Selective catalytic transformations of methanol to C2-C3 hydrocarbons over the new zeolite type LZ 132

The small pore zeolite HLZ 132 exhibits, in comparison with other zeolites, an increased selectivity for the transformation of methanol to ethylene in the reaction temperature range 350–500 °C: the weight ratio of C₂H₄ to C₃H₆ in the products ranges between 1 and 4 at WHSV=2 h^–1. Besides the effect of the reactant shape selectivity this fact may be interpreted by the participation of the asymmetrical methoxy groups in the surface as well as by proton-donor centres of lower acidity which do not catalyze the oligomerization of ethylene but which do the more basic molecule of propylene, thereby generating polyene-type coke.     

Quantitative preparation of long chain thioethers from an oxo-trans-2-enoic ester and a 9,12-dioxo-trans-10-enoic acid

Branched-chain thioethers have been prepared from methyl 4-oxo-trans-2-hexadecenoate and 9,12-dioxo-trans-10-octadecenoic acid. The reagents involved in these preparations were mercaptoacetic and mercaptopropionic acids. The yields of these thioethers are almost quantitative.     

Synthesis of tetrazole from α, β—Unsaturated carbonyl fatty acid

Methyl 4-oxo-trans-2-octadecenoate (II), when treated with excess hydrazoic acid in the presence of BF₃-etherate, produced 66% methyl 5-aza-nonadec-trans-2-enoate (4,5-d)-tetrazole (III), 10% methyl 5-aza-nonadec-4-oxo-trans-2-enoate (IV) and 7% pentadecamide (V). Individual products were characterized by spectral and elemental methods.     

Thermal characterization of n‐alkyl maleate‐styrene‐allyl propionate terpolymers

Thermal characterization of maleic anhydride‐styrene‐allyl propionate (MA‐St‐AP) terpolymer and its ester derivatives named as n‐alkyl maleate and shown as nPr MA‐St‐AP, nBu MA‐St‐AP, nPn MA‐St‐AP, and nBz MA‐St‐AP was carried out. The thermal characterization was performed using thermal analysis techniques such as TGA, DTA, DSC, and TMA. Different results were observed between the original terpolymer and its ester derivatives. Thermal stabilities of the terpolymer and its ester derivatives were compared by using various measurements plotted as TGA, DTA, DSC, and TMA curves. The increase in the alcohols' carbon numbers added to the original terpolymer results in ester derivatives with different thermal stability behavior. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 600–604, 2007     

Structure and dynamics of a pentablock copolymer of polystyrene-polybutadiene in a butadiene-selective solvent

We have examined solutions of a polystyrene-polybutadiene pentablock copolymer in n-heptane, a strongly selective solvent for polybutadiene. Small angle neutron scattering from 7 to 15% samples reveals domains about 10 nm in radius formed by the association of 200 polystyrene blocks. Dynamic light scattering measurements on 8 and 9% samples showed three modes: a fast diffusive mode related to the collective diffusion in semidilute solutions/gels; a relaxational mode related to the local dynamics of polystyrene domains trapped in the gel formed by bridging the domains with the polybutadiene chains; and a very slow diffusive mode. The relaxational dynamics persisted over the entire temperature range, becoming faster with increasing temperature, indicating a decreased microviscosity at higher temperatures. The slow dynamics seems to be connected with heterogeneities in the physical gel due to microsyneresis and almost disappeared above 50 °C. Macroscopic phase separation into two liquid phases was observed in a dilute solution of the un-associated copolymer, and into a liquid and gel phase at higher concentrations. The absence of flower-like micelles in dilute solutions and the macroscopic phase seperation suggest that the gels in the pentablock are formed by random association of multiplet domains and not by bridging of micellar domains.     

A new combined computational and NMR-spectroscopical strategy for the identification of additional conformational constraints of the bound ligand in an aprotic solvent

This study documents the feasibility of switching to an aprotic medium in sugar receptor research. The solvent change offers additional insights into mechanistic details of receptor--carbohydrate ligand interactions. If a receptor retained binding capacity in an aprotic medium, solvent-exchangeable protons of the ligand would not undergo transfer and could act as additional sensors, thus improving the level of reliability in conformational analysis. To probe this possibility, we first focused on hevein, the smallest lectin found in nature. The NMR-spectroscopic measurements verified complexation, albeit with progressively reduced affinity by more than 1.5 orders of magnitude, in mixtures of up to 50% dimethyl sulfoxide (DMSO). Since hevein lacks the compact beta-strand arrangement of other sugar receptors, such a structural motif may confer enhanced resistance to solvent exchange. Two settings of solid-phase activity assays proved this assumption for three types of alpha- and/or beta-galactoside-binding proteins, that is, a human immunoglobulin G (IgG) subfraction, the mistletoe lectin, and a member of the galectin family of animal lectins. Computer-assisted calculations and NMR experiments also revealed no conspicuous impact of the solvent on the conformational properties of the tested ligands. To define all possible nuclear Overhauser effect (NOE) contacts in a certain conformation and to predict involvement of exchangeable protons, we established a new screening protocol applicable during a given molecular dynamics (MD) trajectory and calculated population densities of distinct contacts. Experimentally, transferred NOE (tr-NOE) experiments with IgG molecules and the disaccharide Gal'alpha1-3Galbeta1-R in DMSO as solvent disclosed that such an additional crosspeak, that is, Gal'OH2--GalOH4, was even detectable for the bound ligand under conditions in which spin diffusion effects are suppressed. Further measurements with the plant lectin and galectins confirmed line broadening of ligand signals and gave access to characteristic crosspeaks in the aprotic solvent and its mixtures with water. Our combined biochemical, computational, and NMR-spectroscopical strategy is expected to contribute notably to the precise elucidation of the geometry of ligands bound to compactly folded sugar receptors and of the role of water molecules in protein--ligand (carbohydrate) recognition, with relevance to areas beyond the glycosciences.     

Activities of MFI-Supported Rhenium Catalysts for the Aromatization of Methane: Effect of Cationic Form of the Inorganic Carrier

MFI type inorganic carrier was used in two different cationic forms, hydrogen and calcium respectively. MFI-supported molybdenum and rhenium catalysts were prepared. The activities of the catalysts were compared for the aromatization reaction of methane. Higher activity values were attained with the catalysts supported on HZSM-5. Aromatics were also observed with the catalysts supported on CaZSM-5, despite their deficiency in acid sites. Highly dispersed rhenium is expected to be formed with the use of the inorganic carrier in calcium form. On the other hand, lower reaction rates were observed with rhenium supported on CaZSM-5, in spite of the improved dispersion of the active rhenium species on this catalyst. This was interpreted in terms of the critical role of the acid sites in the conversion of methane to aromatics, compared to the improved dispersion of the active metal.     

CFD SIMULATION OF THE GAS-SOLID FLOW IN THE RISER OF A CIRCULATING FLUIDIZED BED WITH SECONDARY AIR INJECTION

A comprehensive investigation was carried out to study hydrodynamics aspects of secondary air injection in circulating fluidized beds. This article presents modeling and results of computational fluid dynamics simulations of gas-solid flow in the riser section of a laboratory-scale (ID = 0.23 m, height = 7.6 m) circulating fluidized bed with a radial secondary air injector. The gas-solid flow model is based on the two-fluid (Eulerian-Eulerian) approach, where both gas and solids phases are treated as interpenetrating continua. A granular kinetic theory model is used to describe the solids phase stresses. The simulation results are compared with measured pressure drop and axial particle velocity profiles; reasonable agreement is obtained. Qualitatively, excellent agreement is obtained in predicting the increase in solids volume fraction below secondary air ports, the accumulation of solids around the center of the riser due to momentum of secondary air jets, and the absence of the solids down-flow near the wall above the secondary air injection ports, which are the prominent features of secondary air injection observed in the experiments.     

Feedback control for multi-resource usage of virtualised database server

Virtualisation and cloud computing have recently received significant attention. Resource allocation and control of multiple resource usages among virtual machines in virtualised data centres remains an open problem. Therefore, in this paper, our focus is to control CPU (central processing unit) usage and memory consumption of a virtual database machine in a data centre under a time-varying heavy workload. In addition to existing work, we attempt to control multiple outputs, such as the CPU usage and memory consumption of a virtualised database server (DBVM), via changing multiple server parameters, such as the CPU allocation and memory allocation, in real time. We indicated that a virtualised database server might be modelled as a linear time-unvarying system. We obtained and compared both MIMO (multi input–multi output) and multiple SISO (single input–single output) models of that system. We designed multiple SISO feedback controllers to achieve desired CPU usages and memory consumptions under workload.     

Heterogeneous asymmetric reactions. 23. Enantioselective hydrogenation of ethyl pyruvate over cinchonine- and α-isocinchonine-modified platinum catalysts

The enantioselective hydrogenation of ethyl pyruvate to (S)-ethyl lactate over cinchonine- and -isocinchonine-modified Pt/Al₂O₃ catalysts was studied as a function of modifier concentration and reaction temperature. The maximum enantioselectivities obtained under the applied mild conditions were 89% ee using cinchonine (0.014 mmoldm^–3, 1 bar H₂, 23°C, 6% AcOH in toluene), and 76% ee in the case of -isocinchonine (0.14 mmoldm^–3, 1 bar H₂, –10°C, 6% AcOH in toluene). Since -isocinchonine of rigid structure exists only in anti-open conformation these data provide additional experimental evidence to support the former suggestion concerning the dominating role of anti-open conformation in these cinchona-modified enantioselective hydrogenations.