Improvement of thermal stability of NO oxidation Pt/Al2O3 catalyst by addition of Pd

The present work has been undertaken to tailor Pt/Al₂O₃ catalysts active for NO oxidation even after severe heat treatments in air. For this purpose, the addition of Pd has been attempted, which is less active for this reaction but can effectively suppress thermal sintering of the active metal Pt. Various Pd-modified Pt/Al₂O₃ catalysts were prepared, subjected to heat treatments in air at 800 and 830 °C, and then applied for NO oxidation at 300 °C. The total NO oxidation activity was shown to be significantly enhanced by the addition of Pd, depending on the amount of Pd added. The Pd-modified catalysts are active even after the severe heat treatment at 830 °C for a long time of 60 h. The optimized Pd-modified Pt/Al₂O₃ catalyst can show a maximum activity limited by chemical equilibrium under the conditions used. The bulk structures of supported noble metal particles were examined by XRD and their surface properties by CO chemisorption and EDX-TEM. From these characterization results as well as the reaction ones, the size of individual metal particles, the chemical composition of their surfaces, and the overall TOF value were determined for discussing possible reasons for the improvement of the thermal stability and the enhanced catalytic activity of Pt/Al₂O₃ catalysts by the Pd addition. The Pd-modified Pt/Al₂O₃ catalysts should be a promising one for NO oxidation of practical interest.     

Carbon dioxide pressure induced heterogeneous and homogeneous Heck and Sonogashira coupling reactions using fluorinated palladium complex catalysts

The Heck reaction of iodobenzene and methyl acrylate was investigated with CO₂-philic Pd complex catalysts having fluorous ponytails and the organic base triethylamine (Et₃N) in the presence of CO₂ under solventless conditions at 80 °C. The catalysts are not soluble in the organic phase in the absence of CO₂ and the reaction occurs in a solid-liquid biphasic system. When the organic liquid mixture is pressurized by CO₂, CO₂ is dissolved into the organic phase and this promotes the dissolution of the Pd complex catalysts. As a result, the Heck reaction occurs homogeneously in the organic phase, which enhances the rate of reaction. This positive effect of CO₂ pressurization competes with the negative effect that the reacting species are diluted by an increasing amount of CO₂ molecules dissolved. Thus, the maximum conversion appears at a CO₂ pressure of around 4 MPa under the present reaction conditions. The catalysts are separated in the solid granules by depressurization and are recyclable without loss of activity after washing with n-hexane and/or water. When the washing is made with hexane alone, the catalytic activity tends to increase on the repeated Heck reactions, probably due to the accumulation of such a base adduct as Et₃NHI on the catalysts. When the washing is further made with water, however, the base adduct is taken off from the catalysts and they show similar activity levels in the repeated runs. The potential of CO₂ pressure tunable heterogeneous/homogeneous reaction system has also been investigated for Sonogashira reactions of iodobenzene and phenylacetylene under similar conditions.     

Precision die-casting of optical MU/SC conversion sleeve

The performance of MU/SC conversion sleeve produced by bulk metallic glass (Zr₅₅Al₁₀Ni₅Cu₃₀) was examined. A precision die-casting method was applied to improve size accuracy. The size accuracy of the conversion sleeve produced by the precision die-casting method was ±1 μm, and optical insertion loss (Li) was less than 0.3 dB for a standard value. The wear resistance of metallic glass is improved by surface oxidation treatment in air at 673 K. The MU/SC conversion sleeve produced from bulk metallic glass has superior characteristics for optical parts.     

Selective hydrogenation of chloronitrobenzene to chloroaniline in supercritical carbon dioxide over Ni/TiO2: Significance of molecular interactions

The hydrogenation of chloronitrobenzene to chloroaniline was investigated over Ni/TiO₂ at 35 °C in supercritical CO₂ (scCO₂), ethanol, and n-hexane. The reaction rate followed the order of scCO₂ > n-hexane > ethanol. In scCO₂, the selectivity to chloroaniline and to aniline over Ni/TiO₂ were 97–99.5% and <1%, respectively, in the conversion range of 9–100%. The high chemoselectivity to chloroaniline cannot be achieved over Ni/TiO₂ in ethanol and n-hexane. In situ high-pressure Fourier transform infrared measurements were made to study the molecular interactions of CO₂ with the following reactant and reaction intermediates: chloronitrobenzene, chloronitrosobenzene, and N-chlorophenylhydroxylamine. The molecular interaction modifies the reactivity of each species and accordingly the reaction rate and the selectivity. The influence of Cl substituent on the interaction modes of CO₂ with these reacting species is discussed. Possible reaction pathways for the hydrogenation of chloronitrobenzene in scCO₂ over Ni/TiO₂ are also proposed.     

Overexpression and purification of Aspergillus aculeatus beta-mannosidase and analysis of the integrated gene in Aspergillus oryzae

An expression plasmid for the manB gene encoding Aspergillus aculeatus beta-d-mannosidase (MANB) was constructed by using an expression vector carrying an improved promoter. After transformation of A. oryzae by the plasmid, several transformants formed colonies emitting fluorescence on a plate containing 4-methylumbelliferyl beta-d-mannopyranoside (MU-Man) under UV-irradiation. The transformant that displayed the strongest fluorescence, named A. oryzae BMN1, produced about 270 mg MANB/l in liquid culture. Recombinant MANB overproduced in BMN1 was purified by two steps of column chromatography to a single protein band on SDS-polyacrylamide gel electrophoresis and had a molecular weight of 130,000. Analyses by Southern blotting and genomic PCR demonstrated that a single copy of the plasmid was integrated into the chromosome by recombination at the niaD locus.     

Characterization of the Thermo-Viscoelastic Property of Glass and Numerical Simulation of the Press Molding of Glass Lens

A measurement technique for obtaining the thermo-viscoelastic properties of glass with high accuracy is discussed. An unidirectional compression creep test was employed to measure the relaxation modulus of the glass specimens. The creep function derived from the experimental creep test is approximated by a generalized Voigt model, and then converted into a relaxation modulus expressed by a generalized Maxwell model using the Laplace transform and its inversion. Relaxation moduli and shift factors of the glass specimens BK-7 and TaF-3 were estimated according to the presented procedure, and the accuracy of the relaxation modulus was verified by a numerical demonstration using finite element analysis. A fundamental numerical simulation of the press molding of glass lenses was carried out to illustrate the validity of the thermo-viscoelastic properties obtained by the presented approach. Residual stresses under processing conditions were estimated, and the optimal conditions for residual stress minimization are discussed.     

Restoration of solid oxide fuel cell stacks after failure of partial cells

We investigated a solid oxide fuel cell stack that employs anode-supported planar cells in which two intermediate plates are installed every 10 cells to determine the influence of the separation and reconnection of the intermediate plates after high temperature operation. We showed that this separation and reconnection caused no significant degradation in stack performance. A 30-cell stack, which was constructed by removing two 10-cell sub-stacks from a 50-cell stack that had operated stably 1200 h, functioned well. The difference between the average voltages of the cells in the 50- and 30-cell stacks was less than 3% when the current density, fuel utilization, and oxygen utilization were 0.30 A cm⁻², 60%, and 15%, respectively. The 30-cell stack operated stably for about 1200 h with almost no degradation. These findings indicate that our stack can be restored after cells in the stack have broken down simply by removing the 10-cell sub-stacks that contain the broken cells and replacing them with undamaged 10-cell sub-stacks.     

A 65 nm Single-Chip Application and Dual-Mode Baseband Processor With Partial Clock Activation and IP-MMU

Supporting both WCDMA with HSDPA and GSM/GPRS/EDGE, the 9.3 times 9.3 mm² SoC fabricated in triple-Vth 65 nm CMOS, has three CPU cores and 20 separate power domains. Unused power domains can be powered down to reduce the leakage power. Partial clock activation scheme especially focused on music playback scene dynamically stops a PLL and clock trees when not necessary and reduces power consumption from 33.6 mW to 19.6 mW. IP-MMU translates virtual address to physical address for 18 hardware-IPs and virtual address space can be allocated when necessary and can be freed after its operation, reducing external memory by 43 MB. Video performance of D1 (720 times 520) size with 30 frames per second for MPEG/AVC decoding and encoding can be achieved under mixed virtual and physical address usage.     

Regime shifts observed in Lake Kasumigaura,a large shallow lake in Japan: Analysis of a 40‐year limnological record

Lake Kasumigaura, which is composed of the two basins (Nishiura and Kitaura), is a large, shallow, hypereutrophic lake. Phytoplankton and water quality records from the past forty years were analysed to elucidate whether or not, when, and what type of certain regime shifts may have occurred, based on using inferential regime shift detectors. Characteristics of the phytoplankton and water quality changes were similar at 6 sampling sites in the two basins, with 20 water quality parameters being classified into four groups, based on cluster analysis. Shifts in dominant plankton groups (DPGs) and water quality occurring almost concomitantly, concentration on the period from 1987 to 1992 (Shift A) and from 1997 to 2001 (Shift B), with those observed for the two basins usually being similar with small differences. Two types of inferential regime shift detectors (sequential t‐test type; Rodionov's RSD and sequential F‐test type: package strucchange in R) yielded similar timings and significances of the shifts. Furthermore, changes in skewness and conditional heteroskedasticity (package early warnings in R) usually represented early warning signals before the shifts. Correlation analysis and ratios of dissolved inorganic nitrogen (DIN) vs. total phosphorus (TP) supported the hypothesis that phosphorus was the phytoplankton biomass limiting nutrient, except for one period for the Nishiura basin. Neither the nitrogen:phosphorus (N/P) ratio hypothesis and ammonia–nitrate (NH₄‐N/NO₃‐N) hypothesis satisfactorily explain the DPGs before and after Shift A (Microcystis spp. and Planktothrix spp., respectively), although it may be possible that these ratios triggered the DPG change in this shift. A considerable increase in silicon was observed for Shift B when the DPGs changed from cyanobacteria to diatoms. Further studies on the accurate types and triggers of the regime shifts are necessary to better understand the interactions between ecosystem and water quality for this and similar lakes elsewhere.