Improved Chemical Synthesis,X-Ray Crystallographic Analysis,and NMR Characterization of (22R)-/(22S)-Hydroxy Epimers of Bile Acids

We report an improved synthesis of the (22R)- and (22S)-epimers of 3α,7α,12α,22-tetrahydroxy-5β-cholan-24-oic acid and 3α,7α,22-trihydroxy-5β-cholan-24-oic acid from cholic acid (CA) and chenodeoxycholic acid (CDCA), respectively. The principal reactions involved were as follows: (1) oxidative decarboxylation of the bile acid peracetates with lead tetraacetate, and (2) subsequent Reformatsky reaction of the 23,24-dinor-22-aldehydes with ethyl bromoacetate in the presence of activated Zn as a catalyst with the reaction temperature maintained precisely at 75 °C. The absolute configuration of the chiral center at C-22 of each epimer was established by single-crystal X-ray diffraction data using its ethyl ester-peracetate derivative. The ¹H- and ¹³C-NMR spectra that permit the (22R)- and (22S)-epimers to be distinguished are reported as well as the specific ¹H shift effects induced by C₅D₅N. Bile acids having hydroxyl groups at C-22 are present in a variety of animal biles, previously have been difficult to identify, and are known to have distinctive physicochemical and biological properties.     

The Effects of Wet-Milled Wood Flour on the Mechanical Properties of Wood Flour/Polypropylene Composites

The sizes and shapes of wet ball-milled wood flour were investigated based on their average particle size, size distribution, their solution viscosity, and scanning electron microscopy images. The ball-milling conditions were combinations of rotational speed (150, 200, and 250 rpm) and milling time (1 to 16 h). The average diameter of the wood flours decreased and the degree of fibrillation of the wood fibers increased with the ball-milling time at each rotational speed. Ball-milled wood flours having the same average particle size had similar surface fibrils that were tens to hundreds of nanometers wide. Ball-milling at 200 or 250 rpm could pulverize just as effectively as that at 150 rpm because the size reduction and fibrillation progressed more quickly. Tensile and bending properties of the composites prepared from the ball-milled wood flour (4 wt% in polypropylene) were evaluated. Morphological changes in the wood fillers had little effect on the properties of the composites. The tensile and bending properties of the composites containing the wood filler were 10% higher than those for the unfilled resin.     

Seasonal change in the level and the chemical forms of aluminum in soil solution under a Japanese cedar forest

The level of dissolved aluminum and its chemical forms in soil solutions consecutively collected by a porous cup vacuum sampler were monitored over a period from January 2001 to December 2001 at a Japanese cedar (Cryptomeria japonica) forestry area susceptible to acid deposition to characterize current soil dynamics and to evaluate potential tree damages. Distinction and characterization of Al species with differential toxicities were performed by two complementary speciation techniques; cation-exchange HPLC with fluorometric detection using 8-hydroxyquinoline-5-sulfonic acid (HQS) and size-fractionation/inductively coupled plasma atomic emission spectrometry (ICP-AES). The concentrations of free Al (mainly Al3+ and Al(OH)2+) and inert Al (existing as the complexed and/or colloidal forms) ranged between 0-150 microM and 10-50 microM, respectively. The concentrations of inert Al were mostly below 40 microM during an annual cycle and showed no marked seasonal variation, while free Al concentrations showed a clear tendency to increase in the spring and summer seasons (in the period from April to August) probably due to the enhanced activity of microbial nitrification and the resultant soil acidification. Major cations and anions were also regularly determined and their seasonal changes were correlated with that of the dissolved Al concentration. Correlations between total Al (mainly existing as free Al) and the related species (and environmental conditions) were as follows: Al and Mg (R=0.96, P<0.01), Al and Ca (R=0.97, P<0.01), Al and NO3- (R=0.68, P<0.01), Al and temperature (R=0.68, P<0.01), Al and solution pH (R=-0.61, P<0.01), solution pH and NO3- (R=-0.65, P<0.01).     

Water-absorption rate equation of rice for brewing sake

This study was undertaken to analyze the kinetics of water absorption and to derive an equation for the rate at which water is absorbed by rice for brewing sake. We used two rice varieties: Gin-oumi, commonly used as a staple food, and Gohyakumangoku, a variety used particularly for brewing sake. The water-absorption rate equations of Gin-oumi and Gohyakumangoku were postulated based on the following equations. For Gin-oumi (water content, 11.5%), dx/dtheta=k(1-x)(n), n=1, k=(2 x 10(-9))exp(0.0604 x (t+273.15)). For Gohyakumangoku (11.5%), dx/dtheta=k(1-x)(n)(x+a), n=1, a=0.29, k=(2 x 10(-8))exp(0.0534 x (t+273.15)). Here, x, theta (min), and t ( degrees C) are the water absorbing ratio, time, and temperature, respectively. The result shows that the values of the temperature-dependence parameter k (min(-1)), as well as its curves, are different; a typical rice grain has a monotonically smooth curve, whereas that suitable for sake brewing has an S-shaped curve.     

Development of dedicated STEM with high stability

We developed a dedicated scanning transmission electron microscope with high-stability. The mechanical and electronic stabilities of the microscope were substantially improved, e.g. the specimen drift rate was found to be <0.2 nm min(-1). The Fourier transform of an ADF image showed spots of 0.105 nm at an acceleration voltage of 200 kV without spherical aberration corrector. The stabilized STEM instrument allows us to acquire distortion-free STEM images and high-signal to noise ratio analyses. We have shown the outline of the instrument and preliminary results.     

Preparation of (001)-oriented Pb(Zr,Ti)O3 thin films and their piezoelectric applications

Preparation of (001)-oriented Pb(Zr,Ti)O(3) (PZT) thin films and their applications to a sensor and actuators were investigated. These thin films, which have a composition close to the morphotropic phase boundary, were epitaxially grown on (100)MgO single-crystal substrates by RF magnetron sputtering. These (001)-oriented PZT thin films could be obtained on various kinds of substrates, such as glass and Si, by introducing (100)-oriented MgO buffer layers. In addition, the (001) oriented PZT thin films could be obtained on Si substrates without buffer layers by optimizing the sputtering conditions. All of these thin films showed excellent piezoelectric properties without the need for poling treatment. The PZT thin films on the MgO substrates had a high piezoelectric coefficient, d(31), of -100 pm/V, and an extremely low relative dielectric constant, epsilon(r), of 240. The PZT thin films on Si substrate had a very high d(31) of -150 pm/V and an epsilon(r) = 700. These PZT thin films were applied to an angular rate sensor with a tuning fork in a car navigation system, to a dual-stage actuator for positioning the magnetic head of a high-density hard disk drive, and to an actuator for an inkjet printer head for industrial on-demand printers.     

Short term evaluation of material blood compatibility using a microchannel array

New short-term evaluation of material blood compatibility was attempted using a microchannel array with human blood under a flow condition. The microchannel array chips were made of silicon, having 8,736 microchannels of 10 μm-wide, 30 μm-long, and 4.5 μm-deep on the average, as the models of capillary blood vessels. Titanium, chromium, albumin and collagen were coated onto the chips to examine the difference of material blood compatibility and the effect of protein adsorption on it. The time for the first 100 μl portion of whole blood to pass through the channels (blood pass-through time, BPT) was measured under a pressure difference of 20 cmH₂O. Simultaneously, the flow behavior of blood cells was observed by an optical microscope. The BPT tends to correlate well with the level of platelet adhesion. The highest BPT as well as platelet adhesion was observed on collagen, followed by titanium, chromium, silicon, and albumin. These results indicate that the BPT can detect the different levels of platelet adhesion and thrombus formation on microchannel surface and that the protein adsorption onto chip surface can influence BPT. We concluded that this method could be applied to evaluate initial blood compatibility of materials within several minutes in vitro.     

Encapsulation of hemoglobin in mesoporous silica (FSM)-enhanced thermal stability and resistance to denaturants

Hemoblogin (Hb), which is a typical oligomeric protein, was introduced into the pores of mesoporous silica (FSM: folded-sheet mesoporous material) that had a diameter of 7.5 nm. Soret CD spectra of Hb-FSM-7.5 conjugates showed a peak that was identical to that of free Hb. This suggests that Hb retained its highly ordered structure in the mesoporous silica. In addition, the UV-visible absorption spectrum showed that Hb had an increased resistance to heat denaturation in the silica. Even after heat treatment at 85 degrees C, Hb-FSM-7.5 retained its ligand-binding activity. The stability of Hb-FSM-7.5 was examined further by measuring its peroxidase-like activity. Encapsulation of Hb resulted in the retention of activity in the presence of high NaCl or Gdn-HCl levels. This suggests that encapsulation prevented dissociation and denaturing. Thus, it seems that the mesopores created a favorable environment for the oligomeric protein to perform its function, even under harsh conditions.     

New insights into galactose metabolism by Schizosaccharomyces pombe: isolation and characterization of a galactose-assimilating mutant

The fission yeast Schizosaccharomyces pombe cannot use galactose as a carbon or energy source, and little is known about galactose metabolism in this species. Here we report isolation of a galactose-assimilating mutant that grows on a medium containing galactose as a sole carbon source through use of a proofreading-deficient DNA polymerase δ variant encoded by cdc6-1. Based on comparative analysis of gene expression profiles in the wild-type and the mutant (FG2-8), we found that SPBPB2B2.10c (gal7+), SPBPB2B2.12c (gal10+) and SPBPB2B2.13 (gal1+), homologous to Saccharomyces cerevisiae GAL7, GAL10 and GAL1, respectively, and SPBPB2B2.08, SPBPB2B2.09c, and SPBPB2B2.11 that localize close to the gal genes, were highly expressed and dramatically induced by addition of galactose. The gal7Δ strain, carrying an integrated ura4+ marker at the gal7+ locus, grew on 5-fluoroorotic acid (5-FOA)-containing medium. In contrast, the FG2-8 gal7Δ strain could not grow on 5-FOA medium. In addition, expression of gal7+, SPBPB2B2.13, gal10+ and gal1+ genes increased in the wild-type strain when carried on a vector, and these transformants grew on galactose medium. We suggest that gal7+, gal10+, and gal1+ are localized close to a chromosomal terminal repressed by gene silencing in S. pombe. In contrast, gene silencing was defective in the FG2-8 strain making galactose assimilation possible.     

莫高窟第217窟南壁经变新解

本文对敦煌莫高窟第217窟南壁一直被认为是<法华经变>的图像进行重新辨认,找出其佛经依据,并提出整个南壁内容应为<佛顶尊胜陀罗尼经变>的新解释.