The influence of the O–O isotope substitution on spin dynamics of (La0.25Pr0.75)0.7Ca0.3MnO3: La NMR data

The ¹³⁹La NMR spectra and spin–spin relaxation times have been measured for the ¹⁶O and ¹⁸O isotope-substituted manganite (La_0.25Pr_0.75)_0.7Ca_0.3MnO₃ in the external magnetic field of 5 T. The NMR signal wipe-out has been observed in the ¹⁸O-enriched sample in the charge-ordered state. This phenomenon is connected with a sharp increase in the spin–spin relaxation rate. The great isotope-effect observed provides a clear evidence of an essential role of oxygen motion in controlling the long-range magnetic order in manganites.     

Expanding stereochemical and skeletal diversity using petasis reactions and 1,3-dipolar cycloadditions

A short and modular synthetic pathway using intramolecular 1,3-dipolar cycloaddition reactions and yielding functionalized isoxazoles, isoxazolines, and isoxazolidines is described. The change in shape of previous compounds and those in this study is quantified and compared using principal moment-of-inertia shape analysis.     

Relations of electronic energies and magnetic moments of tetra-3d metal (Mn, Fe, Co and Ni) nitrides calculated using a plane-wave basis method

Geometrical optimization of tetra-3d metal nitrides (Mn₄N, Fe₄N, Co₄N, and Ni₄N) has been performed and the relations of their energies (E) and their total magnetic moments (M) are obtained by plane-wave-basis density-functional calculations without any assumption of specific spin arrangement. The E vs. M relations obtained for Fe₄N and Mn₄N have a bimodal character. The ground state of Fe₄N is a high-spin state, which would correspond to the ferromagnetic character, while that of Mn₄N is a low-spin state, which would correspond to the observed ferrimagnetic character. Lattice constants and total magnetic moments of these tetra-3d metal nitrides are almost accurately predicted. From the spin-polarized densities of states curves, Co₄N would have the largest spin polarization ratio of 0.88, which suggests Co₄N can be a candidate material for ferromagnetic electrodes for spin-injection.     

Photoassisted chemical solution deposition method for fabricating uniformly epitaxial VO2 films

Epitaxial VO₂ films were prepared on the TiO₂ (001) substrates by the excimer-laser-assisted metal–organic deposition (ELAMOD). The quality of the epitaxial films obtained by irradiation with a KrF laser was found to be affected by the film structure obtained after preheating at 500 or 300°C. When the films containing crystal domains, which were obtained by preheating at 500°C, were irradiated with the laser at room temperature under a base pressure of 250 Pa, epitaxial and polycrystalline VO₂ phases were simultaneously formed. In contrast, when the amorphous films containing organic components, which were obtained by preheating at 300°C, were irradiated with the laser at room temperature in air, a single phase of epitaxial VO₂ was formed. By using thermal simulations, we determined that the formation of the epitaxial phase was affected both by the temperature distribution within the film during the laser irradiation and by the laser intensity at the interface between the substrate and the film. The latter factor is considered to play a role in the nucleation of crystallization, causing the epitaxial phase to form preferentially compared to the polycrystalline phase in the amorphous matrix of the films. These results indicate that the ELAMOD process is effective for the fabrication of epitaxial VO₂ films at low temperature.     

Direct observation of the target cell for jasmonate-type leaf-closing factor: genus-specific binding of leaf-movement factors to the plant motor cell

We report the synthesis of the novel fluorescence-labeled jasmonate glycoside 2 based on β-d-glucopyranosyl 12-hydroxyjasmonate 1, which is a leaf-closing substance of Albizzia julibrissin Durazz. The fluorescence study using 2 revealed that the target cell for 1 is a motor cell. Probe 2 bound to the motor cells of two plants belonging to genus Albizzia. This result suggested that a receptor for 2, which is common among genus Albizzia would be involved in the nyctinastic leaf movement.     

In situ x-ray diffraction measurements of the capillary fountain jet produced via ultrasonic atomization

In situ x-ray diffraction measurements were carried out for investigating the liquid structure in the ultrasonic fountain jet to consider the mechanism of the "ultrasonic ethanol separation" reported by Sato et al. [J. Chem. Phys. 114, 2382 (2001)]. For pure liquids (water and ethanol), it was found that the high frequency ultrasound does not affect the liquid structure microscopically. For the 20 mol % ethanol-water mixture, the estimated ethanol mole fraction in the ultrasonic fountain jet by using the position of the main maximum in the x-ray diffraction profile coincided with that in the reservoir. This result suggests that the ethanol separation is not caused by any distorted liquid structure under the ultrasound irradiation and occurs when or after the generation of the liquid droplet mist.     

A practical and facile synthesis of azetidine derivatives for oral carbapenem, L-084

An orally active carbapenem L-084, which exhibits high bioavailability in humans, has a 1-(1,3-thiazolin-2-yl)azetidin-3-ylthio moiety at the C-2 position of the 1beta-methylcarbapenem skeleton. We established a practical and cost-effective synthesis of 3-mercapto-1-(1,3-thiazolin-2-yl)azetidine (1) for further scale-up production of L-084. This synthesis method entails an industry-oriented reaction of azetidine ring-closure to yield N-benzyl-3-hydroxyazetidine (16), which is eventually converted to 1 via key intermediates, Bunte salts 19 and 20.     

Efficient synthesis of isothiocyanates based on the tandem Staudinger/aza-Wittig reactions and mechanistic consideration of the tandem reactions

The tandem and stepwise Staudinger/aza-Wittig reactions of several azides were examined in detail. The tandem reaction method (Method I) exhibited superior results in the yield of the corresponding isothiocyanates bearing an electron-withdrawing group than the conventional stepwise method (Method II) which involves the sequential treatment of the azides with triphenylphosphine and then carbondisulfide. The mechanistic consideration for both reaction methods was proposed on the basis of the 1H-NMR analyses.     

Synthesis of tetrasubstituted and functionalized enol ethers by E-selective olefination of esters with ynolates

We have developed the E-selective olefination of ester carbonyls to afford tetrasubstituted, functionalized olefins and the C-S insertion of thiol esters to give beta-keto thiol esters via ynolates.