Studies aimed at the total synthesis of azadirachtin. A modeled connection of C-8 and C-14 in azadirachtin

[reaction: see text] Studies on the connection between the right and left segments of azadirachtin are described. The Ireland-Claisen rearrangement of Li-enolate of the modeled ester with dichlorodimethylsilane in toluene afforded the desired limonoid framework stereoselectively in good yield.     

Rapid determination of 137Cs in environmental samples--purification of 137Cs by ammonium molybdophosphate column separation]

A rapid method for the determination of 137Cs in environmental samples was proposed. The principal technic employed in this study is based on column separation of 137Cs using ammonium molybdophosphate mixed with glass fiber to eliminate contribution of natural radionuclides such as 40K and 87Rb. The separation of cesium from potassium and rubidium was performed by the elution with 0.5m ammonium nitrate solution. The time required for separation of cesium was five hours as compared with the conventional cation exchange separation which required thirteen hours. The chemical yield of cesium carrier was normally more than 90 percent. The results obtained were compared with that by the conventional methods using Bio-Rex cation exchange separation and the good agreement between the two methods was obtained.     

Selective Hydroperoxygenation of Olefins Realized by a Coinage Multimetallic 1-Nanometer Catalyst

The science of particles on a sub-nanometer (ca. 1 nm) scale has attracted worldwide attention. However, it has remained unexplored because of the technical difficulty in the precise synthesis of sub-nanoparticles (SNPs). We recently developed the “atom-hybridization method (AHM)” for the precise synthesis of SNPs by using a suitably designed macromolecule as a template. We have now investigated the chemical reactivity of alloy SNPs obtained by the AHM. Focusing on the coinage metal elements, we systematically evaluated the oxidation reaction of an olefin catalyzed by these SNPs. The SNPs showed high catalytic performance even under milder conditions than those used with conventional catalysts. Additionally, the hybridization of multiple elements enhanced the turnover frequency and the selectivity for the formation of the hydroperoxide derivative. We discuss the unique quantum-sized catalysts providing generally unstable hydroperoxides from the viewpoint of the miniaturization and hybridization of materials.     

Narrowband solid state vuv coherent source for laser cooling of antihydrogen

We describe the design and performance of a solid-state pulsed source of narrowband (< 100 MHz) Lyman-α radiation designed for the purpose of laser cooling magnetically trapped antihydrogen. Our source utilizes an injection seeded Ti:Sapphire amplifier cavity to generate intense radiation at 729.4 nm, which is then sent through a frequency doubling stage and a frequency tripling stage to generate 121.56 nm light. Although the pulse energy at 121.56 nm is currently limited to 12 nJ with a repetition rate of 10 Hz, we expect to obtain greater than 0.1 μJ per pulse at 10 Hz by further optimizing the alignment of the pulse amplifier and the efficiency of the frequency tripling stage. Such a power will be sufficient for cooling a trapped antihydrogen atom from 500 mK to 20mK.     

Growth of epitaxial TmFeCuO4 thin films by pulsed laser deposition

Epitaxial thin films of TmFeCuO₄ with a two-dimensional triangular lattice structure were successfully grown on yttria-stabilized-zirconia substrates by pulsed laser deposition and ex situ annealing in air. The films as-deposited below 500 °C showed no TmFeCuO₄ phase and the subsequent annealing resulted in the decomposition of film components. On the other hand, as-grown films deposited at 800 °C showed an amorphous nature. Thermal annealing converted the amorphous films into highly (0 0 1)-oriented epitaxial films. The results of scanning electron microscopic analysis suggest that the crystal growth process during thermal annealing is dominated by the regrowth of non-uniformly shaped islands to the distinct uniform islands of hexagonal base.     

Encapsulation of anilinonaphthalenesulfonates in carboxylate-terminated PAMAM dendrimer at the polarized water|1,2-dichloroethane interface

Molecular encapsulation of water-soluble anionic fluorescent dye molecules, 8-anilino-1-naphthalenesulfonic acid (ANS), and its bimolecular derivative (bis-ANS), in the generation 3.5 polyamidoamine (G3.5 PAMAM) dendrimer was investigated in the bulk aqueous phase and at the polarized water|1,2-dichloroethane interface. ANS(-) was electrostatically incorporated in the dendrimer, and the fluorescence enhancement with a blue shift of the emission maximum was observed at pH values <6, where the interior of the dendrimer was positively charged. The fluorescence enhancement of ANS was maximized around pH 3 and then decreased under more acidic conditions. The potential dependences of the molecular encapsulation and the interfacial mechanism were studied in detail by means of potential modulated fluorescence (PMF) spectroscopy. Under acidic conditions, the dendrimer incorporated ANS(-) at the positively polarized interface as well as in the aqueous phase. ANS(-) was released from the dendrimer at the intrinsic transfer potential and independently transferred across the interface. Bis-ANS exhibited relatively strong interaction with the dendrimer over a wide pH range (1 < pH < 8), and a negative shift of the transfer potential was observed under the corresponding pH condition. The PMF analysis clearly demonstrated that the interfacial mechanism of the dendrimer involves transfer and adsorption processes depending on the pH condition and the Galvani potential difference.     

Disturbance-free laser diode Sagnac interferometer using direct phase modulation

We exploited the wavelength tunability of the laser diode of a phase-shifting Sagnac interferometer to realize disturbance-free measurements. The Sagnac interferometer is robust against mechanical disturbances because it has a common path configuration and requires no special references. An unbalanced optical path was introduced between p- and s-polarized beams to enable easy phase shifting by direct current modulation. The experimental results indicate that the proposed system is effective for performing precise disturbance-free measurements.     

Channel-switching crystal with guest stress drive

By the addition of a "leverage" mechanism in a host component of a metal-organic crystal, a channel-switching property was developed in a porous single-crystal adsorbent driven by incorporated guest gas stress, which may provide new single-crystal devices with the active controllability of anisotropic guest diffusivity.