Decomposition of chlorofluorocarbons on TiO2ZrO2

The decomposition of chlorofluorocarbons (CFCs) in the presence of water was examined over a variety of solid acid catalysts. The TiO₂ZrO₂ catalyst was found to have the highest activity and longest life among the catalysts examined. The activity of the TiO₂ZrO₂ catalysts depended upon the content of TiO₂. At the contents of TiO₂ from 58 to 90 mole%, the TiO₂ZrO₂ catalysts exhibited high activity, and these catalysts were proven to contain TiZrO₄ crystal. From the study of the XRD peak intensity of the TiZrO₄ crystal, it was highest on the TZ-58 which contained 58 mole% of TiO₂, and decreased with increasing the content of TiO₂. Furthermore, the conversion of CFC113 measured at 673 K was highest at TZ-58, and decreased gradually with increasing TiO₂ content. Therefore, the TiZrO₄ crystal influences the activity of decomposition of CFC113. However, the TiO₂ZrO₂ catalyst was gradually deactivated during the reaction due to the elimination of titanium atoms. A good relationship was found between the activity on TiO₂ZrO₂ catalyst and bond energy of CCl in the compounds of chlorofluorocarbons and hydrochlorocarbons, suggesting that the rate controlling step was the cleavage of CCl bond.     

Controlling the familywise error rate in functional neuroimaging: a comparative review

Functional neuroimaging data embodies a massive multiple testing problem, where 100,000 correlated test statistics must be assessed. The familywise error rate, the chance of any false positives is the standard measure of Type I errors in multiple testing. In this paper we review and evaluate three approaches to thresholding images of test statistics: Bonferroni, random field and the permutation test. Owing to recent developments, improved Bonferroni procedures, such as Hochberg's methods, are now applicable to dependent data. Continuous random field methods use the smoothness of the image to adapt to the severity of the multiple testing problem. Also, increased computing power has made both permutation and bootstrap methods applicable to functional neuroimaging. We evaluate these approaches on t images using simulations and a collection of real datasets. We find that Bonferroni-related tests offer little improvement over Bonferroni, while the permutation method offers substantial improvement over the random field method for low smoothness and low degrees of freedom. We also show the limitations of trying to find an equivalent number of independent tests for an image of correlated test statistics.     

Effect of polymer density on polyethylene hollow fiber membrane formation via thermally induced phase separation

Microporous high‐density polyethylene (HDPE) and low‐density polyethylene (LDPE) hollow fiber membranes were prepared from polyethylene–diisodecyl phthalate solution via thermally induced phase separation. Effect of the polyethylene density on the membrane structure and performance was investigated. The HDPE membrane showed about five times higher water permeability than the LDPE membrane because it had the larger pore and the higher porosity at the outer membrane surface. The formation of the larger pore was owing to both the initial larger structure formed by spinodal decomposition and the suppression of the diluent evaporation from the outer membrane surface due to the higher solution viscosity. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 471–474, 2004     

Observation of single-walled carbon nanotubes by photoemission microscopy

Single-walled carbon nanotube networks grown on SiO₂ pillars were studied by means of scanning photoemission microscopy. The individual nanotubes or nanotube bundles growing from the pillar tops were observed in C 1s images. Band bending near catalytic Fe/nanotube contacts in an end-bonded configuration was studied by measuring C 1s spectra along the tube axes. Within our experimental resolution, no band bending was observed. This implies that the depletion width is less than the spatial resolution of the scanning photoemission microscope (90 nm) or that the amount of the band bending is less than 0.1 eV.     

Design of new catalysts for ecological high-quality transportation fuels by combinatorial computational chemistry and tight-binding quantum chemical molecular dynamics approaches

Recently, we introduced a concept of combinatorial chemistry to computational chemistry and proposed a new method called “combinatorial computational chemistry”, which enables us to perform a theoretical high-throughput screening of catalysts. In the present paper, we reviewed our recent application of our combinatorial computational chemistry approach to the design of new catalysts for high-quality transportation fuels. By using our combinatorial computational chemistry techniques, we succeeded to predict new catalysts for methanol synthesis and Fischer–Tropsch synthesis. Moreover, we have succeeded in the development of chemical reaction dynamics simulator based on our original tight-binding quantum chemical molecular dynamics method. This program realizes more than 5000 times acceleration compared to the regular first-principles molecular dynamics method. Electronic- and atomic-level information on the catalytic reaction dynamics at reaction temperatures significantly contributes the catalyst design and development. Hence, we also summarized our recent applications of the above quantum chemical molecular dynamics method to the clarification of the methanol synthesis dynamics in this review.     

Organic–silicate hybrid catalysts based on various defined structures for Knoevenagel condensation

Two types of organic–inorganic hybrid base catalysts are prepared. Organic-functionalized molecular sieves (OFMSs), particularly “amine-immobilized porous silicates”, are designed based on common idea to immobilize catalytic active sites on silicate surface. Silicate–organic composite materials (SOCMs), such as “ordered porous silicate–quaternary ammonium composite materials”, are the precursors of ordered porous silicates obtained during the synthesis. Both the OFMS and the SOCM are used as the catalysts for Knoevenagel condensation. Among the OFMSs, there is clear tendency that the use of molecular sieve with larger pore volume and/or surface area gives the product in higher yield. Aminopropylsilyl (AP)-functionalized mesoporous silicates such as AP-MCM-41 gives the product in high yield under mild conditions. No loss of activity is observed after repeated use for three times. The SOCMs are also active for the same reaction. The precursors of the mesoporous silicates are more active than those of microporous silicates. This material can be repeatedly used without significant loss of activity. High activity is not due to the leached species. The active sites of the SOCM catalysts are considered to be SiO⁻ moieties located on the pore-mouth. Activity of the SOCM increases when the reaction is carried out without solvent, whereas decrease in activity of the OFMS is observed in the solvent-free system.     

Synthesis of AlPO4 Molecular Sieves with AFI and AEL Structures by Dry-Gel Conversion Method and Catalytic Application of Their SAPO Counterparts on Isopropylation of Biphenyl

AlPO₄-5 and AlPO₄-11 were synthesized by dry-gel conversion (DGC) method. Steam-assisted conversion (SAC) and vapor-phase transport (VPT) techniques were applied for this purpose. The synthesis was successful in presence of a certain minimum amount of external bulk water, without which the crystallization failed. Crystallization by VPT method was slower than corresponding SAC and HTS method. SAPO analogs of the samples, SAPO-5 and SAPO-11 were also synthesized by DGC method. Samples made by DGC methods had higher yield than the conventional hydrothermal synthesis (HTS); otherwise the samples showed similar characteristics as that made by HTS. XRD, SEM and N₂-adsorption results showed high crystallinity and purity of the samples made by DGC, and ²⁷Al MAS NMR spectra indicated the tetrahedral framework nature of Al. SAPO-5 and SAPO-11 were tested for their catalytic activity in isopropylation of biphenyl, and in terms of conversion and selectivity, SAPO-5 was found to be suitable for this application.     

Potential bile acid metabolites. 24. An efficient synthesis of carboxyl-linked glucosides and their chemical properties

A facile and efficient synthesis of the carboxyl-linked glucosides of bile acids is described. Direct esterification of unprotected bile acids with 2,3,4,6-tetra-O-benzyl-d-glucopyranose in pyridine in the presence of 2-chloro-1,3,5-trinitrobenzene as a coupling agent afforded a mixture of the α- and β-anomers (ca. 1∶3) of the 1-O-acyl-d-glucoside benzyl ethers of bile acids, which was separated effectively on a C₁₈ reversedphase chromatography column (isolated yields of α- and β-anomers are 4–9% and 12–19%, respectively). Subsequent hydrogenolysis of the α- and β-acyl glucoside benzyl ethers on a 10% Pd−C catalyst in acetic acid/methanol/EtOAc (1∶2∶2, by vol) at 35°C under atmospheric pressure gave the corresponding free esters in good yields (79–89%). Chemical specificities such as facile hydrolysis and transesterification of the acyl glucosides in various solvents were also discussed.     

Comparative study on the preparation and properties of radiation‐grafted polymer electrolyte membranes based on fluoropolymer films

In this study the fluoropolymers, poly(ethylene‐co‐tetrafluoroethylene) (ETFE) and poly(vinylidene fluoride) (PVDF) films, together with the radiation‐induced crosslinked polytetrafluoroethylene (cPTFE) film were compared on the basis of their preparation and properties of radiation‐grafted polymer electrolyte membranes. The polymer electrolyte membranes were prepared by radiation grafting of styrene into the base films and subsequent sulfonation. The proton conductivity and chemical stability of the three types of membranes with a similar ion exchange capacity (IEC) near 1.0 mmol/g were investigated and are discussed in detail. Although the ETFE‐based polymer electrolyte membrane was relatively more stable, its proton conductivity was lower than those of the PVDF‐ and cPTFE‐based membranes. On the other hand, the cPTFE‐based membrane showed a significantly higher proton conductivity, but its chemical stability was shorter than that of the ETFE‐based membrane. It is considered that the difference in the preparation and properties of the polymer electrolyte membranes was due to the difference in the degree of crystallinity as well as in the chemical structure of the fluoropolymer base films. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1966–1972, 2007     

Effect of metallic ions in photo-induced graft copolymerization onto cellulose

In photo-induced graft copolymerization of methyl methacrylate onto cellulose, the effect of metallic ions as sensitizer was investigated. Some metallic ions were effective in their adsorbed states and accelerated the formation of grafts in the order Fe²⁺ > Ag⁺ > Fe³⁺. However, Cu²⁺ acted negatively, and little effect was observed for Co²⁺, Ni²⁺, Mn²⁺, Zn²⁺, and Cr³⁺. In the systems in which aqueous metallic salt solutions were added, the formation of grafts was generally depressed, but Fe³⁺ was an exception. The effect of metallic ions on the scission reaction of cellulose main chains did not necessarily agree with the effect on the formation of grafts. This is attributed to the varied interaction between cellulose and the different active species produced by irradiation, depending on the type of metallic ions used.