In situ time-resolved XAFS study on the structural transformation and phase separation of Pt3Sn and PtSn alloy nanoparticles on carbon in the oxidation process

The dynamic behavior and kinetics of the structural transformation of supported bimetallic nanoparticle catalysts with synergistic functions in the oxidation process are fundamental issues to understand their unique catalytic properties as well as to regulate the catalytic capability of alloy nanoparticles. The phase separation and structural transformation of Pt(3)Sn/C and PtSn/C catalysts during the oxidation process were characterized by in situ time-resolved energy-dispersive XAFS (DXAFS) and quick XAFS (QXAFS) techniques, which are element-selective spectroscopies, at the Pt L(III)-edge and the Sn K-edge. The time-resolved XAFS techniques provided the kinetics of the change in structures and oxidation states of the bimetallic nanoparticles on carbon surfaces. The kinetic parameters and mechanisms for the oxidation of the Pt(3)Sn/C and PtSn/C catalysts were determined by time-resolved XAFS techniques. The oxidation of Pt to PtO in Pt(3)Sn/C proceeded via two successive processes, while the oxidation of Sn to SnO(2) in Pt(3)Sn/C proceeded as a one step process. The rate constant for the fast Pt oxidation, which was completed in 3 s at 573 K, was the same as that for the Sn oxidation, and the following slow Pt oxidation rate was one fifth of that for the first Pt oxidation process. The rate constant and activation energy for the Sn oxidation in PtSn/C were similar to those for the Sn oxidation in Pt(3)Sn/C. In the PtSn/C, however, it was hard for Pt oxidation to PtO to proceed at 573 K, where Pt oxidation was strongly affected by the quantity of Sn in the alloy nanoparticles due to swift segregation of SnO(2) nanoparticles/layers on the Pt nanoparticles. The mechanisms for the phase separation and structure transformation in the Pt(3)Sn/C and PtSn/C catalysts are also discussed on the basis of the structural kinetics of the catalysts themselves determined by the in situ time-resolved DXAFS and QXAFS.     

Enzymatic epoxide-opening cascades catalyzed by a pair of epoxide hydrolases in the ionophore polyether biosynthesis

Our recent findings of the first epoxide hydrolase Lsd19, involved in lasalocid A biosynthesis, led us to investigate a long-standing controversial issue on the mechanism of enzymatic epoxide-opening cascades. The site-directed mutagenesis and domain dissection analysis to reveal the mechanism of the reaction catalyzed by Lsd19 is examined, especially in the role of acidic amino acid pair and catalytic domains.     

Visualization of the non-steady state oblique detonation wave phenomena around hypersonic spherical projectile

We studied experimentally the shock waves and combustion waves generated by a hypersonic spherical projectile in an explosive mixture. An acetylene/oxygen mixture diluted with argon (2C₂H₂ + 5O₂ + 7Ar) was used with various initial pressures (detonation cell sizes) to observe optically with a shadowgraph imaging system a shock-induced combustion (SIC), a stable oblique detonation wave (ODW), and a wave called a Straw Hat type consisting of a strong SIC and ODW. The criticality of stabilizing an ODW around a projectile is expressed by the ratio of the projectile diameter, d, to the cell size, λ, as d/λ = 3.63–4.84. Although the Straw Hat type wave in the vicinity of criticality is an unstable phenomena, it has been mainly observed by a single frame picture to date, so that it is difficult to discuss the time history of its wave structure. In this study, it was remarkable to directly carry out continuous optical observations using a high speed video camera which can continuously film 100 pictures with a 1 μs frame speed so as to allow an investigation of the sustaining mechanism of the unstable wave structure. Our results allowed the identification of an increase in unsteadiness in the relative distance between the projectile fronts and the transition points to an ODW as the time increased. They also showed local explosions in the SIC region near transition point transformed the ODW front upstream.     

Strong X-ray emission from electrified insulators.

Terasawa reported strong X-ray emission from charged-up insulators, and proposed an X-ray production device only using the electrification. We constructed a similar device and studied the conditions of X-ray emission. It was shown that X-rays could be produced without supplying electrons from a filament.     

Triterpenes and flavonol glucuronides from Oenothera cheiranthifolia

A new ursane-type triterpene, named as cheiranthic acid (1), was isolated from the MeOH extract of whole plants of Oenothera cheiranthifolia (Onagraceae) along with an isomeric pair of known oleanane- and ursane-type triterpenes (arjunolic acid and asiatic acid) and three flavonol glucuronide analogues (quercetin 3-O-glucuronide, its n-butyl ester, and myricetin 3-O-glucuronide). Their structures were elucidated based on spectroscopic evidence.     

Anomalous magnetoresistance in 1T-TaS2

Transverse magnetoresistance of 1T-TaS₂ was measured in magnetic fields up to 100 kOe in the semiconductive region corresponding to the commensurate charge density wave (CDW) state.