Synthesis of 2-substituted 4,5-dihydro-4-oxo-3-furancarboxylates using acylative intramolecular cyclization of sulfonium salts

A simple and efficient synthesis of 4,5-dihydro-4-oxo-3-furancarboxylates using an acylative intramolecular cyclization of sulfonium salts is described. The reaction involved the efficient formation of a mixed anhydride between a linear carboxylic acid and trifluoroacetic anhydride in the presence of N-methylimidazole, followed by the sequential conversion into a highly reactive acylammonium species in situ. This procedure is easily handled, uses readily available inexpensive reagents, and provides a variety of 2-substituted 4,5-dihydro-4-oxo-3-furancarboxylates.     

Discovery of Hexagonal Structured Pd–B Nanocrystals

We report on hexagonal close-packed (hcp) palladium (Pd)–boron (B) nanocrystals (NCs) by heavy B doping into face-centered cubic (fcc) Pd NCs. Scanning transmission electron microscopy–electron energy loss spectroscopy and synchrotron powder X-ray diffraction measurements demonstrated that the B atoms are homogeneously distributed inside the hcp Pd lattice. The large paramagnetic susceptibility of Pd is significantly suppressed in Pd–B NCs in good agreement with the reduction of density of states at Fermi energy suggested by X-ray absorption near-edge structure and theoretical calculations.     

Synthesis and photophysical properties of luminescent mononuclear and dinuclear gold(I) complexes with ethynyl-substituted phenanthrolines

A novel asymmetric dinuclear gold(I) complex with 3,6-diethynylphenanthroline, 3,6-bis{(PPh₃)–Au–C≡C}₂-phen, has been synthesized from Au(PPh₃)Cl (PPh₃ = triphenylphosphine) and 3,6-diethynyl-1,10-phenanthroline. The asymmetrical dinuclear gold(I) complex, 3,6-bis{(PPh₃)–Au–C≡C}₂-phen, demonstrated a weak phosphorescence assignable to the metal-perturbed ³ π–π* transition in the long wavelength region compared to an intense emission of the symmetrical dinuclear complex with 3,8-diethynylphenanthroline, 3,8-bis{(PPh₃)–Au–C≡C}₂-phen. A similar tendency of phosphorescent bands for the mononuclear gold(I) complexes with 5-ethynylphenanthroline, 5-{(PPh₃)–Au–C≡C}-phen, and 3-ethynylphenanthroline, 3-{(PPh₃)–Au–C≡C}-phen was observed. The absorption bands assignable to the π–π*(C≡Cphen) transition and phosphorescent emission assignable to the metal-perturbed ³ π–π* transition for these four gold(I) complexes were reasonably consistent with the results calculated by DFT and TD-DFT.     

A thermodynamic consistency test for the binary constant-temperature VLE data using numerically optimized binary parameters

A thermodynamic consistency (TC) test for the constant-temperature VLE data was investigated by numerically optimizing the binary parameters of the activity coefficient equations to satisfy the Gibbs–Duhem (GD) equation. It was shown that the one parameter Margules equation can best satisfy the GD equation, even if significant experimental errors are involved. A thermodynamic consistency (TC) criterion was defined using the one parameter Margules equation. The TC criterion showed that, of the 37 alkane–alkane, 18 methanol–water and 44 ethanol–water binaries, 36, 16 and 1 binaries are reliable, respectively. Simple liquid mixtures meet the TC criterion.     

First direct visualization of spillover species emitted from pt nanoparticles

We studied the methanol adsorption behavior of Pt nanoparticles that were vacuum-deposited on a TiO(2)(110) surface at room temperature by using an ultrahigh vacuum (UHV) scanning tunneling microscope (STM). A large number of bright spots were observed on fivefold-coordinated Ti (Ti(5c)) rows of the TiO(2)(110) surface after exposure of the Pt/TiO(2)(110) to methanol vapor. We assigned the bright spots to methoxy species. These were mobile and were found to hop along the Ti(5c) rows. In situ time-resolved STM observations of the formation and migration of the bright spots on the Pt/TiO(2)(110) were carried out in the presence of methanol. The bright spots were produced at the periphery of the Pt nanoparticles and migrated to the substrate Ti(5c) rows. We discuss the spillover process and behavior of the methoxy species on the Pt/TiO(2)(110).     

Establishment of absolute stereostructure of falcarindiol, algicidal principle against Heterocapsa circularisquama from Notopterygii Rhizoma

Falcarindiol (1) was isolated as an algicidal principle against the harmful red tide dinoflagellate, Heterocapsa circularisquama, from Notopterygii Rhizoma through bioassay-guided separation. In order to determine the ambiguous absolute structure of this active principle, all three stereoisomers as well as falcarindiol (1) were synthesized. As a result of intensive analysis of their physicochemical properties, the configuration of 1 was revealed to be 3R,8S. On the other hand, (3S,8S)- and (3S,8R)-isomers were found to exhibit more potent algicidal activity than (3R,8S)-falcarindiol (1) isolated from Notopterygii Rhizoma. In addition, the diyne moiety of 1 was established as the crucial structural requirement for algicidal potency.     

The perception of Arabic and Japanese short and long vowels by native speakers of Arabic, Japanese, and Persian

This study examines the perception of short and long vowels in Arabic and Japanese by three groups of listeners differing in their first languages (L1): Arabic, Japanese, and Persian. While Persian uses the same alphabet as Arabic and Iranian students learn Arabic in school, the two languages are typologically unrelated. Further, unlike Arabic or Japanese, vowel length may no longer be contrastive in modern Persian. In this study, a question of interest was whether Persian listeners' foreign language learning experience or Japanese listeners' L1 phonological experience might help them to accurately process short and long vowels in Arabic. In Experiment 1, Arabic and Japanese listeners were more accurate than Persian listeners in discriminating vowel length contrasts in their own L1 only. In Experiment 2, Arabic and Japanese listeners were more accurate than Persian listeners in identifying the length categories in the "other" unknown language as well as in their own L1. The difference in the listeners' perceptual performance between the two experiments supports the view that long-term L1 representations may be invoked to a greater extent in the identification than discrimination test. The present results highlight the importance of selecting the appropriate test for assessing cross-language speech perception.     

Reduced crystallization time of YBCO in a fluorine-free MOD process using uv-lamp irradiation

We have studied the crystallization time dependence of the epitaxial YBCO films (t = 0.8 μm) grown on CeO₂-buffered SrTiO₃ substrates by fluorine-free metal–organic deposition using uv-lamp irradiation (uv-MOD). As increasing the time (T₀) for heat treatment at the reaction temperature (760 °C) from 0 to 90 min, J_c and the YBCO 0 0 l XRD intensity are steeply increased and reach their maximum values at T₀ = 10 min. This suggests that the heat treatment required for YBCO crystallization is significantly shortened in uv-MOD compared to conventional all-pyrolytic F-free MOD processes, which consume T₀ = 90–150 min for crystallizing 0.4–0.5-μm-thick films. Scanning electron microscope measurement revealed a drastic change in surface morphology between T₀ = 8 and 10 min, showing a good correspondence to the J_c and XRD data which suggest that the epitaxial growth reaches the film surface at the very early stage in the heat treatment.     

Hall effect of FeTe and Fe(Se1–xTex) thin films

The Hall effect is investigated in thin-film samples of iron–chalcogenide superconductors in detail. The Hall coefficient (R_H) of FeTe and Fe(Se_1–xTe_x) exhibits a similar positive value around 300 K, indicating that the high-temperature normal state is dominated by hole-channel transport. FeTe exhibits a sign reversal from positive to negative across the transition to the low-temperature antiferromagnetic state, indicating the occurrence of drastic reconstruction in the band structure. The mobility analysis using the carrier density theoretically calculated reveals that the mobility of holes is strongly suppressed to zero, and hence the electric transport looks to be dominated by electrons. The Se substitution to Te suppresses the antiferromagnetic long-range order and induces superconductivity instead. The similar mobility analysis for Fe(Se_0.4Te_0.6) and Fe(Se_0.5Te_0.5) thin films shows that the mobility of electrons increases with decreasing temperature even in the paramagnetic state, and keeps sufficiently high values down to the superconducting transition temperature. From the comparison between FeTe and Fe(Se_1–xTe_x), it is suggested that the coexistence of ‘itinerant’ carriers both in electron and hole channels is indispensable for the occurrence of superconductivity.