The effects of Cl-induced alloying in Pt–Sn/Al2O3 catalysts on butane/H2 reactions

The effects of oxidation/reduction regeneration treatments, with and without 1,2-dichloropropane present as a chlorinating agent, on the structure of Pt(3%)–Sn(4.5%)/Al₂O₃ catalysts have been correlated with selectivities for butane/H₂ reactions. Particles of Pt⁰ fin Cl-free catalysts were partly covered by Sn⁰, but retained exposed ensembles of Pt atoms which were active for isomerisation, hydrogenolysis and dehydrogenation reactions, the latter becoming dominant at high reaction temperatures. Coking reduced Pt ensemble size and, hence, also favoured high selectivities for dehydrogenation as hydrogenolysis and isomerisation sites became poisoned. In contrast, the addition of 1,2-dichloropropane in an oxychlorination step before reduction promoted 1:1 Pt⁰–Sn⁰ alloy formation after reduction, the proportion of the total Pt in alloy being enhanced by increasing 1,2-dichloropropane concentration and oxychlorination temperature. The alloy surfaces were inactive for isomerisation and hydrogenolysis reactions, giving dehydrogenation as the sole catalytic reaction.     

Molecular dynamics model structures for the molten globule state of {alpha}-lactalbumin: aromatic residue clusters I and II

To model the molten globule structure of -lactalbumin, moleculardynamics (MD) simulations were carried out for the protein inexplicit water at high temperature. In these simulations, long-rangeCoulomb interactions were evaluated explicitly with an originalmethod (particle–particle and particle–cell: PPPC)to avoid artifacts caused by the cut-off. The MD simulationswere started from two initial conditions to verify that similarresults would be obtained. From the last 150 ps trajectoriesof the two MD simulations, two partially unfolded average structureswere obtained. These structures had the following common structuralfeatures which are characteristic of the molten globule state.The radii of gyration for these conformations were 7.4 and 9.6%larger than that of the native state. These values were almostthe same as the experimental value (9.6%) observed recentlyby small-angle X-ray scattering (Kataoka,M., Kuwajima,K., Tokunaga,F.and Goto,Y., 1997, Protein Sci., 6, 422–430). Furthermore,aromatic residues of clusters I and II in these structures werefar apart from each other except for Try103–Trp104. Thisresult is in good agreement with NMR experimental results forthe acid-denatured molten globule state (Alexandrescu et al.,1992, 1993); that is, NOE signals between the aromatic residueswere not observed, except for that of Try103–Trp104 inthe molten globule state. Other structural features of thesemodels for the molten globule state are discussed with referenceto native state structures.     

Premodification of Pt/γAl2O3 with Cinchonidine for the Enantioselective Hydrogenation of Ethyl Pyruvate: Effect of Premodification Conditions on Reaction Rate and Enantioselection

The premodification of a 5 wt% Pt/-Al₂O₃ catalyst with cinchonidine (0.01 and 0.2 g g^-1 _catalyst) is described and discussed. Premodification is carried out by treating the catalyst with a solution of cinchonidine followed by solvent removal. Catalysts premodified in this way give the same ee and initial rate of reaction for the enantioselective hydrogenation of ethyl pyruvate as those using the standard in situ modification procedure. Investigations of different solvents for premodification and reaction (dichloromethane, ethanol) show that it is the solvent used for the reaction that controls the observed enantioselection. Premodified catalysts also display the initial transient behavior typically observed with in situ modified catalysts in which the ee increases with conversion in the early part of the reaction. Premodified catalysts show an enhanced rate of reaction when ethanol is used as the reaction solvent compared with in situ modified catalysts under the same conditions. Premodification using aerobic conditions gives the best results and premodified catalysts can be stored prior to use for up to a week without loss of catalytic performance.     

A holistic approach to protein structure alignment

A method of protein structure comparison developed previouslyis extended to incorporate other aspects of protein structurein addition to the inter-atomic vectors on which it was originallybased. Each additional aspect, which included hydrogen bonding,solvent exposure, torsional angles and sequence, was introducedseparately and evaluated for its ability to improve alignmentquality. The components were then combined, suitably weighted,to produce a more holistic comparison method. The method wastested on a group of remotely related ß/ type proteinsthat share a common feature in their overall chain fold. Theresults indicated that while the original inter-atomic vectorcomponent was sufficient to give the correct alignment of mostpairs of topologically equivalent proteins, the inclusion ofhydrogen bonds, torsion angles and a measure of solvent exposureled to improvements in the more difficult comparisons. Considerationof amino acid properties, including hydrophobicity, had no beneficialeffect. The failure of the latter component was not unexpectedconsidering the almost total lack of sequence similarity amongthe proteins considered.     

Algal phagostimulants for marine herbivorous gastropods

Methanol extracts of the green algaUlva pertusa contain four kinds of glycerolipids that are active as feeding-stimulants for marine herbivorous gastropods. These compounds are digalactosyldiacylglycerol (DGDG), 1,2-diacylglycerly-4-O-(N,N,N-trimethyl)-homoserine (DGTH), 1-monoacylglyceryl-4'-O-(N,N,N-trimethyl)-homoserine (MGTH), and 6-sulfoquinovosyldiacylglycerol (SQDG). The various gastropods exhibit marked specificity, however, as young abaloneHaliotis discus respond to DGDG and DGTH at minute dosages of 20–30 g/sample zone, but do not respond to 300 g of SQDG, which is a phagostimulant for two other kinds of gastropods,Turbo comutus andOmphalius pfeifferi.Chemical Studies on Phagostimulants for Marine Gastropods. Part VI. For Part V, see Sakata et al. (1986b).     

羊布鲁菌O链M抗原提纯及其单克隆抗体的研制

目的研制羊布鲁菌O链M纯化抗原及其单克隆抗体。方法采用冷酚法提纯羊布鲁菌16M的O链抗原,并经琼脂糖凝胶免疫扩散和SDS-PAGE鉴定,用灭活的该抗原免疫BALB/c小鼠,制备单克隆抗体,并进行鉴定。结果建立3株分泌单克隆抗体的细胞株2D10、3C6和1E10,ELISA效价分别为1.380、1.109和1.048,与大肠杆菌0:157、小肠结肠炎耶尔森菌0:9、鼠伤寒沙门菌和猪胸膜肺炎放线杆菌均无交叉反应。3C6和1E10与牛布鲁菌544A发生交叉反应,2D10的亲和常数达5.30×10~7M~(-1)。结论已制备出纯化的羊布鲁菌O链M抗原及其单抗。     

Role of La2O3 in Pd-Supported Catalysts for Methanol Decomposition

Systems of Pd supported on various La₂O₃-modified -Al₂O₃ and CeO₂–Al₂O₃ catalysts were tested for catalytic methanol decomposition and characterized by means of XRD, BET, TPR, H₂-chemisorption and CO–FTIR. The addition of lanthanum significantly improved the selectivity of CO and H₂ for all the catalysts but showed a different influence on the catalytic activity in two systems. Methanol conversion decreased on La₂O₃-modified Pd/-Al₂O₃ catalysts, in line with the reduction of Pd dispersion, while the addition of La₂O₃ improved the dispersion of Pd and reinforced Pd–CeO₂ interaction for La₂O₃-modified Pd/CeO₂–Al₂O₃ catalysts, which resulted in a high production rate of CO and H₂. Thus, a synergistic effect between CeO₂ and La₂O₃ was observed on -Al₂O₃-supported Pd catalyst for methanol decomposition.     

Deformation Dynamics of a Reactive Medium During Gasless Combustion

Deformation during gasless combustion of 5Ti + 3Si and Ti + C samples was studied experimentally. The dynamics of motion of the material in a gasless combustion wave was studied using highspeed video recording (500 frames/sec) with a spatial resolution of the order of 10 m. It was shown that behind the combustion front, the medium was first expanded and then compressed. The dimensions of the expansion and compression zones were determined.     

Desulfurization of commercial fuels by π-complexation: Monolayer CuCl/γ-Al2O3

Monolayer CuCl/γ-Al₂O₃ sorbent was studied for desulfurization of a commercial jet fuel (364.3 ppmw S) and a commercial diesel (140 ppmw S). The sorbent was prepared by means of spontaneous monolayer dispersion methods. Deep desulfurization (sulfur levels of <1 ppmw) was accomplished with this sorbent using a fixed-bed adsorber. The CuCl/γ-Al₂O₃ sorbent was capable of removing 6.4 and 11.2 mg of sulfur per gram for jet fuel at breakthrough (at <1 ppmw S) and saturation, respectively. The same sorbent was capable of removing 0.94 and 1.8 mg of sulfur per gram for BP diesel at breakthrough and saturation, respectively. The difference in sulfur capacities for jet fuel and diesel was apparently caused by the difference in concentrations of strongly binding compounds, such as nitrogen heterocycles, heavy (polynuclear) aromatics and fuel additives. In comparison with CuCl/γ-Al₂O₃, Cu(I)Y zeolite has higher sulfur capacities but is less stable and can be easily oxidized to Cu(II)Y by fuel additives (such as oxygenates) and moisture and consequently loses π-complexation ability. However, all these cuprous π-complexation sorbents selectively adsorb thiophenic compounds over aromatics and olefins (as predicted by the high separation factors), which resulted in the observed desulfurization capability. A feasibility study is shown for efficient regeneration of CuCl/γ-Al₂O₃ using ultrasound at ambient temperature. Possible problems associated with desulfurization using π-complexation sorbents for commercial fuels are discussed.     

并行企业运作--基于并行工程的过程企业管理

针对过程企业,基于并行工程的思想,提出了过程企业运作管理的新思想--并行企业运作,并采用IDEFO(ICAM Defintion)功能建模方法,建立了集成并行的业务过程模型,在每个业务过程内部采用"监控-决策-执行"的实时信息反馈系统,以实现企业各业务过程之间的信息交互与资源共享.