Green,Multi‐Gram One‐Step Synthesis of Core–Shell Nanocomposites in Water and Their Catalytic Application to Chemoselective Hydrogenations

We devise a new and green route for the multi‐gram synthesis of core–shell nanoparticles (NPs) in one step under organic‐free and pH‐neutral conditions. Simply mixing core and shell metal precursors in the presence of solid metal oxides in water allowed for the facile fabrication of small CeO₂‐covered Au and Ag nanoparticles dispersed on metal oxides in one step. The CeO₂‐covered Au nanoparticles acted as a highly efficient and reusable catalyst for a series of chemoselective hydrogenations, while retaining C=C bonds in diverse substrates. Consequently, higher environmental compatibility and more efficient energy savings were achieved across the entire process, including catalyst preparation, reaction, separation, and reuse.     

Performance Characteristics of Power Build-Up Cavity for Raman Spectroscopic Measurement

Performance characteristics of power build-up cavity (PBC) as the light source of a Raman spectroscopy based gas sensor were studied. The key parameter to optimize stable and high intra-cavity power operation was beam diameter of the back reflected beam from external cavity to diode laser. The optimum diameter determined by an appropriate distance between the cavity and diode laser was found to be comparable with the waveguide cross section of diode laser for the effective spatial filtering, where inevitable cavity coupling loss caused by slight spatial mode mismatching existed. A PBC with a finesse of ∼10300 achieved a stable TEM₀₀ mode in excess of intra-cavity power of 80 watts pumped by a 10 milliwatts diode laser. Simultaneously, the PBC wavelength is found to be passively locked effectively at 670 +/− 0.15 nm where the center of the gain region exists. A Raman spectrum of nitrogen measurement was demonstrated.     

Differential-pulse anodic stripping voltammetry of copper with a chemically-modified glassy carbon electrode

Copper at the low or fractional ng g^?1 level in 0.1 M oxalic acid solutions at pH 1.6 is electrodeposited on a chemically-modified glassy carbon electrode with surface-bound

groups at ?0.6 V vs. Ag/AgCl (3.3 M KCl). The deposit is then anodically stripped in the same solution, a current-potential curve being recorded by the differential-pulse technique. The advantages of this electrode over an unmodified glassy carbon electrode include higher sensitivity, precision and selectivity; the modified electrode can be used 50–100 times without further treatment.     

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 of mono- and 1,3-disubstituted allenes from propargylic amines via palladium-catalysed hydride-transfer reaction

Mono- and 1,3-disubstituted allenes were synthesized from the corresponding propargylamines via palladium-catalysed hydride-transfer reaction. In the current transformation, propargylic amines can be handled as allenyl anion equivalents and introduced into various electrophiles to be transformed into allenes under palladium-catalyzed conditions.     

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.     

Authentication and chemical study of isodonis herba and isodonis extracts

Isodonis Herba is used as a Japanese dietary supplement and folk medicine. The extract of the herb (Isodonis extract) is also used as a food additive whose major compound is enmein (1). Here we compared internal transcribed spacer sequences of nuclear ribosomal DNA from Isodonis Herba available on the Japanese and Chinese crude drug markets, and found that the former derived from Isodon japonicus and Isodon trichocarpus, while the latter derived from distinct species such as Isodon eriocalyx. The liquid chromatography/mass spectrometry profiles of Isodonis Herba were classified into four chemotypes (A to D) according to the ratio of the major constituents. Types B and C contained 1 and oridonin (2) as major components, respectively. An intermediate (or mixed) form of types B and C in various ratios was designed type A. Type D contained eriocalyxin B (3) as its major component. Japanese herba were types A-C, while Chinese herba were types C and D. The commercial Isodonis extract products tested were classified as type D, suggesting that they originated from Chinese Herba. Understanding the relationship between extract constituents and DNA profiles is important for the official specification of dietary supplements and food additives of plant origin.