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.     

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.     

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   

Synthesis and polymerization of a self-condensable macromonomer

Summary A novel self-condensable macromonomer that has a polymerizable group at one terminal and an initiator at the other was synthesized by the combination of the conventional macromonomer technique and the SmI₂-induced transformation. Namely, living poly(tetrahydrofuran) [poly(THF)] carrying α-methacryloyl group was prepared by using methacryloyl chloride and silver trifluoromethanesulfonate. The living chain end was capped with sodium 2-bromoisobutyrate, and the sequential reduction of the terminal C-Br bond with SmI₂ gave a terminating samarium enolate. The resulting samarium enolate copolymerized the α-methacryloyl group with methyl methacrylate, giving a hyperbranched block copolymer whose dendritic part consists of two kinds of polymer segments. Received: 4 January 1999/Accepted: 2 February 1999     

Design and analysis of a brushless motor for ball screw drives

Design and analysis of brushless motors for ball screw drives, such as application-specific electric motors, are presented. Since the motor should be designed as a built-in structure for machining equipment, the motor dimensions are restricted. A new design concept for such applications is presented. Under various combinations of motor dimensions and electrical parameters, the motor performance is simulated using a personal computer, and the optimized parameter combination is selected. Based on the optimized parameters, a prototype motor is constructed to prove the validity of the proposed design procedure. © 1999 Scripta Technica, Electr Eng Jpn, 127(3): 41–52, 1999     

Synthesis of poly(tetrahydrofuran-b-ε-caprolactone) macromonomer via the Sml2-induced transformation

Summary A novel well-defined macromonomer consisting of different types of monomers in polymerization mechanisms was synthesized for the first time through the SmI₂-induced transformation. The macromonomer, -methacryloylpoly-(tetrahydrofuran-b--caprolactone), was prepared by the reaction of methacryloyl chloride with living poly(tetrahydrofuran-b--caprolactone) [poly(THF-b-CL)] which was obtained by the two-electron reduction of the cationic growing center of poly(THF) by samarium iodide (SmI₂) followed by the polymerization of CL. ¹H NMR analysis indicated the quantitative introduction of the methacryloyl group onto the polymer end. The molecular weight distribution of the macromonomer was relatively narrow, and the unit ratio of THF to CL could be controlled by both polymerization time of THF and the amount of CL, resulting from the living nature of both CL- and THF-polymerizations. Radical copolymerization of the produced macromonomers with methyl methacrylate in the presence of AIBN resulted in a polymethacrylate backbone grafted with poly(THF-b-CL) block copolymers.