Isomerization of n-hexane over mono- and bimetallic Pd–Pt catalysts supported on ZrO2–Al2O3–WOx prepared by sol–gel

The catalytic performance of mono- and bimetallic Pd (0.6, 1.0 wt.%)–Pt (0.3 wt.%) catalysts supported on ZrO₂ (70, 85 wt.%)–Al₂O₃ (15, 0 wt.%)–WO_x (15 wt.%) prepared by sol–gel was studied in the hydroisomerization of n-hexane. The catalysts were characterized by N₂ physisorption, XRD, TPR, XPS, Raman, NMR, and FT-IR of adsorbed pyridine. The preparation of ZrW and ZrAlW mixed oxides by sol–gel favored the high dispersion of WO_x and the stabilization of zirconia in the tetragonal phase. The Al incorporation avoided the formation of monoclinic-WO₃ bulk phase. The catalysts increased their S_BET for about 15% promoted by Al₂O₃ addition. Various oxidation states of WO_x species coexist on the surface of the catalysts after calcination. The structure of the highly dispersed surface WO_x species is constituted mainly of isolated monotungstate and two-dimensional mono-oxotungstate species in tetrahedral coordination. The activity of Pd/ZrW catalysts in the hydroisomerization of n-hexane is promoted both with the addition of Al to the ZrW mixed oxide and the addition of Pt to Pd/ZrAlW catalysts. The improvement in the activity of Pd/ZrAlW catalysts is ascribed to a moderated acid strength and acidity, which can be correlated to the coexistence of W⁶⁺ and reduced-state WO_x species (either W⁴⁺ or W⁰). The addition of Pt to the Pd/ZrAlW catalyst does not modify significantly its acidic character. Selectivity results showed that the catalyst produced 2MP, 3MP and the high octane 2,3-dimethylbutane (2,3-DMB) and 2,2-dimethylbutane (2,2-DMB) isomers.     

Nitrogen dynamics during till and no-till pasture restoration sequences in Rondônia,Brazil

The clearing of tropical rain forest in the Amazon basin has created large areas of cattle pasture that are now declining in productivity. Practices adopted by ranchers to restore productivity to degraded pastures have the potential to alter soil N availability and gaseous N losses from soils. We examined how soil inorganic N pools, net N mineralization and net nitrification rates, nitrification potential and NO and N₂O emissions from soils of a degraded pasture responded to the following restoration treatments: (1) soil tillage followed by replanting of grass and fertilization, (2) no-till application of non-selective herbicide, planting of rice, harvest followed by no-till replanting of grass and fertilization, and (3) the same no-till sequence with soybeans instead of rice. Tillage increased soil NH₄⁺ and NO₃^? pools but NH₄⁺ and NO₃^? pools remained relatively constant in the control and no-till treatments. Cumulative rates of net N mineralization and net nitrification during the first 6 months after treatment varied widely but were hightest in the tilled treatment. Emissions of NO and N₂O fluxes increased with tillage and with N fertilization. There were no clear relationships among rates of N fertilizer application, net N mineralization, net nitrification, NO, N₂O and total N oxide emissions. Our results indicate that pasture restoration sequences involving tilling and fertilizing will increase emissions of N oxides, but the magnitude of the increase is likely to differ based on timing of fertilizer application relative to the presence of plants and the magnitude of plant N demand. Emissions of N oxides appear to be decreased by the use of restoration sequences that minimize reductions in pasture grass cover.     

From Molecules to Behavior in Long-Term Inorganic Mercury Intoxication: Unraveling Proteomic Features in Cerebellar Neurodegeneration of Rats

Mercury is a severe environmental pollutant with neurotoxic effects, especially when exposed for long periods. Although there are several evidences regarding mercury toxicity, little is known about inorganic mercury (IHg) species and cerebellum, one of the main targets of mercury associated with the neurological symptomatology of mercurial poisoning. Besides that, the global proteomic profile assessment is a valuable tool to screen possible biomarkers and elucidate molecular targets of mercury neurotoxicity; however, the literature is still scarce. Thus, this study aimed to investigate the effects of long-term exposure to IHg in adult rats’ cerebellum and explore the modulation of the cerebellar proteome associated with biochemical and functional outcomes, providing evidence, in a translational perspective, of new mercury toxicity targets and possible biomarkers. Fifty-four adult rats were exposed to 0.375 mg/kg of HgCl₂ or distilled water for 45 days using intragastric gavage. Then, the motor functions were evaluated by rotarod and inclined plane. The cerebellum was collected to quantify mercury levels, to assess the antioxidant activity against peroxyl radicals (ACAPs), the lipid peroxidation (LPO), the proteomic profile, the cell death nature by cytotoxicity and apoptosis, and the Purkinje cells density. The IHg exposure increased mercury levels in the cerebellum, reducing ACAP and increasing LPO. The proteomic approach revealed a total 419 proteins with different statuses of regulation, associated with different biological processes, such as synaptic signaling, energy metabolism and nervous system development, e.g., all these molecular changes are associated with increased cytotoxicity and apoptosis, with a neurodegenerative pattern on Purkinje cells layer and poor motor coordination and balance. In conclusion, all these findings feature a neurodegenerative process triggered by IHg in the cerebellum that culminated into motor functions deficits, which are associated with several molecular features and may be related to the clinical outcomes of people exposed to the toxicant.     

Dual‐Layer Hollow Fibers for Sulfur Removal from Fuels

Emission of sulfur compounds to the atmosphere is universally recognized as one key target to be reduced. For membrane pervaporation which is considered as a potential purification process of fuels, dual‐layer polyurethane (PU)/polyethersulfone hollow‐fiber membranes were prepared. A novel fabrication technique is proposed using a quadruple spinneret to produce the fiber with such morphology by simultaneous spinning of two polymer solutions in the presence of two corresponding precipitation media. Activated carbon was added into the PU solution to improve the transport properties of the selective layer. Resulting hollow‐fiber membranes showed very good adhesion between the selective layer and its support, in addition to an effective removal of a sulfur compound such as 2‐methyl thiophene from a typical model fuel, an indication of good prospects for both the fabrication technique and for sulfur removal by pervaporation of fuels.     

Phase Equilibrium Measurements of Sacha Inchi Oil (<Emphasis Type="Italic">Plukenetia volubilis</Emphasis>) and CO<Subscript>2</Subscript> at High Pressures

New data on phase equilibria for Sacha inchi seed oil in carbon dioxide have been measured using a variable volume cell phase equilibria system at temperatures of 303, 313 and 323 K and at pressures ranging from 4.3 to 27.7 MPa. The CO₂ mole fraction varied from 0.7488 to 0.9997. At the studied concentrations, phase transitions of vapor-liquid, liquid-liquid-vapor and liquid-liquid were observed. Sacha inchi oil contains 47% of omega-3 fatty acids, with a ratio of 0.76:1 for omega-6:omega-3, which is good for human health. The Peng-Robinson equation of state was used to describe the experimental data. A qualitative agreement was obtained between experimental and calculated data for the binary system CO₂ and Sacha inchi seed oil.     

Colour assays: An inside look into Alentejo traditional limewash paintings and coloured lime mortars

A series of colour assays were conducted taking into account old bibliographic recommendations and oral testimony regarding traditional lime painting technology from the Alentejo (South Portugal) region. The main objectives were: (a) the colorimetric analysis of paintings made with different limewash preparation methods; (b) the comparison between natural processed red and yellows ochre pigments (“home made” and from industrial origin) and synthetic iron oxides in different concentrations and lime proportions; (c) the evaluation of the colorimetric CIELAB coordinates during the lime carbonation process in coloured mortars and limewashes. The results shows that the evolution of L*, a*, and b* during the carbonation process is independent of pigment concentration and paint thickness but dependent of pigment composition and finishing technique (lime painting or coloured mortar). They also emphasize the importance of surface appearance attributes and its influence on the colorimetric parameters. © 2010 Wiley Periodicals, Inc. Col Res Appl, 36, 61–71, 2011     

Nanocomposites derived from cellulose acetate and highly branched alkoxysilane

Highly branched alkoxysilane (HB) units were prepared in situ via a Michael‐type reaction between pentaerythrithol triacrylate and aminopropyltriethoxysilane. These units were used as an inorganic component for the modification of cellulose acetate (CA) films using the sol–gel process. The thermal and dynamic‐mechanical behaviors, the morphology, and the dimensional stability of the modified CA films were analyzed. The siloxane‐modified CA films showed thermal stability similar to pure CA, but the residue content at 900°C increased with the addition of HB units. The morphology of these films was characterized by siloxane nanodomains dispersed in the CA matrix, with good interfacial adhesion between the phases. Moreover, the CA/siloxane nanocomposite films showed improved dimensional stability in comparison with CA, i.e., in the presence of HB, the dimensional change was reduced to around 50% of the value observed for pure CA. Finally, a complex dynamic‐mechanical behavior was obtained for the nanocomposite films, as a consequence of the heterogeneous morphology. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and structure-activity relationship of the isoindolinyl benzisoxazolpiperidines as potent,selective, and orally active human dopamine D4 receptor antagonists

A new class of potent dopamine D(4) antagonists was discovered with selectivity over dopamine D(2) and the alpha-1 adrenoceptor. The lead compound was discovered by screening our compound collection. The structure-activity relationships of substituted isoindoline rings and the chirality about the hydroxymethyl side chain were explored. The isoindoline analogues showed modest differences in potency and selectivity. The S enantiomer proved to be the more potent enantiomer at the D(4) receptor. Several analogues with greater than 100-fold selectivity for D(4) over D(2) and the alpha-1 adrenoreceptor were discovered. Several selective analogues were active in vivo upon oral or intraperitoneal administration. A chiral synthesis starting from either D- or L-O-benzylserine is also described.     

Morphological and mechanical properties of polypropylene [PP]/poly(ethylene vinyl acetate) [EVA] blends. II: Polypropylene‐(ethylene‐propylene) heterophasic copolymer [PP‐EP]/EVA systems

Morphological characteristics and mechanical properties of PP‐EP/EVA blends were studied and compared to those of PP/EVA previously reported. For the PPEP/EVA blends, interfacial interactions in amorphous zones, which were associated with shifts in T_g, were well defined compared to those of PP/EVA blends, although the nature of crystalline zones was similar for both systems. At EVA concentrations up to 20%, the elongation at break and impact strength slightly increased in both systems. However, PP‐EP/EVA displayed higher values of these properties compared with PP/EVA. At high EVA concentrations (above 20%), the indicated properties were enhanced in both polymeric systems, and the same proportional behavior was maintained. The decrease in tensile strength of PP‐EP/EVA was not as marked as in PP/EVA with the addition of EVA, and it remained below PP/EVA at high EVA concentrations. The improvement in properties of PP‐EP/EVA was attributed to favorable interactions between the ethylene groups contained in both copolymers. These interactions rendered a high degree of compatibility between the PP‐EP and EVA components.     

Drag Reduction by Wormlike Micelles of a Biodegradable and Non-Biodegradable Surfactants

This study describes the effects of wormlike micelles formed by the commercial surfactants tallowalkylamidopropyl dimethylamine oxide (Aromox APA-TW) and oleyl methyl bis(2-hydroxyethyl) ammonium chloride (Ethoquad O/12) as drag reducers. Ethoquad O/12 is immune to degradation by heat and microorganisms. Conversely, Aromox APA-TW is biodegradable in the environment, and its susceptibility to heat-induced degradation was previously assessed. This work considers the effects of temperature, salt, and time on the drag-reduction capacity (in different Reynolds number) of wormlike micelles of these two surfactants. Wormlike micelles formed by Aromox APA-TW are able to reduce drag at higher temperatures compared to wormlike micelles formed by Ethoquad O/12. However, Aromox APA-TW can degrade after being heated to 80 °C and also after storage of the wormlike micelle solutions. Ethoquad O/12 does not undergo degradation after being heated or stored. These surfactants have the potential to be used as additives in industrial operations, as the wormlike micelles formed are able to reduce drag in systems with long pumping distances or recirculation, even in solutions with high salt concentrations (brine) and high temperatures.