Photocycloaddition of acetylacetonatoboron derivatives with simple olefins

Acetylacetonatoboron difluoride (AABF₂) and oxalate (AABO) undergo cycloaddition from their singlet excited state with cyclic and terminal olefins to give stereospecific but non-regiospecific products; the latter oxalate reacted slightly faster than the former difluoride. A conjugated diene, 1,3-cyclooctadiene, and methyl substituted benzenes also reacted similarly but with slower rates owing to electron transfer at the encounter stage. The resulting radical ion pairs may undergo radical ion type reactions and/or reverse electron transfer, which leads to the partial waste of the photoenergy. For the same reasons, the reaction occurs more efficiently in non-polar solvents, such as ether, dioxane and methylene chloride than in acetonitrile.     

The first total synthesis and structural determination of (+)-BE-52440A

The first total synthesis and structural determination of (+)-BE-52440A have been achieved by enantiodivergent synthesis. S-Bridging dimerization including S_N2 epoxy-opening reaction of tetrasubstituted epoxide 2 with sodium sulfide has been achieved in excellent yield with high regioselectivity. The structure of (+)-BE-52440A was determined to be the dimer of kalafungin type pyranonaphthoquinone.     

Angle-resolved and resonant photoemission study of the ZrO-like film on ZrC(1 0 0)

Angle-resolved photoemission spectroscopy (ARPES) and resonant photoemission spectroscopy (RPES) have been used to study the electronic structure of the ZrO-like film formed on a ZrC(1 0 0) surface. It is found that, in addition to the O 2p band observed at 6-8 eV, states exist at 0.15 and 0.75 eV around the point. ARPES measurements show that the states at 0.15 and 0.75 eV disperse towards the lower binding energy side and cross the Fermi level along the direction. RPES measurements show that the former state shows a resonant behavior characteristic of the intra-atomic Zr 4d resonance, suggesting that the state includes substantial contribution of Zr 4d orbitals. On the other hand, the latter state shows a resonant behavior similar to that of the O 2p state in ZrO. The resonance is thought to be caused through the inter-atomic deexcitation mechanism involving the emissions of O 2p electrons, and thus the latter state is ascribed to that mostly composed of the O 2p component.     

Cryopreservation of basal stem buds of in vitro-grown mat rush (Juncus spp.) by vitrification

An optimal protocol for the cryopreservation of in vitro-grown mat rush (igusa) buds by vitrification has been successfully developed. Established multiple stemmed cultures, which were induced in liquid MS medium containing 8.9 microM BA by roller culture, were cut into small clumps, plated on solid MS medium and cultured for three weeks at 25 degree C. Clumps that grew many buds were cold-hardened at 5 degrees C, with an 8 h photoperiod, for more than 30 d. The basal stem bud (1 to 2 mm long) was dissected from the clumps and precultured at 5 degrees C for 2 d on solid MS medium containing 0.3 M sucrose. The precultured buds were placed in 2 ml plastic cryotubes and osmoprotected with 1 ml loading solution containing 2 M glycerol and 0.6 M sucrose for 30 min at 25 degree C. Then they were dehydrated in 1 ml PVS2 solution at 25 degree C for 30 min and immersed in liquid nitrogen. Using this protocol, the survival level of cryopreserved igusa 'NZ219' buds reached 87 percent. This protocol was successfully applied to 42 different lines from three Juncus species, which had relatively high survival levels ranging from 30 to 90 percent and an average of 63 percent.     

Argon K-shell and bound-free emission from OMEGA direct-drive implosion cores

We discuss calculations of synthetic spectra for the interpretation and analysis of K-shell and bound-free emission from argon-doped deuterium-filled OMEGA direct-drive implosion cores. The spectra are computed using a model that considers collisional-radiative atomic kinetics, continuum-lowering, detailed Stark-broadened line shapes, line overlapping, and radiation transport effects. The photon energy range covers the moderately optically thick n = 3 → n = 1 and n = 4 → n = 1 line transitions in He- and H-like Ar, their associated satellite lines in Li- and He-like Ar, and several radiative recombination edges. At the high-densities characteristic of implosion cores, the radiative recombination edges substantially shift to lower energies thus overlapping with several line transitions. We discuss the application of the spectra to spectroscopic analysis of doped implosion cores.     

Observation of reversed-shear Alfvén eigenmodes excited by energetic ions in a helical plasma

Reversed-shear Alfvén eigenmodes were observed for the first time in a helical plasma having negative q?' (the curvature of the safety factor q at the zero shear layer). The frequency is swept downward and upward sequentially via the time variation in the maximum of q. The eigenmodes calculated by ideal MHD theory are consistent with the experimental data. The frequency sweeping is mainly determined by the effects of energetic ions and the bulk pressure gradient. Coupling of reversed-shear Alfvén eigenmodes with energetic ion driven geodesic acoustic modes generates a multitude of frequency-sweeping modes.     

Raman spectral features of longer polyynes HC2 nH ({\sf n=4}–8) in SWNTs

Size-selected linear hydrocarbon molecules, polyynes HC_2nH, were contacted in solutions with single-wall carbon nanotubes (SWNTs) prepared from laser-ablated metal/carbon composite rods (Rh/Pt/C) to produce polyyne-encapsulating SWNTs, HC_2nH@SWNT(RhPt). New Raman spectral features were observed at 2120, 2061, 2017, 1982, and 1963 cm^-1 for five polyynes of n=4–8, respectively, and identified as the vibrational excitation of symmetric stretching modes of the molecules inside the SWNTs. The Raman spectra were compared with those observed for polyynes on Ag islands (SERS) and in solutions. The filling factor was investigated from the concentration dependence of the Raman intensity for HC₁₀H@SWNT(NiCo) to give an estimate of one polyyne molecule per ~350 carbon atoms of SWNTs, providing a picture for head-to-tale filling of aligned C₁₀H₂ molecules inside the SWNTs.     

Visualization of flow and vortex structure around a swimming loach by dynamic stereoscopic PIV

Loach has a unique swimming style of bending the whole body and staying at the bottom of water. We studied the three-dimensional flow field around and behind the loach using stereoscopic-PIV. We captured flow fields in horizontal and vertical plane, and it seems loach leaves vortex tube arches. From the analysis of body motion and flow field, we propose flow structure with vortex tube arches connected along the loach body. After being released, they are separated and flow away and dissipate. This research article was submitted for the special issue on Animal locomotion: The hydrodynamics of swimming (Vol. 43, No. 5).     

Suzuki-Miyaura coupling catalyzed by polymer-incarcerated palladium, a highly active, recoverable, and reusable Pd catalyst

[reaction: see text] Suzuki-Miyaura coupling using a highly efficient and reusable polymer-incarcerated palladium (PI Pd) is described. Various coupling reactions proceeded smoothly using PI Pd with phosphine ligands, and the catalyst could be recovered by simple filtration and reused several times without loss of activity.