Distinction of Leu and Ile Using a Ruthenium(II) complex by MALDI-LIFT-TOF/TOF-MS analysis

The novel N-terminal labeling method using a ruthenium(II) complex derivative characteristically indicated a(n) and d(n) (N-terminal) fragment ions in high sensitivity by MS/MS analysis (MALDI-LIFT or ESI-CID). Although these fragment ions depended on a fragmentation process by MS/MS analytical methods to some degree, each case indicated similar side-chain cleavage patterns. The labeling method allows accurate distinction of amino acid residues by MS/MS analysis even if the residues are structural isomers such as leucine and isoleucine. The method was applied to long-chain peptides and provided easy and rapid N-terminal sequencing.     

Metal-ligand bifunctional catalysis for asymmetric hydrogenation

Chiral diphosphine/1,2-diamine-Ru(II) complexes catalyse the rapid, productive and enantioselective hydrogenation of simple ketones. The carbonyl-selective hydrogenation takes place via a non-classical metal-ligand bifunctional mechanism. The reduction of the C=O function occurs in the outer coordination sphere of an 18e trans-RuH2(diphosphine)(diamine) complex without interaction between the unsaturated moiety and the metallic centre. The Ru atom donates a hydride and the NH2 ligand delivers a proton through a pericyclic six-membered transition state, directly giving an alcoholic product without metal alkoxide formation. The enantiofaces of prochiral ketones are differentiated on the chiral molecular surface of the saturated RuH2 species. This asymmetric catalysis manifests the significance of 'kinetic' supramolecular chemistry.     

Silicon carbide coating on molybdenum by chemical vapor deposition and its stability under thermal cycle conditions

Silicon carbide film (as thick as 25 μm) was chemically vapor deposited on molybdenum in the temperature range of 1050–1300°C by reaction of hydrogen and ethyltrichlorosilane as an application of a low-Z material to fusion reactor protective plates. The films were characterized by using scanning electron microscopy, X-ray diffraction, electron microprobe analysis, and infrared absorption spectroscopy. The deposits consisted of α and β-SiC and a small amount of SiO₂. Underlayer coatings were also attempted to improve the thermal cycling behavior. The coating with a boron underlayer was successfully cycled 2100 times between 800 and 1000°C, and then 560 times between 600 and 1200°C in air under thermal cycling conditions with a heating rate of 20°C/min. Problems in applying SiC-coated molybdenum to the first wall protective plates in a fusion reactor are discussed.     

Inhibitory effect of fermentation byproducts on formation of advanced glycation end-products

Distilled residues (DR) of rice spirit and its derived vinegar produced a negligible inhibitory effect on advanced glycation end-products (AGE) formation. However, recycled DRs of rice spirit and barley spirit and their derived vinegars inhibited formation of N^ε(carboxymethyl)lysine (CML), a major AGE. Unlike the aforementioned DR and derived vinegars, the DR of sweet potato spirit and vinegar, contained very little protein, lysine and arginine, but they most potently inhibited CML formation. The DRs of various spirits and vinegars showed similar free radical-scavenging activities.     

High-performance C60 and picene thin film field-effect transistors with conducting polymer electrodes in bottom contact structure

C₆₀ and picene thin film field-effect transistors (FETs) in bottom contact structure have been fabricated with poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) electrodes for a realization of mechanical flexible organic FETs. The C₆₀ thin film FETs showed n-channel enhancement-type characteristics with the field-effect mobility μ value of 0.41 cm² V^?1 s^?1, while the picene thin film FET showed p-channel enhancement-type characteristics with the μ of 0.61 cm² V^?1 s^?1. The μ values recorded for C₆₀ and picene thin film FETs are comparable to those for C₆₀ and picene thin film FETs with Au electrodes.     

Radiation-induced polymerization of ethylene in a pilot plant. I. Bulk process

Radiation-induced bulk polymerization of ethylene was carried out with use of a pilot plant with a 10 liter reactor at pressures of 225–400 kg/cm², temperatures of 30–95°C, ethylene feed rates of 5–28 kg/hr, and dose rate of 3.8 × 10⁵ rad/hr. Characteristics of the process are mild polymerization conditions and capability of producing medium density polyethylene in powder form. The spacetime yield and molecular weight of polymer were in the range of 3.5 to 13.1 g/liter hr and 2.2 × 10⁴ to 14 × 10⁴, respectively. The space-time yield increased with mean residence time and 2.4 powders of pressure, and decreased with temperature. Molecular weight changed similarly with the reaction conditions. These results were consistent with those of the bench plant experiment and the scale effect was small. Polymer deposit to the reactor wall limited a period of continuous operation of the plant. The amount of deposited polymer was increased with the square of reaction time. The rate of polymer deposit was proportional to polymer concentration and to the cube of pressure. The polymer deposit cannot be solved in the bulk process.     

Photocatalytic partial oxidation of methylpyridine isomers on TiO2 particles under an anaerobic condition

Photocatalytic oxidation of methylpyridine isomers (2-methylpyridine, 3-methylpyridine, and 4-methylpyridine) was investigated in a mixed solution of acetonitrile and water or acetonitrile using various kinds of TiO₂ powders as photocatalysts. The main products from methylpyridine isomers were pyridinecarboxaldehyde isomers (2-pyridinecarboxaldehyde, 3-pyridinecarboxaldehyde, and 4-pyridinecarboxaldehyde). Rutile large TiO₂ particles showed the highest level of activity for oxidation of 2-methylpyridine probably because band bending was necessary for the oxidation of 2-methylpyridine. On the other hand, a fine particle having an anatase or rutile phase showed a higher level of activity than large TiO₂ particles for oxidation of 3-methylpyridine. A rutile fine particle showed the highest level of activity for the reaction. It was found that pure rutile or pure anatase particles were inactive for oxidation of 4-mathylpyridine. If the particles are not extremely small, pure rutile and pure anatase powders show fairly high levels of activity, and those containing both anatase and rutile phases show the highest level of activity. The activity of pure rutile particles was also enhanced by physically mixing them with a small amount of small anatase particles, which were inactive for this reaction. These results can be explained by the synergism between rutile and anatase particles. All of these reactions effectively proceeded even under anaerobic conditions. Photocatalytic reduction of methylpyridine isomers concomitantly proceeded on TiO₂ particles under the conditions used. These results suggest that the activities of TiO₂ photocatalysts for oxidation of methylpyridine isomers are dominated by the oxidation potential of alkylpiridine and band bending of TiO₂ particles.     

Effects of isocyanuric acid on the monochlorodimedone chlorinating rates with free chlorine and ammonia chloramine in water

Changes in monochlorodimedone (MCD) chlorinating rates with free chlorine (mixture of HOCl and OCl-) and ammonia monochloramine (NH2Cl) in water at pH 7 by the addition of isocyanuric acid (H3Cy) were determined at room temperature. Decreases in MCD absorbance at 290nm in equimolar (0.04mM) reactions of MCD and free available chlorine solutions containing H3Cy (0.01-1.60 mM) were recorded in a stopped-flow spectrophotometer. The rates indicate second-order reactions. Since the rate with free chlorine was high (> 7.6 x 10(6) M(-1) s(-1)), the amounts of free chlorine in the solutions could be distinguished from that of chlorinated cyanurates. The chlorinating rates with chlorinated cyanurates decreased with an increase in H3Cy concentrations. Plotting the rates against the molar ratio of chlorine to H3Cy showed a linear correlation and the rates with chlorinated cyanurates (H2ClCy) was estimated at 0.5 x 10(5) M(-1) s(-1). In contrast, the rates with the NH2Cl solution containing H3Cy increased with an increase in H3Cy concentrations, increasing from 1.2 x 10 to 2.7 x 10 M(-1) s(-1) by the addition of 1.55 mM H3Cy. The DPD color development rates (OD512/t1/2/M) with free available chlorine (0.015mM) declined from 1.3 x 10(5) to 0.9 x 10(5)M(-1) by the addition of 0.61 mM H3Cy.     

Experimental visualization of lithium diffusion in LixFePO4

Chemical energy storage using batteries will become increasingly important for future environmentally friendly ('green') societies. The lithium-ion battery is the most advanced energy storage system, but its application has been limited to portable electronics devices owing to cost and safety issues. State-of-the-art LiFePO4 technology as a new cathode material with surprisingly high charge-discharge rate capability has opened the door for large-scale application of lithium-ion batteries such as in plug-in hybrid vehicles. The scientific community has raised the important question of why a facile redox reaction is possible in the insulating material. Geometric information on lithium diffusion is essential to understand the facile electrode reaction of LixFePO4 (0相似文献