Carboncarbon bond formation using bismuth in a water medium

In the presence of bismuth and ammonium chloride, allyl halides were found to react with aldehydes in a water medium at room temperature to give the corresponding homoallylic alcohols.     

3-D PTV measurement on turbulence modification due to an oil droplet in a plane Couette water flow

Three-dimensional particle tracking velocimetry (3-D PTV) measurements with a two-camera system have been conducted for a turbulent water plane Couette flow with an oil droplet in order to understand the modification of shear-dominant turbulence by the droplet. The parameters of the stereogrammetry, which are crucial for calculating the spatial coordinate of tracer particles from 2-D images of two cameras, have been determined with a careful calibration. The experimental results show that the axial and wall-normal turbulence intensities and the turbulent kinetic energy are enhanced locally in the confluence regions where axial main flow over the interface meets the secondary flow along the interface in the wall-normal direction. The secondary flows were observed only around the equator of the droplet. The wall-normal and transverse turbulence intensities are found to increase in the region above the droplet. This is due to the change in the direction of the primary flow over the top of the droplet. The turbulence in the other region is attenuated mainly because of the attenuation of the generation and evolution of the coherent structure in the neighbourhood of the droplet.     

Effect of primary filter using theoretical intensity of fluorescent X‐rays and scattered X‐rays

A primary filter is often used for low‐concentration analysis by energy‐dispersive X‐ray fluorescence spectrometer. We determined the material and thickness of the primary filter and calculated the theoretical intensities of the fluorescent X‐rays and scattered X‐rays using lead in brass, for which the concentration is known. The filter materials were zirconium, nickel, titanium, aluminum, and molybdenum with a thickness between 20 and 125 µm. For verification, we calculated the lower limits of detection using theoretical intensities for several filters and compared them with values calculated using the measured intensities. For example, both values were similar for a 125 µm zirconium filter: 128.0 ppm using theoretical intensities and 147.7 ppm using measured intensities. The theoretical intensity values are obtained by measurements and calculations, but require no primary filters for the measurements. This method is extremely effective for selecting the optimal filter for multiple samples and elements. Copyright © 2010 John Wiley & Sons, Ltd.     

Preparation and evaluation of solid dispersions of nitrendipine prepared with fine silica particles using the melt-mixing method

Solid dispersions (SD) of nitrendipine (NTD), a poorly water-soluble drug, were prepared using the melt-mixing method with hydrophilic silica particles (Aerosil and Sylysia) with different particle size and specific surface areas as carriers. Powder X-ray diffraction and differential scanning calorimetry evaluation showed that NTD in the SDs treated with the melt-mixing method was dispersed in the amorphous state. FT-IR spectroscopy obtained with the SDs indicated the presence of hydrogen bonding between the secondary amine groups of NTD and silanol groups of silica particles. The dissolution property of NTD in the SDs was remarkably improved regardless of the grade of silica. At the end of the dissolution test (60 min) the concentrations of NTD for the SDs with Aerosil 200 and Sylysia 350 were 8.88 and 10.09 microg/ml, corresponding to 28 and 31 times that of the original NTD crystals, respectively. The specific surface area and the adsorbed water amount of the SDs were also significantly improved. The rapid dissolution rate from the SDs was attributed to the amorphization of drug, improved specific surface area and wettability than the original drug crystals. In the stability test, powder X-ray diffraction pattern indicated that amorphous NTD in the SD with Aerosil 200 was stable for at least 1 month under the humid conditions (40 degrees C/75% RH).     

Control of dominant conduction orbitals by peripheral substituents in paddle-wheel diruthenium alkynyl molecular junctions

Control of charge carriers that transport through the molecular junctions is essential for thermoelectric materials. In general, the charge carrier depends on the dominant conduction orbitals and is dominantly determined by the terminal anchor groups. The present study discloses the synthesis, physical properties in solution, and single-molecule conductance of paddle-wheel diruthenium complexes 1R having diarylformamidinato supporting ligands (DArF: p-R-C₆H₄-NCHN-C₆H₄-R-p) and two axial thioanisylethynyl conducting anchor groups, revealing unique substituent effects with respect to the conduction orbitals. The complexes 1R with a few different aryl substituents (R = OMe, H, Cl, and CF₃) were fully characterized by spectroscopic and crystallographic analyses. The single-molecule conductance determined by the scanning tunneling microscope break junction (STM-BJ) technique was in the 10⁻⁵ to 10⁻⁴G₀ region, and the order of conductance was 1OMe > 1CF3 ≫ 1H ∼ 1Cl, which was not consistent with the Hammett substituent constants σ of R. Cyclic voltammetry revealed the narrow HOMO–LUMO gaps of 1R originating from the diruthenium motif, as further supported by the DFT study. The DFT-NEGF analysis of this unique result revealed that the dominant conductance routes changed from HOMO conductance (for 1OMe) to LUMO conductance (for 1CF3). The drastic change in the conductance properties originates from the intrinsic narrow HOMO–LUMO gaps.

Dominant conduction orbitals of paddle-wheel organodiruthenium complexes can be facilely controlled by the substituents embedded in the amidinato ligands.     

Efficient synthesis of the functional central core lactides, a constituent of antibiotic fattiviracins

An efficient convergent synthetic method has been developed for preparation of various stereoisomers and derivatives of fattiviracins via a common lactide. The synthetic route comprises seco acids prepared by the β-selective glycosylation of chiral 3-hydroxy-4-pentanoate obtained by enzymatic kinetic resolution. The regioselective protection of four individual hydroxy groups was achieved via the 4,6-O-benzylidenation of the glucose moiety from its TMS ethers. The dimeric cyclization of the seco acids under control of reaction concentration afforded the desired lactide without using KH. Our convergent synthetic method was successfully applied to direct installation of side chains to the lactide by cross metathesis to synthesize fattiviracin derivatives. We achieved improvements to the reported method with respect to: (1) synthesis of a convergent synthetic intermediate; (2) stereoselectivity in glycosylation; and (3) establishment of a low cost route suitable for large scale synthesis.     

Porritoxins, metabolites of Alternaria porri, as anti-tumor-promoting active compounds

To search for possible cancer chemopreventive agents from natural sources, we performed primary screening of metabolites of Alternaria porri by examining their possible inhibitory effects on Epstein-Barr virus early antigen (EBV-EA) activation induced by 12-O-tetradecanoylphorbol-13-acetate (TPA) in Raji cells. The ethyl acetate extract of A. porri showed the inhibitory effect on EBV-EA activation. Three porritoxins (1-3) were obtained as inhibitory active compounds for EBV-EA from ethyl acetate extract. 6-(3',3'-Dimethylallyloxy)-4-methoxy-5-methylphthalide (2) showed the strongest activity among them. Inhibitory effect of porritoxin (1) and (2) was superior to that of beta-carotene, a well-known anti-tumor promoter. Furthermore, the structure-activity correlation of porritoxins and their related compounds were discussed.