Catalyst pore plugging effects on hydrocracking reactions in an Ebullated bed reactor operation

This paper analyzes the deactivation effects of NiMo/Al₂O₃ catalyst during the operation in an Ebullated bed reactor for Heavy residue hydrocracking. The spent catalysts were characterized by chemical analysis, ¹³C NMR, ESM, DRX, and by using thermal programmed oxidation and diffusion studies in a shallow bed micro-reactor. The deactivations were performed in a 5 l continuously stirred tank reactor, while the spent catalysts were tested in a 0.05 l micro-reactor. The study focused on determining the properties of the external layer of the catalyst and on evaluating the internal coke and metal deposition. The results indicated that initial deactivation is mainly due to coke depositions, while its impact on mass transfer reaction control depends on temperature. In long-term deactivation, the metal deposition plays a more important role in blocking the internal micro- and meso-structures and in building up the external layer of the pellets.     

Identification of two glutamic acid residues essential for catalysis in the {beta}-glycosidase from the thermoacidophilic archaeon Sulfolobus solfataricus

The Sulfolobus solfataricus, strain MT4, ß-glycosidase(Ssßgly) is a thermophilic member of glycohydrolasefamily 1. To identify active-site residues, glutamic acids 206and 387 have been changed to isosteric glutamine by site-directedmutagenesis. Mutant proteins have been purified to homogeneityusing the Schistosoma japonicum glutathione S-transferase (GST)fusion system. The proteolytic cleavage of the chimeric proteinwith thrombin was only obtainable after the introduction ofa molecular spacer between the GST and the Ssß-glydomains. The Glu387 Gin mutant showed no detectable activity,as expected for the residue acting as the nucleophile of thereaction. The Glu206 Gin mutant showed 10- and 60-fold reducedactivities on aryl-galacto and aryl-glucosides, respectively,when compared with the wild type. Moreover, a significant K_mdecrease with plo-nitrophenyl-ß-D-glucoside was observed.The residual activity of the Glu206 Gln mutant lost the typicalpH dependence shown by the wild type. These data suggest thatGlu206 acts as the general acid/base catalyst in the hydrolysisreaction.     

A comparison of lipids from liver and hepatoma subcellular membranes

Subcellular fractions of nuclei, mitochondria, endoplasmic reticulum, plasma membrane and cytosol were prepared from liver and hepatoma 72288CTC. Marker enzyme activities, biochemical compositions and electron microscopy were used to establish purity. Hepatoma NADH: cytochrome C reductase and 5′-nucleotidase exhibited abnormal subcellular distributions. The lipids from the subcellular fractions were examined in detail. Mitochondria and plasma membranes were characterized by elevated percentages of diphosphatidylglycrerol and sphingomyelin, respectively, in both tissues. All hepatoma subcellular fractions contained dramatically elevated levels of sphingomyelin and cholesterol, two components that form preferential strong complexes in vitro. The fatty acid composition of hepatoma sphingomyelin differed markedlg from liver and, unlike liver, did not exhibit organelle specific compositions. Some hepatoma lipid classes contained reduced percentages of palmitate while others contained higher levels. Hepatoma phosphatidylcholine and phosphatidylethanolamine from organelles contained lower percentages of long chain polyunsaturated fatty acids than liver. Generally, unique fatty acid profiles exhibited by individual phospholipid classes of liver subcellular fractions were absent or much reduced in the hepatoma. The ratios of oleate to vaccenate were near one for most of the phospholipid classes of most liver fractions, but all hepatoma classes, with few exceptions, contained a much higher percentage of oleate in all subcellular fractions. The hypothesis is proposed that the origin of some acyl moieties for the biosynthesis of various hepatome lipid classes differs from liver sources. The possible changes in acyl pools, sources and compartments for complex lipid biosynthesis could result in change in the quantities of molecular species that could contribute to the abnormal properties of the hepatoma membranes.     

Variability for oil and fatty acid composition in castorbean varieties

Thirty-six castorbean varieties were surveyed for oil and fatty acid composition, in order to determine variability of these seed compounds. A large variability of seed oil percentage was observed, ranging from 39.6 to 59.5%. Concerning the fatty acids, little variability was observed for ricinoleic acid, which was the most abundant in the oil, ranging from 83.65 to 90.00%. The other fatty acids appeared in small concentrations and showed a small range: 0.87 to 2.35, 0.68 to 1.84, 2.96 to 5.64, 3.19 to 5.98, and 0.34 to 0.91%, for palmitic, stearic, oleic, linoleic, and linolenic acid, respectively. Non-significant correlations were observed between fatty acids and seed oil percentage. However, significant correlations were observed among fatty acid concentrations: positive and negative ones. These significant correlations could be associated with the biosynthetic pathways of the fatty acids, which are not fully elucidated. They suggest, however, that selection for a particular fatty acid will tend to increase those positively correlated, and decrease those negative ones. Selection and plant breeding techniques could then be applied to modify the oil content of the castorbean seeds, considering the variability observed. For the fatty acid composition, however, the variability was not large enough to make substantial changes in their concentrations by selection procedures. More varieties should be surveyed to find out if such variability is available.     

An Accessible Platform for People With Disabilities

This article discusses a modular, accessible platform that provides a computing environment for people with disabilities accessible through adapted control devices and the television set at users’ homes. Relying on a standard television set as the presentation device allows dependent individuals, especially people with disabilities, to introduce new technological advances in communication and information management in their everyday lives. As a proof-of-concept, the solution presented offers a collection of educational and training services related to teleworking and the search of employment targeted to people with disabilities. A smart job advisor included among these services, which was designed to help our target users to locate job offers that best suit the abilities and disabilities of a particular individual, is also discussed to illustrate how semantic technologies can be applied to increase the perceived accessibility and inclusion by reducing the dependence from other persons. The platform developed, the introduction of semantic technologies, and the way adapted interfacing and presentation devices were integrated may also serve as inspiration to provide services to people with disabilities.     

Influence of water vapour on high-temperature oxidation of Al2O3-MgO-doped hot-pressed silicon nitride

Silicon nitride is particularly sensitive to high-temperature oxidation. The intensity of oxidation is influenced by the chemical composition of the amorphous phases present at the grain boundaries and consequently by the sintering additives responsible for their formation. The presence of water vapour increases Si₃N₄ oxidation also in intermediate temperature conditions. In this study the influence of water vapour pressure at high temperature (1200°C) on the corrosion of hot-pressed silicon nitride (HPSN) doped with Al₂O₃-MgO was evaluated. The water vapour has a great influence on the devitrification of the amorphous oxide upper layer, due to the formation of crystalline oxides (primarily cristobalite and tridymite). This process increases the oxidation rate, consequently increasing the porosity of the exposed surface. The microstructural evolution of HPSN in the presence of water vapour at 1200°C was analysed by SEM and XRD.     

Induced Defensive Response of Myrtle Oak to Foliar Insect Herbivory in Ambient and Elevated Co2

The rising level of atmospheric CO2 has stimulated several recent studies attempting to predict the effects of increased CO2 on ecological communities. However, most of these studies have been conducted in the benign conditions of the laboratory and in the absence of herbivores. In the current study, we utilized large octagonal chambers, which enclosed portions of an intact scrub-oak community to investigate the interactive effects of CO2 and insect herbivory on myrtle oak, Quercus myrtifolia. Specifically, we assessed the effects of ambient and elevated CO2 (2x current concentrations) on percent foliar nitrogen, C:N ratio, total relative foliar tannin content, and the presence of leaf damage caused by leaf mining and leaf chewing insects that feed on myrtle oak. Total foliar N declined and C:N ratios increased significantly in oaks in elevated CO2 chambers. The percentages of leaves damaged by either leafminers or leaf chewers tended to be lower in elevated compared to ambient chambers, but they co-occurred on leaves less than expected, regardless of CO2 treatment. Leaves that had been either mined or chewed exhibited a similar wounding or defensive response; they had an average of 25 and 21% higher protein binding ability, which is correlated with tannin concentration, compared to nondamaged control leaves, respectively. While the protein-binding ability (expressed as total percent tannin) of leaves from elevated CO2 was slightly higher than from leaves grown in ambient chambers, this difference was not significant.     

Sintering-driven effects on the band gap of (Pb,La)(Ti,Ni)O3 photovoltaic ceramics

In this work, the influence of the sintering temperature on the physical properties of (Pb_0.8La_0.2)(Ti_0.9Ni_0.1)O₃ (PLT-Ni) ceramics is reported. The experimental data revealed that the energy band gap of PLT-Ni ceramics could be tailored from approximately 2.7 to 2.0 eV by changing the sintering temperature from 1100°C to 1250°C. It is demonstrated that the simple substitution of Ti⁴⁺ by Ni²⁺ cations is effective to decrease the intrinsic band gap while increasing the tetragonality factor and the spontaneous polarization. However, the additional red-shift observed in the absorption edge of the PLT-Ni with increasing the sintering temperature was associated with a continuous increase in the oxygen vacancies () amount. It is believed that the impact of the creation of these thermally induced is manifold. The presence of and Ni²⁺ ions generate the Ni²⁺- defect-pairs that promoted both a decrease in the intrinsic band gap and an additional increase of the tetragonality factor, consequently, increasing the spontaneous polarization. The creation of Ni²⁺- defects also changed the local symmetry of Ni²⁺ ions from octahedral to a square pyramid, thus lifting the degeneracy of the Ni²⁺ 3d orbitals. With the increase in the sintering temperature, lower-energy absorbing intraband states were also formed due to an excess of , being responsible for an add-on shoulder in the absorption edge, extending the light absorption curve to longer wavelengths and leading to an additional absorption in “all investigated” spectrum as well.     

Organo-zincate molten salts as immobilising agents for organometallic catalysis

The combination of 1-n-butyl-3-methylimidazolium chloride with ZnCl₂ affords ionic mixtures with different melting point temperatures depending on the zinc molar fraction. RuCl₂(PPh₃)₃ immobilised in the low melting mixture (60°C) promotes the 1-hexene hydrogenation (turnover frequencies up to 44 min^–1) and the recovered solid catalyst phase can be reused several times.     

Lecithin-protein interaction in the GTP-dependent acyl-CoA synthase

The enzymic activity of the GTP-dependent acyl-CoA synthase isolated from rat liver mitochondria is affected by removal and addition of lecithin (3). Purified preparations of this enzyme contain bound lecithin. In this presentation the nature of the lecithin-protein interaction is examined. From binding measurements at different temperatures it is possible to postulate which type of secondary valence bonds is holding the protein and lecithin together. Presented at AOCS Meeting, Chicago, October 1967.