Hydrogen production by oxidative methanol reforming on Pd/ZnO: Catalyst preparation and supporting materials

Pd and Pd–Zn alloy were supported on various supporting materials using impregnation, co-precipitation and microemulsion methods, and their catalytic performances in oxidative methanol reforming (OMR) were investigated. Pd/ZnO exhibited much higher selectivity than either Pd/Al₂O₃ or Pd/ZrO₂ in the OMR for hydrogen production. This was attributed to the presence of Pd–Zn alloy on the ZnO support. Elemental Pd on Al₂O₃ or ZrO₂ promotes methanol decomposition reaction and increases CO formation. Using a microemulsion method, a highly selective Pd/ZnO can be obtained with much lower Pd loading than that in samples prepared by co-precipitation. Modification of Al₂O₃ with ZnO produced a ZnAl₂O₄ phase, which was found to be a good support for the Pd/ZnO catalyst. Highly active and selective Pd/ZnO/ZnAl₂O₄ catalysts for the OMR reaction, containing much lower Pd loadings have been developed by impregnation of the supports with an aqueous solution of Pd(NO₃)₂ + Zn(NO₃)₂.     

A comparative study of fracture behavior between carbon black/poly(ethylene terephthalate) and multiwalled carbon nanotube/poly(ethylene terephthalate) composite films

Fracture behavior of amorphous poly(ethylene terephthalate) (PET) films added multiwalled carbon nanotube (MWCNT) has been compared with that of the PET films added with carbon black (CB) to elucidate the effects of the large aspect ratio of MWCNT. Fracture toughness has been evaluated using the essential work of fracture tests. Evolution of the crazes has been analyzed by conducting time‐resolved small‐angle X‐ray scattering measurements during tensile deformation of the films at room temperature using synchrotron radiation. CB and MWCNT increased the fracture toughness of the PET film by increasing the plastic work of fracture. This resulted from the effects of the fillers to prevent the localization of deformation upon the crazes formed at earlier stages of tensile deformation and to retard the growth of the fibrils in the crazes to a critical length. The CB particles provided a number of sites where the crazes were preferably formed due to stress concentration. In the case of MWCNT, on the other hand, the widening of the crazes formed at earlier stages was suppressed due to the bridging effect arising from the large aspect ratio of MWCNT. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Analyses of homo-oligomer interfaces of proteins from the complementarity of molecular surface, electrostatic potential and hydrophobicity

To extract the general structural features of interacting protein pairs, the non-redundant homo-oligomer interfaces (393 interfaces) in the PDB were analyzed using the fine-grained molecular surface, electrostatic potentials and the hydrophobicity calculated as the solvation free energy using empirical parameters. For each property, statistical analyses of the degree of complementarity were carried out, and we developed a method to judge whether interfaces were shape-complementary, electrostatic-complementary and/or hydrophobic-complementary or not. In order to search for the correlation between the property complementarity and structure of the interfaces, at first, we roughly classified all the interfaces into the following five groups according to the structure of the interface and surveyed the correlation between the shape classification and the complementary: cyclic-oligomer (69), twisted-dimer (27), dimer-parallel (14), dimer-perpendicular (109) and dimer-circular (174), where the number in the parenthesis is the number of interfaces in each group. As a result, we found the new characteristic trends as the possible necessary conditions in the formation of homo-oligomer interfaces, especially from the viewpoint of electrostatic complementarity. In addition, we also show that complementarity analyses can be used to discriminate the biological-interface from the crystallographic-interface in homo-oligomer proteins.     

Effects of fiber gripping methods on the single fiber tensile test: I. Non-parametric statistical analysis

Single fiber tensile tests using two different gripping methods were carried out on various fiber lengths. One method (the glue-tab grip method) consists of mounting a fiber onto a rigid tab as specified in ASTM C1557-03 using an adhesive, while the other (the direct grip method) involves directly clamping a fiber using poly(methyl methacrylate) blocks. The tensile moduli obtained by the glue-tab grip as a function of the fiber gauge length are clearly different from those of the direct grip for fiber length between 2 and 10 mm, based on graphical statistical analyses using kernel density and q–q plots. This difference is caused by the gripping effect. In addition, the tensile strains and strengths obtained by the glue-tab grip were different from those of the direct grip at the short fiber gauge lengths (i.e., 2–10 mm). The differences between the tensile properties (i.e., modulus, strain, and strength) for the two grips measured with the 60-mm fiber length were not statistically significant compared to the results with the short fiber lengths.     

Fabrication of CdS/β-SiC/TiO2 tri-composites that exploit hole- and electron-transfer processes for photocatalytic hydrogen production under visible light

In this work, CdS/SiC/TiO₂ tri-composite photocatalysts that exploit electron- and hole-transfer processes were fabricated using an easy two-step method in the liquid phase. The photocatalyst with a 1:1:1 M ratio of CdS/SiC/TiO₂ exhibited a rate of hydrogen evolution from an aqueous solution of sodium sulfite and sodium sulfide under visible light of 137 μmol h^?1 g^?1, which is 9.5 times that of pure CdS. β-SiC can act as a sink for the photogenerated holes because the valence band level of β-SiC is higher than the corresponding bands in CdS and TiO₂. In addition, the level of the conduction band of TiO₂ is lower than those of CdS and β-SiC, so TiO₂ can act as the acceptor of the photogenerated electrons. Our results demonstrate that hole transfer and absorption in the visible light region lead to an effective hydrogen-production scheme.     

A study on the tie‐set graph theory and network flow optimization problems

Aiming at establishing a firm basic theory to ring‐based information network management systems, our paper proposes a tie‐set graph theory. We define a binary vector representing a tie‐set in a biconnected undirected graph G=(V,E) as a tie‐set vector. The set of tie‐set vectors forms a vector space over the proposed law of composition, then a basis of the vector space, μ linear independent tie‐set vectors, is defined as a tie‐set basis. The essential key concept in our theory is a tie‐set graph, which has a one‐to‐one correspondence to a tie‐set basis and represents a relation between two tie‐set vectors of the basis. Some important properties of tie‐set graphs and their application to survivable mesh networks in modern high‐speed backbone networks are also presented. Furthermore, as a general approach to network flow optimization problems, tie‐set flow vector space is proposed based on the tie‐set graph theory. A distributed algorithm for the network flow optimization problems and its application are also presented in this paper. Copyright © 2004 John Wiley & Sons, Ltd.     

Influence of pH,concentration of sodium lactate as an additive and ultrasonic treatment on synthesis of zinc phosphate white pigments

Zinc oxide that has the photocatalytic activity is used as a white pigment for cosmetics. A certain degree of sebum on the skin is decomposed by the ultraviolet radiation in sunlight. In this work, zinc phosphates were prepared from zinc nitrate and phosphoric acid at pH 5 and 7 with and without the addition of sodium lactate and ultrasonic treatment as a novel white pigment for use in cosmetics. The chemical composition, powder properties, photocatalytic activity, colour phase, moisture retention and smoothness of the zinc phosphates were studied. The obtained materials had a Zn/P ratio of about 1.5, which corresponds to zinc orthophosphate Zn₃(PO₄)₂. Samples prepared with ultrasonic treatment indicated the high ratios of large particles in scanning electron microscopy images and particle‐size distributions. The photocatalytic activity of these zinc phosphate particles was too less to protect the sebum on the skin. The materials obtained and their thermal products at 100°C showed a high reflectance within the range of visible light. The slipping resistance and roughness of the powder were enough low for use in cosmetics.     

Importance of an N-terminal extension in ribonuclease HII from Bacillus stearothermophilus for substrate binding

The gene encoding ribonuclease HII from Bacillus stearothermophilus was cloned and expressed in Escherichia coli. The overproduced protein, Bst-RNase HII, was purified and biochemically characterized. Bst-RNase HII, which consists of 259 amino acid residues, showed the highest amino acid sequence identity (50.2%) to Bacillus subtilis RNase HII. Like B. subtilis RNase HII, it exhibited Mn2+-dependent RNase H activity. It was, however, more thermostable than B. subtilis RNase HII. When the Bst-RNase HII amino acid sequence is compared with that of Thermococcus kodakaraensis RNase HII, to which it shows 29.8% identity, 30 residues are observed to be truncated from the C-terminus and there is an extension of 71 residues at the N-terminus. The C-terminal truncation results in the loss of the alpha9 helix, which is rich in basic amino acid residues and is therefore important for substrate binding. A truncated protein, Delta59-Bst-RNase HII, in which most of the N-terminal extension was removed, completely lost its RNase H activity. Surface plasmon resonance analysis indicated that this truncated protein did not bind to the substrate. These results suggest that the N-terminal extension of Bst-RNase HII is important for substrate binding. Because B. subtilis RNase HII has an N-terminal extension of the same length and these extensions contain a region in which basic amino acid residues are clustered, the Bacillus enzymes may represent a novel type of RNase H which possesses a substrate-binding domain at the N-terminus.     

Role of repetitive nine-residue sequence motifs in secretion, enzymatic activity, and protein conformation of a family I.3 lipase

A family I.3 lipase from Pseudomonas sp. MIS38 (PML) contains 12 repeats of a nine-residue sequence motif in the C-terminal region. To elucidate the role of these repetitive sequences, mutant proteins PML5, PML4, PML1, and PML0, in which 7, 8, 11, and all 12 of the repetitive sequences are deleted, and PMLdelta19, in which 19 C-terminal residues are truncated, were constructed. Escherichia coli DH5 cells carrying the Serratia marcescens Lip system permitted the secretion of the wild-type and all of the mutant proteins except for PMLdelta19, although they were partially accumulated in the cells in an insoluble form as well. Both the secretion level and cellular content of the proteins decreased in the order PML > PML5 > PML4 > PML1 > PML0, indicating that repetitive sequences are not required for secretion of PML but are important for its stability in the cells. All the mutant proteins were purified in a refolded form and their biochemical properties were characterized. CD spectra, the Ca2+ contents, and susceptibility to chymotryptic digestion strongly suggested that the five repetitive sequences remaining in PML5 are sufficient to form a beta-roll structure, whereas the four in PML4 are not. PML5 and PMLdelta19 showed both lipase and esterase activities, whereas PML4, PML1, and PML0 were inactive. These results suggest that the enzymatic activity of PML is not seriously affected by a deletion or truncation at the C-terminal region as long as a succession of repetitive sequences can build a beta-roll structure.     

Viscosity measurements of ethylene glycol solution with flow drag reduction additives

The viscous characteristics of ethylene glycol (EG) solution with flow drag reduction additive have been investigated experimentally. In this study, oleyldihydoroxyetyl amineoxide (ODEAO) was used as the flow drag reduction additive, and an aqueous solution of EG was used as a secondary refrigerant. The viscosity of the EG solution with ODEAO was measured with a rotational rheometer. The experimental parameters of viscosity measurement were the temperature of the EG solution with ODEAO, the ODEAO concentration, and the EG concentration. From the experimental results, the apparent viscosity of the EG solution with ODEAO showed SIS (shear induced state). The non‐linear dependence of shear stress on shear rate has been well approximated by the power‐law model under high shear conditions. The power‐law contents, pseudoplastic viscosity, and index number have been estimated for each experimental parameter. Using the measured viscosity and non‐dimensional analysis, the flow drag and heat transfer reduction effect of the EG solution with ODEAO has been investigated. © 2006 Wiley Periodicals, Inc. Heat Trans Asian Res, 35(8): 553–567, 2006; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/htj.20134