = 1-6) clusters was analyzed by electronic and infrared spectroscopy. For the n = 1 and 2 clusters, further spectroscopic investigation was carried out by Ar atom attachment, which has been know as a useful technique for discriminating isomers of the clusters. The coexistence of multiple isomers was confirmed for the n = 1 and 2 clusters, and remarkably, preferential production of the specific isomers occurred in the Ar attachment. The most stable isomer of the n = 1 cluster was suggested to be of the "on-ring" structure where the nonbonding electrons of the methanol moiety directly interact with the pi orbital of the benzene cation moiety. This is a sharp contrast to [benzene-(H(2)O)(1)](+), exhibiting the "side" structure, where the water moiety is bound to the C-H sites of the benzene cation moiety. The structure of the n = 2 cluster was discussed with the help of density functional theory calculations. Spectral signatures of the intracluster proton-transfer reaction were found for n > or = 5. The intracluster electron-transfer reaction leading to the (methanol)(m)()(+) fragment was also seen upon vibrational and electronic excitation of n > or = 4.     

New electron states that float on semiconductor and metal surfaces

We report first-principle electronic-structure calculations using the local density approximation in the density functional theory for Si(1 0 0) and Al(1 0 0) surfaces. We find a novel class of surface electron states that are distributed not near atomic arrays but float around with the maximum amplitudes being substantially separated from matters. We also find that the origin of the unusual character is quantum spill of electron density from matters and exchange-correlation effects among electrons.     

Memory of chirality generated by spontaneous crystallization and asymmetric synthesis using the frozen chirality

Asymmetric synthesis using frozen chirality generated by spontaneous crystallization was performed. Achiral asymmetrically substituted imide with a tetrahydronaphthyl group on the nitrogen atom crystallized in a chiral fashion, with space group P2(1)2(1)2(1). The molecular chirality generated by spontaneous crystallization was retained in cold THF. The half-life determined on the basis of decreasing optical activity followed by CD spectrometer was 7.8, 33.1, and 150.0 min at -20, -30, -40 degrees C, respectively. The energy barrier (DeltaG()) of racemization was calculated with the temperature dependence of the kinetic constant to be 18.24-18.36 kcal mol(-)(1) at 233-253 K. The memorized frozen chirality was transferred to permanent optically active alcohols by nucleophilic addition with n-buthyllithium.