Reusability, Durability and Treatability of Palladium Catalyst on a Semiconductor Plate: Comparison with Commercially Available Solid-Supported Palladium Catalysts

A palladium catalyst supported on a semiconductor plate underwent the Heck reaction effectively to afford a coupling product. The catalytic plate was easily recovered from the reaction mixture with tweezers and reused several times without any special treatment. Comparison of reusability, durability, and treatability of seven kinds of commercially available solid-supported palladium catalysts and the semiconductor-supported catalyst plate was studied.     

Characterization of the ybdT gene product of Bacillus subtilis: Novel fatty acid β-hydroxylating cytochrome P450

We have characterized the gene encoding fatty acid α-hydroxylase, a cytochrome P450 (P450) enzyme, from Sphingomonas paucimobilis. A database homology search indicated that the deduced amino acid sequence of this gene product was 44% identical to that of the ybdT gene product that is a 48 kDa protein of unknown function from Bacillus subtilis. In this study, we cloned the ybdT gene and characterized this gene product using a recombinant enzyme to clarify function of the ybdT gene product. The carbon monoxide difference spectrum of the recombinant enzyme showed the characteristic one of P450. In the presence of H₂O₂, the recombinant ybdT gene product hydroxylated myristic acid to produce β-hydroxyristic acid and α-hydroxymyristic acid which were determined by high-performance liquid chromatography (HPLC) and gas chromatography-mass spectrometry. The amount of these products increased with increasing reaction period and amount of H₂O₂ in the reaction mixture. The amount of β-hydroxyl product was slightly higher than that of α-hydroxyl product at all times during the reaction. However, no reaction products were detected at any time or at any concentration of H₂O₂ when heat-inactivated enzyme was used. HPLC analysis with a chiral column showed that the β-hydroxyl product was nearly enantiomerically pure R-form. These results suggest that this P450 enzyme is involved in a novel biosynthesis of β-hydroxy fatty acid.     

Synthesis and properties of cobalt-dispersed carbons by pressure pyrolysis of organocobalt polymers

Cobalt-dispersed carbons were synthesized by pressure pyrolysis of cobaltocene-divinylbenzene and phenylallylcobaltocene-divi nylbenzene at 125 MPa below 700° C. The carbons resulting from cobaltocene-divinylbenzene contained uniformly dispersed fine particles, < 20 nm diameter, of metallic cobalt of lower crystallinity, which were composed of ferromagnetic and superparamagnetic particles. Metallic cobalt particles of cubic and hexagonal structures with higher crystallinity were formed during pyrolysis of phenylallylcobaltocene-divinyibenzene. Cobaltucence-divinylbenzene and phanylallylcobaltocene-divinylbenzene changed their magnetic properties from diamagnetism to paramagnetism at 250 and 200° C, respectively. The infrared absorption band of the cyclopentadienyl ring at 995 cm^–1 disappeared at 350° C in cobaltocene divinylbenzene and at 300° C in phenylallylcobaltocene-divinylbenzene. Superparamagnetic particles from cobaltocene-divinylbenzene aggregated and crystallized to produce larger particles of diameter 30 to 100 nm, which increased the magnetization during thermomagnetic measurement. The saturation magnetization of cobalt-dispersed carbons from phenylallylcobaltocene-divinylbenzene was higher by about 10% than that from cobaltocene-divinylbenzene. The coercive forces of cobalt-dispersed carbon from phenylallylcobaltocene-divinylbenzen and cqbaltocene-divinylbenzene were 350 and 250 Oe (2.79 × 10⁴ and 1.99 × 10⁴ Am^–1), respectively.     

Organic dyes with oligo-n-hexylthiophene for dye-sensitized solar cells: Relation between chemical structure of donor and photovoltaic performance

Organic dyes with the oligohexylthiophene linkage having several donor parts, carbazole, indole, and indoline, were newly synthesized as sensitizers for dye-sensitized solar cells. The carbazole was most efficient donor moiety for DSSCs among these dyes with the oligothiophene linkage. Carbazole dyes were adsorbed with larger amount of molecules on the TiO₂ film than both indole dyes and indoline dyes. Therefore, both the V_OC and the electron lifetime of DSSCs with the carbazole dyes were highly observed. The decreasing of J_SC of DSSCs with indole and indoline dyes also caused by the reducing the adsorption amount of dyes.     

Mitochondrial phospholipid hydroperoxide glutathione peroxidase plays a major role in preventing oxidative injury to cells

Phospholipid hydroperoxide glutathione peroxidase (PHGPx) is synthesized as a long form (L-form; 23 kDa) and a short form (S-form; 20 kDa). The L-form contains a leader sequence that is required for transport to mitochondria, whereas the S-form lacks the leader sequence. A construct encoding the leader sequence of PHGPx tagged with green fluorescent protein was used to transfect RBL-2H3 cells, and the fusion protein was transported to mitochondria. The L-form of PHGPx was identified as the mitochondrial form of PHGPx and the S-form as the non-mitochondrial form of PHGPx since preferential enrichment of mitochondria for PHGPx was detected in M15 cells that overexpressed the L-form of PHGPx, whereas no similar enrichment was detected in L9 cells that overexpressed the S-form. Cell death caused by mitochondrial injury due to potassium cyanide (KCN) or rotenone (chemical hypoxia) was considerably suppressed in the M15 cells, whereas the L9 cells and control RBL-2H3 cells (S1 cells, transfected with the vector alone) succumbed to the cytotoxic effects of KCN. Flow cytometric analysis showed that mitochondrial PHGPx suppressed the generation of hydroperoxide, the loss of mitochondrial membrane potential, and the loss of plasma membrane integrity that are induced by KCN. Mitochondrial PHGPx might prevent changes in mitochondrial functions and cell death by reducing intracellular hydroperoxides. Mitochondrial PHGPx failed to protect M15 cells from mitochondrial injury by carbonyl cyanide m-chlorophenylhydrazone, which directly reduces membrane potential without the generation of hydroperoxides. M15 cells were more resistant than L9 cells to cell death caused by direct damage to mitochondria and to extracellular oxidative stress. L9 cells were more resistant to tert-butylhydroperoxide than S1 cells, whereas resistance to t-butylhydroperoxide was even more pronounced in M15 cells than in L9 cells. These results suggest that mitochondria might be a target for intracellular and extracellular oxidative stress and that mitochondrial PHGPx, as distinct form non-mitochondrial PHGPx, might play a primary role in protecting cells from oxidative stress.     

Insulation properties of a CO2/N2 50% SF6 gas mixture in a nonuniform field

This paper describes partial discharge (PD) inception and breakdown voltage characteristics of a CO₂/N₂/SF₆ gas mixture in a nonuniform field. These voltage characteristics were investigated with ac high voltage by changing the mixture rate of each gas of CO₂, N₂, and SF₆ gas and the gas pressure from 0.1 MPa to 0.6 MPa. It was found that adding a small amount of CO₂ gas into a N₂/SF₆ mixture causes a drastic increase in the breakdown voltage. For instance, when the mixture rate of SF₆ in N₂/SF₆ gas mixture is 50%, with the addition of 1% CO₂ the maximum breakdown voltage becomes 1.31 and 1.15 times higher than that of a 50% N₂/50% SF₆ gas mixture and pure SF₆ gas, respectively. Moreover, those voltage characteristics of a CO₂/N₂/SF₆ gas mixture were also investigated by changing the electric field utilization factor as well as by applying positive and negative standard lightning impulse voltages in order to discuss the corona stabilization effect, which seems to be one reason for the drastic increase in the breakdown voltage. These results and breakdown mechanism of the CO₂/N₂/SF₆ gas mixture are discussed on the basis of the corona stabilization effect and the dissociation energies of the component gases by observing PD light images, PD light intensities through a blue and red filter, and PD current waveforms. © 2002 Wiley Periodicals, Inc. Electr Eng Jpn, 140(3): 34–43, 2002; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/eej.10019     

A Study of Contact Temperature Due to Frictional Heating of UHMWPE

Contact temperature of ultra-high molecular weight polyethylene (UHMWPE) bearing was measured by the infrared radiometric microscope. Lubricant temperature near the contact band was measured simultaneously and compared with the contact temperature. Contact temperature increases of up to 12°C in 30 min were observed under a mean contact pressure 12.7 MPa and sliding speed 50 mm/s. Young's modulus of UHMWPE was estimated as 0.5 GPa from the contact dimensions. The coefficient of friction was evaluated for variety of contact conditions and material combinations for UHMWPE, CoCrMo alloy and sapphire glass. It was confirmed that the contact stress has a large effect on the coefficient of friction and the fluid film has little effect on the coefficient of friction. Under sliding conditions, the thermal property of the moving material has a large effect on an increment of lubricant temperature.