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.     

Discovering social structures of local influence by using tweetStimuli

Information diffusion in large-scale networks has been studied to identify the users influence. The influence has been targeted as a key feature either to reach large populations or influencing public opinion. Through the use of micro-blogs, such as Twitter, global influencers have been identified and ranked based on message propagation (retweets). In this paper, a new application is presented, which allows to find first and classify then the local influence on Twitter: who have influenced you and who have been influenced by you. Until now, social structures of tweets’ original authors that have been either retweeted or marked as favourites are unobservable. Throughout this application, these structures can be discovered and they reveal the existence of communities formed by users of similar profile (that are connected among them) interrelated with other similar profile users’ communities.     

Texture prediction of Bi2Te3 electroplated layers using Hartman's theory of crystal growth

An experimental study of electroplated thin films of bismuth telluride, R3m crystal structure, shows that fibre textures are observed during the growth of the layers. Several orientations 00.1, 10.10, 11.0, 10.4, 10.8, 01.5 and 10.0 are developed during the deposition process, then reach a final orientation. Hartman's theory of crystal growth based on the periodic bond chain (PBC) in a crystal lattice is usually applied. This explains the equilibrium shape of a crystal defined by F faces and the faces observed during the growth (S and K faces). It also successfully predicts the orientations observed in bismuth telluride from the beginning to the end of the layer deposition. The theory may also be applied to other deposition processes.     

On the inhibiting effect of phenolic compounds in the photopolymerization of acrylates under high‐intensity and polychromatic UV/visible lights

The photopolymerization of wood coatings under UV and visible light in industrial type conditions has been investigated. The inhibiting effect of the phenolic compounds found in wood extractives, especially quercetin, on the final properties of the coating (hardness, gel content) as well as the polymerization kinetics (rates, final conversion) has been discussed. Model clear‐coating formulations — based on an acrylate oligomer, a reactive diluent and a bis‐acylphosphine oxide as photo‐initiator — have been used. This article focuses on the influence of the nature of the acrylate oligomer (polyester, epoxy, polyurethane), the type of phenolic derivative (POHs) and the irradiation conditions (UV conveyor, Xe lamp). It appears that lead to through the strong inner‐filter effect in the presence of quercetin is responsible for the loss of all the observed properties. In order to mimic what happens at the wood–coating interface, the role of the diffusion of the phenolic derivatives have been also investigated and discussed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3285–3298, 2007     

Ethanolysis of rapeseed oil: Quantitation of ethyl esters,mono-, di-, and triglycerides and glycerol by high-performance size-exclusion chromatography

High-performance size-exclusion chromatography (HPSEC) was used to evaluate the influence of different variables affecting the transesterification of rapeseed oil (RSO) with anhydrous ethanol and sodium ethoxide as catalyst. The effect of temperature, ethanol/RSO molar ratio, catalyst concentration, and time can be interpreted by observing the variations of the reaction medium composition. HPSEC has made the quantitation of ethyl esters, mono-, di-, and triglycerides and glycerol possible. The best results for laboratory-scale reactions were obtained at 80°C with a 6:1 molar ratio of EtOH/RSO and 1% of NaOEt by weight of RSO.     

Diastereoselective Heterogeneous Catalytic Hydrogenation of Aromatic or Heteraromatic Compounds

The diastereoselective hydrogenation catalyzed by heterogeneous metallic catalysts uses a covalently bound chiral auxiliary to induce the chirality. It remains an active synthetic methodology in the asymmetric synthesis of chiral products and may proceed with high diastereoselectivity. This review describes recent examples using this method, such as hydrogenation of C=C, C=O, and C=N bonds. The use of a chiral auxiliary group has also been successfully applied to the hydrogenation of aromatic and heteroaromatic rings. The choice of the chiral auxiliary was found to play a key role in the asymmetric hydrogenation. The results could be explained in terms of steric effect, with a preferred conformation of the adduct substrate and the addition occurring from the less bulky side. The catalytic metal, the support and the presence of additives were also found to have a significant influence.     

A study about the effect of the temperature of hydrogen treatment on the properties of Ru/Al2O3 and Ru/C and their catalytic behavior during 1-heptyne semi-hydrogenation

The 1-heptyne selective hydrogenation carried out at 150 kPa, and at 283 and 303 K using Ru/Al₂O₃ and Ru/C as catalysts, was studied. Catalysts were prepared by the incipient wetness impregnation technique using RuCl₃ as precursor. Ru/Al₂O₃ was treated in hydrogen at 373 or 573 K and Ru/C only at the last temperature. Catalysts were characterized by hydrogen chemisorption, TPR and XPS. Ru dispersion after treatment in hydrogen at the highest temperature is similar for both catalysts. Ru is present as Ru⁰ in Ru/C, while Ru⁰ and Ru electron-deficient species are present on the catalysts surface after hydrogen treatment at the two temperatures using Al₂O₃ as support. The best catalytic behavior was observed for the highest temperature of hydrogen treatment and for 303 K reaction temperature. As a consequence of a shape selectivity effect of the C support, the best conversion is obtained with the alumina supported catalyst.     

Interaction between dietary protein and fat in triglyceride metabolism in the rat: Effects of soy protein and menhaden oil

The objective of the present study was to determine the mechanisms by which dietary proteins interact with dietary lipids in the regulation of triglyceridemia in rats. Male Sprague-Dawley rats (n=56) were subjected to 28-d experimental diets containing different combinations of proteins (20% w/w) and lipid sources (14% w/w): (i) casein-menhaden oil, (ii) casein-beef tallow, (iii) soy protein-menhaden oil, and (iv) soy protein-beef tallow. Significant protein-lipid interactions were observed on triglyceridemia and hepatic cholesterol in fasted rats. The combination of casein and beef tallow was associated with high plasma TG and hepatic cholesterol concentrations, which were reduced by substitution either of soy for casein or of menhaden oil for beef tallow. Therefore, triglyceridemia and liver cholesterol remained low with soy protein feeding, independently of the lipid source, as well as with menhaden oil feeding, regardless of the protein source. The menhaden oil diets reduced plasma cholesterol, hepatic TG, and TG secretion compared with beef tallow diets independently of the dietary protein source. Modifying the source of dietary proteins and lipids had no effect on post-heparin plasma lipoprotein lipase activity. These results demonstrate that soy protein can lower rat triglyceridemia relative to casein when associated with beef tallow consumption, whereas menhaden oil can attenuate hypertriglyceridemia when rats are fed casein. The data further suggest that part of the hypotriglyceridemic effect of soy protein in the rat may be mediated by reduced hepatic lipid synthesis, as is the case for menhaden oil.     

Toxicokinetics of 2,4-dihydroxy-7-methoxy-1,4-benzoxazin-3-one (DIMBOA) in the European corn borer,Ostrinia nubilalis (Hübner)

2,4-Dihydroxy-7-methoxy-1,4-benzoxazin-3-one (DIMBOA), the major hydroxamic acid present in corn, and its tritiated derivative, were prepared synthetically for use in the determination of the toxicokinetics of this insect deterrent in the European corn borer (ECB),Ostrinia nubilalis. In growth studies with DIMBOA (0, 0.05, 0.2, and 0.5 mg/g diet), the mean time to pupation and adult emergence were significantly lengthened by an increase in concentration. Pupal and adult weights, for both female and male, decreased with an increase in concentration. Increased larval and pupal mortality occurred at the highest concentration of DIMBOA. DIMBOA, at concentrations of 0.2 and 0.5 mg/g diet, resulted in a decrease in the number of egg masses produced per female, and at 0.5 mg/g diet, in a decrease in the number of eggs per egg mass. Larvae fed from the neonate stage on a diet containing 0.2 mg [³H]- + [¹H]DIMBOA/g diet showed an increase in the content of label from fourth to fifth instar, but levels declined at pupation and emergence. A large amount of the labeled compounds was excreted by the insect in the pupal case. In dose-related studies, both uptake and excretion increased with an increase in concentration of DIMBOA (0.05, 0.2, 0.4 mg/g diet), while a body burden (concentration in the tissues/concentration in the frass) of approximately 0.25 was maintained for all concentrations. At the highest dose of DIMBOA (0.4 mg/g), the ECB increased consumption, possibly to compensate for the toxic effects of the compound. In topical application studies, elimination of the labeled compound in the frass was rapid, reaching 65% by 4 hr and 88% by 48 hr. Accumulation of label in tissues other than hemolymph was low. The results show that the ECB does possess adaptive mechanisms to deal with the effects of this host-derived compound.     

Relationship between microstructure and mechanical properties of polyether block amide foams

The mechanical behaviors of five polyether block amide foams, obtained by mold-opening foam injection process, were investigated with regard to their microstructures. The materials vary in mass ratios of hard versus soft segments, and/or in process packing time. The resulting microstructures have been characterized in terms of cavity size and shape ratios, by analyzing scanning electron microscope images after careful sample preparation. The foam mechanical responses have been characterized in compression at small and large strain. At small strain, the initial linear part of the stress–strain curve is enhanced firstly by the hard segment mass ratio and secondly by the fineness of the microstructure. Similar results have been obtained at large strain. The foam viscoelasticity at large strain has been characterized by stress relaxation and strain recovery tests, relevant for foam applications. Reduced packing time and pressure have been shown to lead to the presence of undesired large cavities. The morphological defects appear to have a negligible impact on the macroscopic mechanical behavior of the foams at infinitesimal strain, but lead to critical inconsistency at large strain. Furthermore, the mechanical behavior of the tested polyether block amide foams is controlled first by hard versus soft segments ratio, and second by the microstructure fineness.