Development of Molecular Sieves‐Supported Palladium Catalyst and Chemoselective Hydrogenation of Unsaturated Bonds in the Presence of Nitro Groups

The chemoselective hydrogenation of unsaturated bonds and azide functionalities is achieved in the presence of nitro groups by a heterogeneous palladium catalyst supported on molecular sieves (MS3A). The present method shows a wide‐range of applicability with regard to substrates and the catalyst can be easily prepared and reused at least three times without any loss of activity.     

Analysis of glycosyl bond cleavage and related isotope effects in collision-induced dissociation quadrupole-time-of-flight mass spectrometry of isomeric trehaloses

The configuration isomers alpha,alpha-, alpha,beta-, and beta,beta-trehalose are distinguishable by a relative ion abundance analysis using collision-induced dissociation MS/MS measurements in electrospray ionization quadrupole-time-of-flight mass spectrometry. The relative abundance of the Y-type fragment ion of alpha,alpha-trehalose is the highest and that of beta,beta-trehalose is the lowest, indicating that alpha-glycosyl bonds cleave more easily than beta-glycosyl bonds. The relative ion abundance depends on both the alpha- and beta-glycosyl linkage type and the number of alpha-glycosyl bonds. The reaction path of glycosyl bond cleavage is calculated computationally using the molecular orbital method in the form of Hartree-Fock theory in conjunction with the 6-31G(d) basis set. The results are consistent with the experimental data. Isotope effects on the fragmentation of the glycosyl bonds are detected in the experiments of the H2O/D2O solvent systems. Furthermore, the isotope effect regarding beta,beta-trehalose is larger than those of alpha,alpha- and alpha,beta-trehalose, indicating that the isotope effect on the beta-glycosyl bond cleavage is larger than that on the alpha-glycosyl bond cleavage. The thermal energy increase in trehalose-d8 molecules over the corresponding trehalose molecules is calculated from the vibrational modes.     

Thermal degradation characteristics of oil‐filled cable joint with extremely degraded tan δ oil

Much of oil‐filled (OF) cable has been used for a long time as 66‐ to 500‐kV extrahigh‐voltage cable. Sometimes we can see extremely degraded tan δ oil (several tens of percent of tan δ, for example) in joint boxes, etc. The values of tan δ calculated by a simple combination model of paper/oil show that the oil‐impregnated paper with such a high tan δ oil likewise has an extremely high tan δ, which must result in thermal breakdown. However, such an event has not taken place up to the present in actually operated transmission lines. This fact suggests that some mechanism for the suppression of tan δ has acted in the paper insulation impregnated with degraded tan δ oil. Therefore, we investigated in detail the tan δ characteristics of paper impregnated with extremely high tan δ oil. In addition, based on the investigation results, we developed a method for simulation of heat generation by dielectric loss in an OF cable joint (which has degraded tan δ oil). © 2011 Wiley Periodicals, Inc. Electr Eng Jpn, 178(1): 1–10, 2012; Published online in Wiley Online Library ( wileyonlinelibrary.com ). DOI 10.1002/eej.21184     

A New Hybrid Phosphine Ligand for Palladium‐Catalyzed Amination of Aryl Halides

A new hybrid phosphine was designed. The phosphine combines two common structural characteristics found among the effective phosphine ligands reported recently, namely, three tert‐alkyl substituents binding to the phosphorus and an aryl group at an appropriate position. A hybrid phospine/palladium system is versatile and effective for the coupling reaction of various aryl halides with primary and secondary amines including carbazole.     

Synthesis and Characterization of Glycidyl Azide‐r‐(3,3‐bis(azidomethyl)oxetane) Copolymers

Glycidyl azide‐r‐(3,3‐bis(azidomethyl)oxetane) copolymers were synthesized by cationic copolymerization of epichlorohydrin and 3,3‐bis(bromomethyl)oxetane, using butane‐1,4‐diol as an initiator and boron trifluoride etherate as a catalyst, followed by azidation of the halogenated copolymer. The main objective of this work is the preparation of an OH‐terminated amorphous polymer with energetic content higher than that of the well‐known glycidyl azide homopolymer. The effect of experimental conditions, i.e., the rate of monomer feeding, on the final molecular weight and functionality of the copolymer has also been investigated. The obtained copolymers were extensively characterized to determine their composition and thermal stability. The heat of reaction for the polymerization of the halogenated key precursors has also been measured. It was found that even though both the operating conditions and the catalytic system were chosen in order to favor a living character of the polymerization, the final product seems to be the result of a combined living and active chain end mechanism. In particular, the latter is responsible for the formation of oligomers and not hydroxyl‐terminated chains. Nevertheless, the average number of OH groups is high enough to allow a cross‐linking of the polymeric chains, by addition of polyisocyanates and subsequent formation of inter‐chain urethanic bonds.     

Structure-Based Design,Synthesis, and Biological Evaluation of Imidazo[4,5-b]Pyridin-2-one-Based p38 MAP Kinase Inhibitors: Part 2

We identified novel potent inhibitors of p38 mitogen-activated protein (MAP) kinase using a structure-based design strategy, beginning with lead compound, 3-(butan-2-yl)-6-(2,4-difluoroanilino)-1,3-dihydro-2H-imidazo[4,5-b]pyridin-2-one ( 1 ). To enhance the inhibitory activity of 1 against production of tumor necrosis factor-α (TNF-α) in human whole blood (hWB) cell assays, we designed and synthesized hybrid compounds in which the imidazo[4,5-b]pyridin-2-one core was successfully linked with the p-methylbenzamide fragment. Among the compounds evaluated, 3-(3-tert-butyl-2-oxo-2,3-dihydro-1H-imidazo[4,5-b]pyridin-6-yl)-4-methyl-N-(1-methyl-1H-pyrazol-3-yl)benzamide ( 25 ) exhibited potent p38 inhibition, superior suppression of TNF-α production in hWB cells, and also significant in vivo efficacy in a rat model of collagen-induced arthritis (CIA). In this paper, we report the discovery of potent, selective, and orally bioavailable imidazo[4,5-b]pyridin-2-one-based p38 MAP kinase inhibitors.     

Effect of texture on oxidation resistance of Ti3AlC2

Oxidation resistance of textured Ti₃AlC₂ ceramics was measured in the temperature range 1273–1573?K. It was found that the oxidation was markedly anisotropic and the samples exhibited a better oxidation resistance when tested along a direction transverse to the c-axis. This behavior was attributed to the rapid diffusion of Al within its basal planes to form a passivating Al₂O₃ scale and it respected Ellingham diagrams. The scales formed had different compositions depending on the testing direction; this response was clearly resulting from the crystallographic orientation. Even at 1473?K after 20?h exposure, the samples tested in a direction transverse to the c-axis showed a reduced weight gain which was 45 times lower than one seen on a basal plane.     

Development of measuring system for radial non-repetitive run-out (NRRO) and perception about present state of angular contact ball bearing for machine tools

This paper deals with the non-repetitive run-out (NRRO) of an angular contact ball bearing for machine tools. First, a measuring system for the rotational accuracy of the bearing was developed. Then, the following results were obtained using the developed measuring system.

(1)

The NRRO of ball cage rotation increased with rotational speed.

(2)

The influence of form errors in the inner and outer rings on NRRO was small.

(3)

The influences of form errors in the balls of the bearing and the diameter difference of balls on NRRO were significant.

     

Fabrication of lead-free piezoelectric (Bi<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>)TiO<Subscript>3</Subscript>–BaTiO<Subscript>3</Subscript> ceramics using electrophoretic deposition

Electrophoretic deposition (EPD) process has certain advantages such as it can be applied for a mass production and also can be combined with magnetic crystal alignment technique. In this work, we prepared lead-free 85(Bi_0.5Na_0.5)TiO₃–15BaTiO₃ (85BNT–15BT) piezoelectric ceramics by conventional uniaxial pressing and EPD process. Various conditions were optimized such as suspension media, applied electrical field, and deposition time in order to yield dense green ceramics of 85BNT–15BT composition using EPD process. 85BNT–15BT ceramics prepared using EPD process revealed the Curie temperature of about 250 °C, coercive field of about 30 kV/cm, and piezoelectric constant (d ₃₃) of 75 pC/N. The EPD-processed samples exhibited structural and electrical properties similar to that of the conventionally processed one suggesting the successful fabrication of 85BNT–15BT piezoelectric ceramics by EPD method without composition deviation. This study lays a foundation on the fabrication of Bi-based lead-free piezoelectric ceramics by an alternative route other than the conventionally practiced solid-state reaction method maintaining the similar chemical composition, moreover, leaving a large space to explore more in the future.     

Electrodeposition and growth mechanism of preferentially orientated nanotwinned Cu on silicon wafer substrate

Homogeneous columnar Cu film with fully embedded nanotwins was successfully fabricated on Ti/Cu seed layer on silicon wafer. The nanotwins with thickness of tens of nanometers are generally parallel to the silicon surface, showing a strong (111) preferred orientation. The acid concentration was found to be important in influencing the formation of nanoscale twins. By adjusting the acid concentration, the nanotwins can be induced from the top columnar grain to middle columnar grain and reach the bottom equiaxed grain, and a microstructural transformation model was given. A theory focusing on the cathode overpotential was proposed to reveal the effect of acid concentration on the growth mechanism of nanoscale twins. An appropriate adsorption proportion of hydrogen on cathode (acid concentration 17 ml L^?1) could increase the overpotential which supplies adequate nucleation energy for nanoscale twins formation.