Structural characterization of photoreduced complete and incomplete cubane-type molybdenum oxide clusters in CO and their catalytic behavior in propene metathesis reaction

SiO2-impregnated complete and incomplete cubane-type molybdenum oxide clusters such as [(RhCp*)₄Mo₄O₁₆] (I) and [(RhCp*)₂Mo₃O₉(OMe)₄] (II) were photoreduced with a UHP-Hg lamp (> 365 nm) in CO, resulting in the formation of catalytically active species for propene metathesis at 300 K. The CO-photoreduced Mo oxide clusters were characterized by EXAFS, IR, XPS and TPD technique. The results suggest that the Mo-O_4c (four-centered bridging oxygens) in I were specifically reduced with CO under the illumination to produce two sets of subcarbonyl species, e.g., those characteristic of the IR bands at 2061 and 2021 cm^–1, which were thermally inactive for the¹³CO exchange reaction but very active under illumination at 300 K, possibly assignable to Mo(CO)x (x = 2, 3), whereas those at 2092 and 2035 cm^–1 due to Rh(CO)₂, which were readily exchangeable with¹³CO at 300 K in dark. Removal of both carbonyls attached on Rh and Mo in photoreduced I and II by evacuation at 375–440 K led to the formation of oxygen-deficient Mo⁴+/Mo⁵⁺ sites, which exhibited high catalytic activities in propene metathesis at 300 K to produce an equimolar mixture of ethene and 2-butenes. The CO-photoreduced incomplete cubane Mo oxide cluster (II) exhibited higher activities and higher trans/cis ratios of 2-butenes in the reaction, compared with those on the photoreduced I.     

Vapor-phase carbonylation of methanol over lead on active carbon catalyst

Lead supported on active carbon showed a catalytic activity for the vapor phase carbonylation of methanol under pressurized conditions in the presence of methyl iodide promoter.     

Catalytic Behavior of Bis(Pyrrolide-Imine) and Bis(Phenoxy-Imine) Titanium Complexes for the Copolymerization of Ethylene with Propylene, 1-Hexene,or Norbornene

This contribution reports the catalytic behavior of bis(pyrrolide-imine)Ti complexes 1 and 2 , [2-(RNCH)-C₄H₃N]₂TiCl₂ ( 1 , R = Ph; 2 , R = cyclohexyl), and bis(phenoxy-imine)Ti complex 3 , [2-(Ph-NCH)-3-t Bu-C₆H₃O]₂TiCl₂ for the copolymerization of ethylene with propylene, 1-hexene, or norbornene. An inspection of the X-ray structures of complexes 1–3 suggested that complexes 1 and 2 with pyrrolide-imine ligands would provide more space for olefin polymerization than complex 3 with phenoxy-imine ligands. In addition, DFT calculations also showed that active species derived from complexes 1 and 2 possess higher electrophilicity of the Ti center compared to that from complex 3 . Complexes 1 and 2 on activation with methylalumoxane (MAO) had higher affinity for propylene and 1-hexene and incorporated higher amounts of propylene ( 1 ; 30.5 mol%, 2 ; 23.4 mol%) and 1-hexene ( 1 ; 1.9 mol%, 2 ; 1.7 mol%) than complex 3 (propylene; 4.5 mol%, 1-hexene; 0.4 mol%). The incorporation levels of propylene and 1-hexene displayed by complexes 1 and 2 were lower than those for Cp₂TiCl₂ (propylene; 41.6 mol%, 1-hexene; 5.1 mol%) under identical conditions. In contrast, complexes 1 and 2 exhibited higher incorporation ability for norbornene and produced copolymers with much higher norbornene contents ( 1 ; 32.0 mol%, 2 ; 26.5 mol%) than Cp₂TiCl₂ (1.2 mol%) under the same conditions. Additionally, complex 3 also promoted higher norbornene incorporation (4.3 mol%) than Cp₂TiCl₂ and provided a copolymer with extremely narrow molecular weight distribution (M_w/M_n 1.14). A correlation exists between electrophilicity of the Ti center in active species and norbornene incorporation.     

Low‐frequency sound absorption of organic hybrid comprised of chlorinated polyethylene and N,N′‐dicyclohexyl‐2‐benzothiazolyl sulfenamide

We investigated the sound absorption characteristics of an organic hybrid material comprised of chlorinated polyethylene (CPE) as the matrix polymer and N,N′‐dicyclohexyl‐2‐benzothiazolyl sulfenamide (DBS) as the second component of an organic low‐molecular‐weight compound. We found specific crystallites, obtained by annealing, that generated new absorption for a low‐frequency sound in a CPE/DBS blend. We observed two sound absorption peaks, around 300 and 1000 Hz, in the annealed CPE/DBS (50 : 50 w/w) blends, whereas those peaks were not observed in the untreated sample. There were two kinds of crystals with different melting points in the annealed samples. It was confirmed that the crystals with the lower melting point brought about sound absorption at a low frequency. The crystals that had the lower melting point were smaller and/or more disordered than the crystals that had the higher melting point. We calculated the fraction of these two types of crystals from differential scanning calorimetry and wide‐angle X‐ray diffraction measurements. The annealing or reannealing temperature specified the fraction of the crystal with the lower melting point, and the obtained crystal fraction characterized sound absorption frequency. Therefore, it is possible to control the sound absorption frequency of an organic hybrid by heat treatment such as annealing. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Enrichment of arachidonic acid: Selective hydrolysis of a single-cell oil fromMortierella withCandida cylindracea lipase

Three lipases, isolated previously in our laboratory, and a known lipase fromCandida cylindracea were screened for the enrichment of arachidonic acid (AA). The enzyme fromC. cylindracea was the most effective for the production of oil with high concentration of AA. When a single-cell oil fromMortierella alpina, containing 25% AA, was hydrolyzed with this lipase for 16 h at 35°C, the resulting glycerides contained 50% AA at 52% hydrolysis. After this, no further hydrolysis occurred, even with additional lipase. However, when the glycerides were extracted from the hydrolyzate and were hydrolyzed again with new lipase, the resulting oil contained 60% AA, with a recovery of 75% of its initial AA content. Triglycerides were the main components of the resulting oil. The release of each fatty acid from the oil depended on the hydrolysis rate of its ester. The fatty acid, whose ester is the poorest substrate for the enzyme, is concentrated in the glycerides.     

Heterodimerization of Group I Ribozymes Enabling Exon Recombination through Pairs of Cooperative trans‐Splicing Reactions

Group I (GI) self‐splicing ribozymes are attractive tools for biotechnology and synthetic biology. Several trans‐splicing and related reactions based on GI ribozymes have been developed for the purpose of recombining their target mRNA sequences. By combining trans‐splicing systems with rational modular engineering of GI ribozymes it was possible to achieve more complex editing of target RNA sequences. In this study we have developed a cooperative trans‐splicing system through rational modular engineering with use of dimeric GI ribozymes derived from the Tetrahymena group I intron ribozyme. The resulting pairs of ribozymes exhibited catalytic activity depending on their selective dimerization. Rational modular redesign as performed in this study would facilitate the development of sophisticated regulation of double or multiple trans‐splicing reactions in a cooperative manner.     

Numerical Simulation of Solidification Process on Single Crystal Ni-Based Superalloy Investment Castings

Bridgman directional solidification of investment castings is a key technology for the production of reliable and highly efficient gas turbine blades. In this paper, a mathematical model for three-dimensional （3D） simulation of solidification process of single crystal investment castings was developed based on basic heat transfer equations. Complex heat radiation among the multiple blade castings and the furnace wall was considered in the model. Temperature distribution and temperature gradient in superalloy investment castings of single blade and multiple ones were investigated, respectively. The calculated cooling curves were compared with the experimental results and agreed well with the latter. It is indicated that the unsymmetrical temperature distribution and curved liquid-solid interface caused by the circle distribution of multiple turbine blades are probably main reasons why the stray grain and other casting defects occur in the turbine blade.     

Analysis of photometric factors based on photometric linearization

We propose a method for analyzing photometric factors, such as diffuse reflection, specular reflection, attached shadow, and cast shadow. For analyzing real images, we utilize the photometric linearization method, which was originally proposed for image synthesis. First, we show that each pixel can be photometrically classified by a simple comparison of the pixel intensity. Our classification algorithm requires neither 3D shape information nor color information of the scene. Then, we show that the accuracy of the photometric linearization can be improved by introducing a new classification-based criterion to the linearization process. Experimental results show that photometric factors can be correctly classified without any special devices. A further experiment shows that the proposed method is effective for photometric stereo.     

Effect of thermal cycles on the mechanical strength of quad flat pack leads/Sn-3.5Ag-X (X=Bi and Cu) solder joints

Quad Flat Pack (QFP) Leads/Sn-3.5Ag-X (X=Bi and Cu) joint was thermally cycled between 243 K and 403 K or 273 K and 373 K, and both metallographic examination and mechanical pull test were performed to evaluate thermal fatigue damage of the joint. The addition of bismuth drastically degrades the thermal fatigue resistance of Sn-3.5Ag solder. On the other hand, the pull strength of Sn-3.5Ag-Cu solder joints slightly decreased with increasing number of thermal cycles, though it still remains higher in comparison to that for conventional Sn-37Pb or bismuth containing solder joint. The behavior observed here reflects the isothermal fatigue properties of bulk solder, because thermal fatigue crack initiates at the surface of solder fillet and propagates within the fillet in an early stage of fatigue damage. Furthermore, the lead phases lying at the interface between lead-frame and bismuth containing solder joint may promote the crack propagation at the interface, resulting in the extremely low thermal fatigue resistance of the joint.     

Bendability of aluminiumand steel-clad chromium plates

The present paper describes how the cladding of chromium plate with dissimilar metals improves the plastic bendability of the chromium. Three-point bending tests at various temperatures were performed for three types of chromium specimens: a monolithic chromium plate, aluminium- and steel-clad chromium plate. The aluminium-clad chromium plate was bent at 343 K up to a bent angle of 90 degrees without failure, even when the chromium layer was located outside of the plate (tension side), while the monolithic chromium plate could be bent exclusively at temperatures above 403 K. When the chromium layer was located inside of the steel-clad chromium plate (compression side), the plate was successfully bent at 307 K. The FE stress analysis of bending proved that the cladding of chromium plates with proper metals of different kinds is effective to reduce the tensile stress in chromium induced during bending and also the residual stress existing after bending operation.