Dehydrogenation and Isomerization of n-Butane or Isobutane Over Cr Catalysts Supported on Zeolites

Dehydrogenation and isomerization of n-butane or isobutane into isobutene over Cr catalysts supported on zeolites were investigated. We found that Cr catalyst supported on H-SSZ-35-type zeolite, having one-dimensional cage-type channel structure, was very effective for this reaction and the yield of isobutene was 5.44% from n-butane and 9.57% from isobutane. In this reaction, it is suggested that dehydrogenation of butanes is accelerated by Cr₂O₃ loading, and solid acidity of the zeolite support favors isomerization.     

Shift of the Curie Point of Barium Titanate Ceramics with Sintering Temperature

Definite increases in the Curie point (T_C) of undoped and lanthanum- (La-) doped (<0.5 at.%) barium titanate (BaTiO₃) ceramics sintered at elevated temperatures in the range of 1300°-1450°C were observed. Both undoped and 0.3 at.% La-doped BaTiO₃ (chosen as a typical doping concentration to yield semiconducting materials) ceramics showed almost the same T_C behavior; their T_C values increased by ∼3.5°C as the sintering temperature was increased from 1300° to 1450°C. Semiconducting 0.3 at.% La-doped materials increased in room-temperature bulk resistivity and TC with increased sintering temperature. The bulk resistivity of the La-doped materials, which was obtained from complex impedance analysis, increased from ∼2 omega cm for the material sintered at 1350°C to ∼6 ω cm at 1450°C. The phenomenon of bulk resistivity increase with sintering temperature was observed in the materials with a doping concentration of ≥ 0.2 at.% La, but was not observed in those doped with <0.2 at.% La. The mechanisms of TC and the bulk resistivity increase observed in the present materials with increased sintering temperature are discussed based on various models found in the literature, particularly in terms of the defect chemistry in semiconducting BaTiO₃ ceramics and the influence of liquid phases present during sintering.     

Chemical modification at and within nanopowders: Synthesis of core‐shell Al2O3@TiON nanopowders via nitriding nano‐(TiO2)0.43(Al2O3)0.57 powders in NH3

Here, we demonstrate the potential utility of using chemical modification to reorganize metastable nanoparticles into nanostructured nanoparticles without coincidentally inducing extensive necking/sintering. The motivation for this effort derives from the concept that chemical reduction in a single component in a mixed‐metal nanoparticle will create segregated islands of a second immiscible phase. Given the very high chemical energies inherent in nanoparticles, the formation of even smaller islands of a second phase can be anticipated to lead to extremely high interfacial energies that may drive these islands to diffuse to cores or surfaces to form core‐shell structures that minimize such interfacial energies. Thus, ammonolysis of (TiO₂)_0.43(Al₂O₃)_0.57 composition nanopowders where both elements are approximately uniformly mixed at atomic length scales, under selected conditions (1000°C) for various periods of time at constant NH₃ flow rates leads primarily to the reduction in the Ti species to form TiN or TiON which then appears to diffuse to the surface of the particles. The final products consist of Al₂O₃@TiON core‐shell nanopowders that remain mostly unaggregated pointing to a new mechanism for modifying nanopowder chemistries and physical properties.     

Development of a chlorine‐resistant polyamide nanofiltration membrane and its field‐test results

For the development of chlorine‐resistant nanofiltration membranes, a thin‐film‐composite membrane was prepared by the interfacial polymerization of N‐phenylethylenediamine and 1,3,5‐benzenetricarbonyl trichloride on a microporous polysulfone support substrate. The polymerization on the substrate surface was confirmed by Fourier transform infrared measurements, and membrane surface properties such as the roughness and ζ potential were characterized. Rejections of NaCl and isopropyl alcohol of the prepared membrane were 95 and 50%, respectively. The membrane showed much higher chlorine resistance than a commercial polyamide membrane when the membranes were immersed in an aqueous NaOCl solution. A field test was carried out with a spiral‐type membrane module. Tap water was treated by this module for more than 70 days under the condition of continuous NaOCl injection. The prepared membrane module was quite stable, and no distinguished change in the rejection and flux was recognized. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Phosphorylation of CrkII adaptor protein at tyrosine 221 by epidermal growth factor receptor

CrkII adaptor protein becomes tyrosine-phosphorylated upon various types of stimulation. We examined whether tyrosine 221, which has been shown to be phosphorylated by c-Abl, was phosphorylated also by other tyrosine kinases, such as epidermal growth factor (EGF) receptor. For this purpose, we developed an antibody that specifically recognizes Tyr221-phosphorylated CrkII, and we demonstrated that CrkII was phosphorylated on Tyr221 upon EGF stimulation. When NRK cells were stimulated with EGF, the tyrosine-phosphorylated CrkII was detected at the periphery of the cells, where ruffling is prominent, suggesting that signaling to CrkII may be involved in EGF-dependent cytoskeletal reorganization. The EGF-dependent phosphorylation of CrkII was also detected in a c-Abl-deficient cell line. Moreover, recombinant CrkII protein was phosphorylated in vitro by EGF receptor. These results strongly suggest that EGF receptor directly phosphorylates CrkII. Mutational analysis revealed that the src homology 2 domain was essential for the phosphorylation of CrkII by EGF receptor but not by c-Abl, arguing that these kinases phosphorylate CrkII by different phosphorylation mechanisms. Finally, we found that the CrkII protein phosphorylated upon EGF stimulation did not bind to the phosphotyrosine-containing peptide and that CrkII initiated dissociation from EGF receptor within 3 min even with the sustained tyrosine phosphorylation of EGF receptor. This result implicated phosphorylation of Tyr221 in the negative regulation of the src homology 2-mediated binding of CrkII to EGF receptor.     

Properties of localized oscillatory excitation in a nonlinear oscillatory field

We analyzed the dynamics of a nonlinear oscillatory field composed of radial isochron clocks (RICs) or Stuart-Landau (SL) oscillators, which are the simplest dynamic systems that have one stable limit cycle around one unstable equilibrium. According to our computer simulation results, the nonlinear oscillatory field with two kinds of Mexican-hat-type connection had the function of several peak detections of the external input by localized oscillatory excitation areas. Moreover, the nonlinear oscillatory field could realize in-phase phase locking within each localized oscillatory excitation area, and could maximize the phase difference between the different localized oscillatory excitation areas. As the Amari (1977) model of the nerve field provided a mathematical base for the self-organizing map (SOM) algorithm, this nonlinear oscillatory field is expected to provide a theoretical base for the oscillatory SOM algorithm.     

Evaporation behavior of various elements contained in compounds solar cells

The evaporation behavior of various elements, such as Cd, Te, S, Se, and Mo, contained in compound solar cells such as CdTe and Cu-In-Se (CIS), have been studied to obtain baseline data for the assessment of the environmental effects of fire accidents. The combustion test on the CdTe cell simulating the conditions of a fire accident showed that Cd and Te were volatilized in the temperature region above approximately 600 °C and that the amounts volatilized hardly changed above approximately 800 °C. The combustion test for the CIS, on the other hand, indicated that Se and Mo were volatilized above approximately 200 and 400 °C, respectively, in an air atmosphere, whereas virtually no volatilization occurred in a nitrogen atmosphere. Those experimental results were in good agreement with the prediction made using a thermodynamic calculation.     

Effect of agriculture on water quality of Lake Biwa tributaries, Japan

We investigated the effects of natural environments and human activity on Lake Biwa, central Japan. We determined the concentrations of 19 elements and the compositions of stable S and Sr isotopes in the main tributaries of the lake and compared them with the corresponding values obtained from the lake water during the circulation period. Results of a principal component analysis indicated that the components dissolved in the lower reaches of the tributaries can be divided into group 1 (HCO(3), SO(4), NO(3), Ca, Mg, Sr) and group 2 components (Cl, Br, Na, K, Ba, Rb, Cs). The concentrations of group 1 components were high in the rivers of the southern area, which is urbanized and densely populated, and the eastern area, which consists of plains where agriculture predominates, compared with the rivers of the northern and western areas, which are mostly mountainous and sparsely populated. The concentrations of group 2 components tended to be high in the river water of industrial areas. The delta(34)S values of SO(4) in the river water converged to 0+/-2 per thousand as the SO(4) concentration increased and, excluding the areas where limestone is extensively distributed, as the HCO(3) concentration increased. In particular, both the delta(34)S values (0+/-2 per thousand) and the (87)Sr/(86)Sr ratios (0.7117+/-0.0005) fell within narrow ranges in the small and medium rivers of the eastern plain area, where rice is widely grown. These values agreed respectively with the delta(34)S values of the fertilizers used in the Lake Biwa basin and the soil-exchangeable (87)Sr/(86)Sr in the eastern plain. The characteristics of water quality in the small and medium rivers of the eastern area can be explained by a model in which sulfuric, nitric, and bicarbonic acids generated by the decomposition of agricultural fertilizer and paddy rice selectively leached out alkaline-earth elements adsorbed on the soil and sediments of the plain or dissolved calcium carbonate enriched with Mg and Sr. Compared with tributary waters, the lake water was depleted in NO(3), owing to denitrification, and in Mn, owing to mineralization, which occur under the redox condition of bottom sediments. Excluding NO(3) and Mn, the compositions of both the dissolved elements and the Sr and S isotopes in the water of Lake Biwa can be approximately reproduced by simple mixing of the tributary water, indicating that these components provide effective indices for evaluating the relationship between the waters of the lake and its tributaries.     

Sulfur and strontium isotope geochemistry of tributary rivers of Lake Biwa: implications for human impact on the decadal change of lake water quality

To study the deterioration of the water quality in Lake Biwa, Japan, over the last 40 years, we measured the concentrations and isotopic ratios of sulfur and strontium of water in 41 inflowing rivers and one discharging river. The concentrations of SO4 and Sr of inflowing rivers at downstream sites were generally high in the southern urban area and in the eastern area, where a large agricultural plain is situated, but low in the northern and western areas, whose watersheds are mountainous and with low population density. SO4 and Sr concentrations are also lower at upstream sites, which are closer to mountainous areas. Thus, the inflowing river receives large amounts of SO4 and Sr as it flows across the plain, where human activity levels are high. The delta34S or 87Sr/86Sr values of most eastern rivers at downstream sites are lower than those of water in Lake Biwa, and values become more uniform as the proportion of the plain area in the watershed increases. River water in other areas has higher values of delta34S or 87Sr/86Sr than the lake water. This result indicates that the decadal decrease of delta34S and 87Sr/86Sr in the lake water has been caused mainly by the increased flux of SO4 and Sr from rivers in the eastern plain. We assume that in the plain, sulfur, nitrogen, and organic compounds induced by human activities generate sulfuric, nitric, and organic acids in the water, which accelerate the extraction of Sr from bedrocks, leading to the generation of Sr in the river water in the area.