Reusable montmorillonite-entrapped organocatalyst for asymmetric Diels-Alder reaction

A chiral organocatalyst was successfully entrapped by montmorillonite clay using the cation-exchange method. The mont-entrapped organocatalyst acted as a highly efficient and reusable heterogeneous catalyst for the asymmetric Diels-Alder reaction, without loss of its initial activity.     

Synthesis and stereochemistry-activity relationship of small bacteriocin, an autoinducer of the symbiotic nitrogen-fixing bacterium Rhizobium leguminosarum

The four stereoisomers of small bacteriocin, an autoinducer of the symbiotic nitrogen-fixing bacterium Rhizobium leguminosarum, were synthesized via a versatile methodology for 3'-hydroxyacyl homoserine lactones based on the Nagao asymmetric aldol reaction. The synthetic isomers were much less effective at inhibiting the growth of R. leguminosarum RBL5523 than the natural isomer, showing the importance of stereochemistry for activity.     

Effect of DNA on filament formation of tau microtubule-binding domain: structural dependence of DNA

To examine whether or not DNA accelerates the paired helical filament (PHF) formation of tau, the effect of various types of DNAs on filament formations of three-repeated and four-repeated microtubule-binding domains (3RMBD and 4RMBD, respectively) of tau protein was investigated by monitoring the change of thioflavin S fluorescence intensity, that is parallel to the filament formation. Consequently, the followings were clarified: 1) the structurally rigid double-stranded DNA such as poly(dG-dC) or calf thymus DNA has the high potency of promoting the filament formations of 3RMBD and 4RMBD, 2) the filament formation of 3RMBD was more promoted than that of 4RMBD, due to the intermolecular dimer formation of 3RMBD, 3) the DNA-promoted filament formations of these MBDs were temperature-dependent, and the single-stranded DNA such as poly(dA) or poly(dT) reversely protected 4RMBD from the molecular assembly at 20 degrees C. These are the first report on the function of DNA for the PHF formation of tau protein.     

Unique catalysis of gold nanoparticles in the chemoselective hydrogenolysis with H2: cooperative effect between small gold nanoparticles and a basic support

Gold nanoparticles on hydrotalcite act as a heterogeneous catalyst for the chemoselective hydrogenolysis of various allylic carbonates to the corresponding terminal alkenes using H(2) as a clean reductant. The combination of gold nanoparticles and basic supports elicited significantly unique and selective catalysis in the hydrogenolysis.     

Serum metabolomics as a novel diagnostic approach for gastrointestinal cancer

Conventional tumor markers are unsuitable for detecting carcinoma at an early stage and lack clinical efficacy and utility. In this study, we attempted to investigate the differences in serum metabolite profiles of gastrointestinal cancers and healthy volunteers using a metabolomic approach and searched for sensitive and specific metabolomic biomarker candidates. Human serum samples were obtained esophageal (n = 15), gastric (n = 11), and colorectal (n = 12) cancer patients and healthy volunteers (n = 12). A model for evaluating metabolomic biomarker candidates was constructed using multiple classification analysis, and the results were assessed with receiver operating characteristic curves. Among the 58 metabolites, the levels of nine, five and 12 metabolites were significantly changed in the esophageal, gastric and colorectal cancer patients, respectively, compared with the healthy volunteers. Multiple classification analysis revealed that the variations in the levels of malonic acid and l ‐serine largely contributed to the separation of esophageal cancer; gastric cancer was characterized by changes in the levels of 3‐hydroxypropionic acid and pyruvic acid; and l ‐alanine, glucuronoic lactone and l ‐glutamine contributed to the separation of colorectal cancer. Our approach revealed that some metabolites are more sensitive for detecting gastrointestinal cancer than conventional biomarkers. Our study supports the potential of metabolomics as an early diagnostic tool for cancer. Copyright © 2011 John Wiley & Sons, Ltd.     

Development of High Performance Heterogeneous Catalysts for Selective Cleavage of C−O and C−C Bonds of Biomass‐Derived Oxygenates

The environmental impact of CO₂ emissions via the use of fossil resources as chemical feedstock and fuels has stimulated research to utilize renewable biomass feedstock. The biogenic compounds such as polyols are highly oxygenated and their valorization requires the new methods to control the oxygen to carbon ratio of the chemicals. The catalytic cleavage of C?O bonds and C?C bonds is promising methods, but the conventional catalyst systems encounter the difficulty to obtain the high yields of the desired products. This review describes our recent development of the high performance heterogeneous catalysts for the valorization of the biogenic chemicals such as glycerol, furfural, and levulinic acid via selective cleavage of C?O bonds and C?C bonds in the liquid‐phase. Selective C?O bond cleavage by hydrogenolysis enables production of various diols useful as engineering plastics, antifreeze, and cosmetics in high yields. The success of the selective C?C bond scission of levulinic acid can be applied to a wide range of the biogenic oxygenates such as carboxylic acids, esters, lactones, and primary alcohols, in which the selective C?C bond scission at adjacent to the oxygen functional groups are achieved. Furthermore, valorization of glycerol by selective acetylation and acetalization, and of levulinic acid by hydrogenation is described. Our catalysts show excellent performance compared to the reported catalysts in the aforementioned valorization.     

Designing magnetics of capped perpendicular media with minor-loop analysis

A novel method of analyzing the switching field distribution (SFD) and magnetic correlation length of perpendicular magnetic recording media that uses major and minor magnetization loops is proposed. By applying the analysis to a series of capped perpendicular media, we found that a thick capping layer with a low saturation magnetization effectively reduced SFD without rapidly increasing the magnetic correlation length. Transmission electron microscope observation suggests that the SFD is narrowed by the increased uniformity of intergranular exchange coupling via the thick capping layer. Evaluations of recording characteristics demonstrated a close correlation between narrower SFDs and improved recording performance. Reducing exchange coupling dispersion is a clear solution for improving the performance of recording media.     

Deviatoric stress and mean pressure in MgO compressed in a Kawai-type apparatus above 30 GPa: Evidence for reduction of deviatoric stress by annealing

By applying the numerical tensor analysis proposed by Yoneda and Kubo [Simultaneous determination of mean pressure and deviatoric stress based on numerical tensor analysis: a case study for polycrystalline X-ray diffraction of gold enclosed in a methanol-ethanol mixture. J. Phys.: Condens. Matter 18(2006)S979], we have determined deviatoric stress and mean pressure of polycrystalline MgO compressed in the Kawai-type apparatus. After the compression at room temperature, the mean pressure and the deviatoric stress in MgO were determined as 34.5 and 3.2 GPa, respectively. The mean pressure is significantly lower than the nominal pressure of 37.2 GPa determined by the conventional pressure determination method. By heating the sample to 1850 K with the constant press load, the deviatoric stress dramatically decreased to 0.1 GPa with a mean pressure of 34.2 GPa at room temperature after the heating. These results show both the importance of stress analysis to determine pressure more accurately and the effectiveness of annealing to reduce deviatoric stress in the sample.