连铸中间包内三维湍流流动的数值模拟

连铸中间包的操作条件决定了其内流动现象的复杂性，为此，本文选择两种不同的湍流模型ｋ－ε和ＬＥＳ（Ｌａｒｇｅｅｄｄｙｓｉｍｕｌａｔｉｏｎ），建立了描述连铸中间包内三维湍流流动的数学模型，并实施了数值计算和模型验证，对单流中间包内的流动现象进行了描述，考察了有，无流动控制情况下中间包内的流动特征和湍流模型的合理性，结果表明，合理的流动控制有利于中间包内非金属夹杂的上浮和吸附，用ｋ－ε模型基本上能够描述     

Chemical Modification of Phage-Displayed Helix-Loop-Helix Peptides to Construct Kinase-Focused Libraries

Conformationally constrained peptides hold promise as molecular tools in chemical biology and as a new modality in drug discovery. The construction and screening of a target-focused library could be a promising approach for the generation of de novo ligands or inhibitors against target proteins. Here, we have prepared a protein kinase-focused library by chemically modifying helix-loop-helix (HLH) peptides displayed on phage and subsequently tethered to adenosine. The library was screened against aurora kinase A (AurA). The selected HLH peptide Bip - 3 retained the α-helical structure and bound to AurA with a K_D value of 13.7 μM. Bip - 3 and the adenosine-tethered peptide Bip - 3 - Adc provided IC₅₀ values of 103 μM and 7.7 μM, respectively, suggesting that Bip - 3 - Adc bivalently inhibited AurA. In addition, the selectivity of Bip - 3 - Adc to several protein kinases was tested, and was highest against AurA. These results demonstrate that chemical modification can enable the construction of a kinase-focused library of phage-displayed HLH peptides.     

Synthesis of Sn-Incorporated Folded Sheets Mesoporous Materials (Sn-FSM-16)

Sn-incorporated folded sheets mesoporous materials (Sn-FSM-16) with various contents of Sn were synthesized by using a mixture of water glass, SnCl₄ and NaOH as starting materials. Hexadecyltrimethyl-ammonium chloride (surfactant) was used to intercalate into the layered silicate. The reaction process was followed by measurements of XRD patterns of intermediates. The Sn-FSM-16 was formed via the following mechanism: (1) layered silicates such as - - and -Na₂Si₂O₅ were formed as intermediates by the calcination of the mixture of the starting materials; (2) the surfactant was intercalated into the layered silicates; (3) the surfactant-silicate complex with hexagonal structure was obtained as a precursor of Sn-FSM-16; (4) the precursor was calcined to decompose the surfactant in the interlayer and was changed to Sn-FSM-16. The structural aspect of Sn in Sn-FSM-16 was studied by XPS profiles of Sn 3d _5/2 and Si_2p, ²⁹ Si MAS NMR and FTIR. The content of Sn in Sn-FSM increased with increasing concentrations of both Sn and NaOH in the starting materials. The surface area of Sn-FSM-16 decreased with an increase of Sn content in Sn-FSM (1160–620 m²/g).     

Vapor phase hydroformylation of ethene over Co/SiO2 promoted by noble metals: dynamic in situ diffuse reflectance FT-IR study of surface species

An in situ diffuse reflectance FT-IR technique was employed to investigate the active surface species and the reaction mechanism of the oxygenate formation in the vapor phase hydroformylation of ethene on Co/SiO₂ promoted with various noble metals such as Ir, Rh, Pt, Re, Ru, and Pd. Co(A)/SiO₂ and Ir(CO)/SiO₂ which were derived from cobalt(II) acetate and Ir₄(CO)₁₂, respectively, were quite inactive in the reaction, and showed only quite small peaks of adsorbed CO under the conditions of 1.1 MPa of C₂H₄/CO/H₂ at 298 K. In contrast, Co(A)-Ir(CO)/SiO₂, which were very active in the reaction, exhibited strong absorption bands of linear and bridged CO species. At 423–463 K, propanal adsorbed on the catalyst and acyl species which is suggested as the intermediate for the formation of propanal were also observed on this catalyst. By exposing CO preadsorbed on this catalyst to C₂H₄/H₂ at 289 K and 0.1 MPa, the intensity of the linear CO band decreased, and the bands of propanal and acyl species emerged simultaneously, whereas that of the bridged CO band remained constant after the initial drop. These results suggested that the oxygenates are formed via the CO insertion into adsorbed ethyl species, and linear CO species plays a major role in the CO insertion on these noble metal-promoted cobalt catalysts.     

Formation of Small-Sized CdSxSe1-x Crystals in Sol-Gel-Derived SiO2 Glasses

Silica glasses doped with small-sized CdS_x-Se_1-x crystals were prepared by the sol-gel method. Gels synthesized by the hydrolysis of Si(OC₂H₅)₄, in the presence of CdSeO₄ with NH₄SCN dissolved in HNO₃ or NH₄OH, were heated in H₂-N₂ atmosphere. The pH value of solutions for CdSeO⁴ and NH⁴SCN primarily determined the fraction of anions in CdS^xSe^1-x crystals. The anion content in crystals was dependent on the pH value of the solvent and/or heat-treatment temperature, and the sulfur fraction changed from 0.1 to 0.6. The optical absorption spectra were red-shifted as the selenium content and the crystal size increased, and the emission spectra showed a sharp band near the absorption edge position and a broad tail extending into the long wavelength. The optical band gap energies increased reciprocally proportional to the square of the crystal size.     

Synthesis and properties of N,N'-unsymmetrical dialkyl-3,4:9,10-perylenebis(dicarboximide)s

N,N'- Unsymmetrical dialkyl-3,4:9,10-perylenebis(dicarboximide)s (in which alkyl = methyl, ethyl, propyl, butyl, isobutyl, pentyl, hexyl and octyl) were prepared by the condensation of N-alkyl-3,4:9,10-perylene-tetracarboxylic monoanhydride monoimide with the appropriate alkyl-amines. The properties of these derivatives as pigments were tested and their thermal stability measured.     

Effect of medium-chain fatty acid positional distribution in dietary triacylglycerol on lymphatic lipid transport and chylomicron composition in rats

The present study was carried out to examine if the positional distribution of medium-chain fatty acid (MCF) in dietary synthetic fat influences lymphatic transport of dietary fat and the chemical composition of chylomicrons in rats with permanent cannulation of thoracic duct. Four types of synthetic triacylglycerol were prepared: (i) sn-1(3) MCF-sn 2 linoleic acid, (ii) interesterified sn-1(3) MCF-sn 2 linoleic acid, (iii) sn-2 MCF-sn-1(3) linoleic acid, and (iv) interesterified sn-2 MCF-sn-1(3) linoleic acid. A purified diet composed of equal amounts of the synthetic fat and cocoa butter was given to rats with permanent lymph duct cannulation. The positional distribution of MCF in the dietary fat had no significant effect on the lymph flow, triacylglycerol output, phospholipid output, lipid composition of chylomicrons, or the particle size. The positional distribution of MCF in the synthetic triacylglycerol was maintained in the chylomicron triacylglycerol. These results showed that MCF in the dietary triacylglycerol is transported into lymphatics and the positional distribution is well preserved in chylomicron triacylglycerol.     

Characterization of highly active silver catalyst for NOx reduction in lean-burning engine exhaust

A new Ag/Al₂O₃ catalyst for removing NOx in lean exhaust gas was developed. Oxidized Ag/Al₂O₃ catalyst is highly active for reduction of NOx with ethanol and propene, whereas reduced Ag/Al₂O₃ catalyst is less active for these reactions. Selectivity to N₂ is also high on the oxidized Ag/Al₂O₃ compared to that on the reduced Ag/Al₂O₃. XRD and SEM studies of these two types of Ag catalysts suggest that oxidation induces an interaction between Ag and the support, where the particles are grown in large size. In contrast, the metallic Ag particles are finely dispersed by the reduction process. Although dispersion of Ag particles is decreased by the oxidation process, the catalytic activity is increased. This suggests that the Ag-alumina sites created in the high temperature oxidizing environment are active in catalytic reduction of NOx. This revised version was published online in July 2006 with corrections to the Cover Date.     

Influence of activated carbon pore structure on oxygen reduction at catalyst layers supported on rotating disk electrodes

Carbon materials are often used as catalyst supports, and for catalysts in electrodes of a polymer electrolyte fuel cell, carbon black has been used. Recently, it was found, however, that activated carbon could replace carbon black and besides, significantly improve the activity of the electrode catalyst layer for oxygen reduction. In the present study, to optimize the pore structure of activated carbon for further activity improvement, the influence of the pore structure on the activity was investigated using activated carbon of various specific surface areas and mean pore diameters. A catalyst layer was formed from activated carbon loaded with platinum and a polymer electrolyte. The activity of the layer was measured in an oxygen-saturated perchloric acid solution, supporting the layer on a rotating glassy carbon disk electrode. We found that increases in the specific surface area and mean pore diameter increased the activity and that the latter was more effective than the former mainly due to the enhanced mass-transfer in the pores; the catalyst layer formed from activated carbon with the largest mean pore diameter was the most active. Unless pores excessively develop and lose connections between particles, a large pore diameter is therefore desired for the fuel cell electrodes.     

Elevated temperature instrumented Charpy impact of a sintered silicon carbide

A commercially available, densely sintered alpha silicon carbide was tested in air from room temperature to 1700°C using a modified instrumented pendulum unit and standard Charpy size test specimens. The resistance heated silicon carbide specimens exhibited only elastic behavior, even at 1700°C. A compliance analysis of the test revealed a linear elastic decrease of the absorbed impact energy and also a decrease of the fracture stress of the silicon carbide with increasing temperature.