In situ XAFS analysis of Pd–Pt catalysts during hydrotreatment of model oil

Supported Pd–Pt catalysts are efficient for hydrodesulfurization (HDS) and hydrodearomatization (HDA) reactions of diesel fuel and their activity varied with the kinds of supports. Concerning HDA, alumina supported catalysts showed four times higher TOF (turn over frequency) than silica supported one. In order to elucidate the difference in activity, the structural analysis of the active phase was performed. After reduction pretreatment, relatively uniform and large metallic alloy Pd–Pt particles were formed on SiO₂, whereas, Pd and Pt atoms formed rather segregated particles on Al₂O₃. Subsequent X-ray absorption of fine structure (XAFS) analysis under HDS conditions showed no contribution of sulfur for SiO₂ supported catalyst, whereas, formation of sulfided metal species was observed in XAFS spectra for the Al₂O₃ supported catalyst. It is suggested that on Pd–Pt/SiO₂, thin sulfide layer on the metal cluster surface blocked the active sites and lowered the HDA activity. Presence of partially sulfided phase originated from rather segregated structure like Pd–Pt/Al₂O₃ is thought to be requisite for high HDA activity.     

Reaction Kinetics of Methanol Carbonylation to Methyl Formate Catalyzed by CH3O− Exchange Resin

The carbonylation of methanol with CO using CH₃O⁻ exchange resin as a heterogeneous catalyst at temperatures near 350 K is examined systematically in an attempt to derive kinetic rate expressions for the reaction. The activation energies for the carbonylation and decarbonylation reactions are found to be 68 kJ/mol and 105 kJ/mol, respectively. The CH₃O⁻ exchange resin is also shown to suffer no degradation of catalytic activity upon repeated separation and re-use at 353 K.     

Application of land use regression to regulatory air quality data in Japan

A land use regression (LUR) model has been used successfully for predicting traffic-related pollutants, although its application has been limited to Europe and North America. Therefore, we modeled traffic-related pollutants by LUR then examined whether LUR models could be constructed using a regulatory monitoring network in Shizuoka, Japan. We used the annual-mean nitrogen dioxide (NO₂) and suspended particulate matter (SPM) concentrations between April 2000 and March 2006 in the study area. SPM accounts for particulate matter with an aerodynamic diameter less than 8 μm (PM₈). Geographic variables that are considered to predict traffic-related pollutants were classified into four groups: road type, traffic intensity, land use, and physical component. Using geographical variables, we then constructed a model to predict the monitored levels of NO₂ and SPM. The mean concentrations of NO₂ and SPM were 35.75 μg/m³ (standard deviation of 11.28) and 28.67 μg/m³ (standard deviation of 4.73), respectively. The final regression model for the NO₂ concentration included five independent variables. R² for the NO₂ model was 0.54. On the other hand, the regression model for the SPM concentration included only one independent variable. R² for the SPM model was quite low (R² = 0.11). The present study showed that even if we used regulatory monitoring air quality data, we could estimate NO₂ moderately well. This result could encourage the wide use of LUR models in Asian countries.     

Characterization of acidic property of sulfo-group functionalized microporous and mesoporous silica by adsorption microcalorimetry

Sulfo-group functionalized microporous and mesoporous silica based-on a MCM-41 framework which showed solid acid property were synthesized and characterized by adsorption microcalorimetry. Both the sulfo-functionalized microporous and mesoporous silica (Micro-SO₃H and Meso-SO₃H) were prepared by the oxidation of thiol group (–SH) included mesoporous silica which was obtained through the hydrolysis and co-condensation of tetramethoxysilane (TMOS) and mercaptopropyl trimethoxysilane (MPTMS). The samples have an ordered two-dimensional hexagonal pore array similar to that of MCM-41 as depicted from the XRD patterns. Nitrogen adsorption also shows that both microporous and mesoporous silica have pore characteristics similar to MCM-41, i.e. high surface area and high pore volume. However, pore regularity, surface area and pore volume decreased as the MPTMS loading increased. Solid-state ²⁹Si NMR indicated that the sulfo groups were successfully incorporated into both microporous and mesoporous silica frameworks. This sulfo-functionalized porous silica have high NH₃ uptakes and high differential heats of NH₃ adsorption, suggesting the presence of strong acidic sulfo groups on the silica surface. Acid catalyses of the samples were characterized by the isomerization reaction of but-1-ene to cis, trans-but-2-ene.     

Tribological properties of asperity arrays coated with self-assembled monolayers

The effects of a self-assembled monolayer (SAM) coating on the friction and pull-off forces were determined by using two-dimensional asperity arrays on silicon wafers. The arrays were coated with SAM composed of one of five different alkylchlorsilanes. First, two-dimensional asperity arrays were created by using a focussed ion beam (FIB) system to mill patterns on silicon plates. Each silicon plate had different patterns of equally spaced asperities. Each pattern (5 × 5 μm²) had a different radius of curvature of the asperity peaks, ranging from about 200 to 2500 nm. Then, each silicon plate was immersed in a solution of a different alkylchlorsilane in hexane (either hexyltrichlorosilane, octyltrichlorosilane, dodecyltrichlorosilane, tetradecyltrichlorosilane, or octadecyltrichlorosilane), thus coating the asperity arrays with SAM. The friction and pull-off forces on the SAM-coated arrays were measured by using an atomic force microscope (AFM) that had a square flat probe. The pull-off force for SAM-coated silicon was roughly proportional to the radius of curvature of the asperity peaks. The magnitude of the pull-off force corresponded approximately to the capillary force calculated by using the contact angle of water on the surface of SAM. The friction coefficient correlated with the inverse of the alkyl-chain length of the SAM.     

Review Peripheral nerve regeneration using non-tubular alginate gel crosslinked with covalent bonds

We have developed a nerve regeneration material consisting of alginate gel crosslinked with covalent bonds. in the first part of this study, we attempted to analyze nerve regeneration through alginate gel in the early stages within 2 weeks. in the second part, we tried to regenerate cat peripheral nerve by using alginate tubular or non-tubular nerve regeneration devices, and compared their efficacies. Four days after surgery, regenerating axons grew without Schwann cell investment through the partially degraded alginate gel, being in direct contact with the alginate without a basal lamina covering. One to 2 weeks after surgery, regenerating axons were surrounded by common Schwann cells, forming small bundles, with some axons at the periphery being partly in direct contact with alginate. At the distal stump, numerous Schwann cells had migrated into the alginate 8–14 days after surgery. Remarkable restorations of the 50-mm gap in cat sciatic nerve were obtained after a long term by using tubular or non-tubular nerve regeneration material consisting mainly of alginate gel. However, there was no significant difference between both groups at electrophysiological and morphological evaluation. Although, nowadays, nerve regeneration materials being marketed mostly have a tubular structure, our results suggest that the tubular structure is not indispensable for peripheral nerve regeneration.     

Compact ellipsometer employing a static polarimeter module with arrayed polarizer and wave-plate elements

A portable ellipsometer with a compact static polarimeter using an arrayed polarizer, an arrayed wave plate, and a CCD image sensor is developed. A high level of repeatability at a measurement speed of 0.3 s is demonstrated by measurement of SiO(2) films ranging from 2 to 300 nm in thickness deposited on an Si wafer. There is the potential to realize an ultracompact ellipsometer module by integrating the optical source and receiver, suitable for deployment in a variety of manufacturing equipment and measurement instruments.     

Minute mixed hepatoma with two components: hepatocellular and cholangiocarcinoma, which developed on liver cirrhosis with HCV

Mixed type hepatoma with two components, hepatocellular and cholangiocellular carcinoma, is very rare. We encountered a case of a single and minute mixed type hepatoma developing on liver cirrhosis in a patient with persistent hepatitis C viral infection. Histologically, the two-type cancer tissue existed in a nodule with a maximal diameter of approximately 20 mm, and the cholangiocellular carcinoma occupied about 70% of the tumor. The original cell of the mixed type hepatoma is unknown, but this case suggests that a bipotential cell developing into hepatocellular and cholangiocellular carcinoma may be the origin.     

A linear-time algorithm for finding a sparsek-connected spanning subgraph of ak-connected graph

We show that anyk-connected graphG = (V, E) has a sparsek-connected spanning subgraphG′ = (V, E′) with ¦E′¦ =O(k¦V¦) by presenting anO(¦E¦)-time algorithm to find one such subgraph, where connectivity stands for either edge-connectivity or node-connectivity. By using this algorithm as preprocessing, the time complexities of some graph problems related to connectivity can be improved. For example, the current best time boundO(max{k ²¦V¦^1/2,k¦V¦}¦E¦) to determine whether node-connectivityK(G) of a graphG = (V, E) is larger than a given integerk or not can be reduced toO(max{k ³¦V¦^3/2,k ²¦V¦²}).     

Translation among CNFs, characteristic models and ordered binary decision diagrams

We consider translation among conjunctive normal forms (CNFs), characteristic models, and ordered binary decision diagrams (OBDDs) of Boolean functions. It is shown in this paper that Horn OBDDs can be translated into their Horn CNFs in polynomial time. As for the opposite direction, the problem can be solved in polynomial time if the ordering of variables in the resulting OBDD is specified as an input. In case that such ordering is not specified and the resulting OBDD must be of minimum size, its decision version becomes NP-complete. Similar results are also obtained for the translation in both directions between characteristic models and OBDDs. We emphasize here that the above results hold on any class of functions having a basis of polynomial size.