Notes on the Asymmetric Hydrogenation of Methyl Acetoacetate in Neoteric Solvents

Asymmetric hydrogenation of methyl acetoacetate to methyl (R)-3-hydroxybutyrate by [(R)- RuCl(binap)(p-cymen)]Cl has been studied in methanol-ionic liquid and methanol- dense CO₂ solvent systems. The ionic pairs triethylhexylammonium and 1-methylimidazolium with bis(trifluoromethane sulfonyl) imide and hexafluorophosphates were used. The role of ionic pairs on the kinetic parameters and (enantio)selectivity has been demonstrated. Although the CO₂ expanded methanol system suffered from a reduction in both reaction rate and product selectivity, this changed in the presence of water. The high selectivity of the optimized methanol-CO₂-water-halide system was designed as a consequence of observed additive effects.     

From coffee industry waste materials to skin‐friendly products with improved skin fat levels

Spent coffee grounds (SCG), which are the residue obtained from the treatment of coffee with hot water or steam, can be used for industrial applications, due to the high content in lipids. The cosmetic products might be a suitable application for these types of residues because the barrier properties of the stratum corneum (SC) are largely dependent on the intactness of the lipid lamellae that surrounds the corneocytes. The purpose of this work was to assess the feasibility of using the lipid fraction of SCG extracted with supercritical carbon dioxide in the development of new cosmetic formulations with improved skin lipids (sebum) and hydration. The use of spent coffee lipid extract in cosmetic industry seems to be a suitable approach to recycle the wastes from coffee industry. Emulsion containing 10% of the lipid fraction of SCG (SpentCofOil cream) presented promising characteristics in the improvement of sebum skin levels with a good acceptance by consumers when compared to an emulsion containing 10% w/w of green coffee oil (GreenCofOil cream) and a placebo without coffee oil (NoCofOil cream). Practical applications: In this work, the authors develop and characterize a cream containing 10% of the lipid fraction of SCG extracted with supercritical carbon dioxide with improved skin lipids (sebum) and hydration.     

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     

NiMo/C Used as Magnetic Support for SILP Catalysts

In this work, supported ionic liquid (IL) phases catalysts were prepared based on Pd dispersed in IL phases supported on magnetic particles of nickel/molybdenum covered with carbon (NiMo/C). The magnetic support was prepared via CVD method at 800 °C. XRD analysis showed the phases of metallic nickel and molybdenum carbide. The presence of carbon in these materials was confirmed by TEM/EDS and thermogravimetric analysis (TG) analysis. Pd particles were dispersed in 1 and 2.5 wt% of the IL 1-butyl-3-methylimidazolium tetrafluoroborate (BMIm·BF₄), which were immobilized on the support surface via impregnation method. TG analysis shows a weight loss between 300 and 420 °C attributed to the BMIm·BF₄, confirming the existence of IL on the support surface. The prepared materials were investigated in hydrogenations reactions of 1,5-cyclooctadiene and nitrobenzene, and the influence of IL on the activity and selectivity of these catalysts were observed. These materials have great potential for catalysis applications, because they bring together the advantages of the IL in the catalyst surface and the facility of magnetic materials separation.     

Changes in Lipid Class and Fatty Acid Composition of Cultures of <Emphasis Type=Italic>Pavlova lutheri</Emphasis>, in Response to Light Intensity

Aquaculture is a growing commercial activity worldwide, which resorts more and more often to microalgae as feed; the lipid composition of such microalgae is a critical factor with regard to the fish growth rate upon ingestion. The aim of this work was thus to study the influence of light intensity on the lipid profile of a known microalga, Pavlova lutheri. Several semi-continuous cultures were carried out, and biochemical parameters such as lipid, protein, carbohydrate, and chlorophyll contents were quantified. Lipids were specifically fractionated into classes by TLC, and those in each class were subjected to GC afterwards in an attempt to ascertain their fatty acid profile. Evidence was consequently provided which showed that cultures grown under low light intensity (9 W m⁻²) possess a higher fraction of eicosapentaenoic (EPA) and docosahexaenoic (DHA) acids esterified in polar classes—which are those with a more favorable role in aquaculture. It was also demonstrated that intermediate levels of light intensity (19 W m⁻²) may be misleading in terms of favorable effects upon EPA and DHA contents—because there is an increase in their total yields and productivities, but they appear mostly esterified into triacylglycerols; this may be a favorable deed for production and purification, but is metabolically not so effective in aquaculture. The highest EPA and DHA productivities attained were 1.29 and 0.69 mg L⁻¹ day⁻¹, respectively, at intermediate levels of light intensity (19 W m⁻²).     

Use of Ozonated Water for Disinfecting Gastrointestinal Endoscopes

The reprocessing of endoscopes is a complex procedure due to their structural design. In the constant search for new antimicrobial substances, recent studies with ozone have yielded great benefits. The present study evaluated the effects of ozonated water used to disinfect endoscopes comparing its efficacy with the conventional technique (2% glutaraldehyde). According to the results obtained, when ozonated water was used (330 mg.min.L^?1), induced a 2 log reduction of the viable microorganisms under the conditions tested. Ozonated water was a potent gastrointestinal endoscopic sanitizer, suggesting it is a feasible alternative for disinfection.     

Valley floor landscape change following almost 100 years of flood embankment abandonment on a wandering gravel‐bed river

Critical to restoring the nature conservation value of many river corridors is an understanding of how alluvial landscapes will respond to cessation of river management and land use practices that have previously degraded the environment. This paper analyses changes in valley floor landforms and vegetation patch dynamics, in relation to fluvial disturbance, over a period of almost 100 years following flood embankment abandonment on a wandering gravel‐bed river, namely the River Tummel, Scotland. Such rivers were once typical of many draining upland areas of northern maritime Europe. Prior to abandonment the valley floor landscape was agriculturally dominated and the river for the most part was single thread confined between flood embankments. The pattern of landform change and vegetation patch development over time following a decision in 1903 not to maintain embankments was tracked by geomorphic and land cover mapping utilizing successive sets of aerial photography for the period 1946 to 1994. A historical context for these changes was also feasible because the channel planform in 1900 and earlier channel planform changes dating back to 1753 were known due to the availability of old maps and earlier geomorphic studies. The land cover mapping was validated by comparison of results produced from the interpretation work on the 1994 aerial photographs with the field‐based UK National Vegetation Classification protocol. The findings of the study illustrate that bordering the River Tummel fluvial landforms and vegetation patch mosaics, presumably resembling those that occurred before valley floor land use intensification, evolved in less than 50 years after flood embankment abandonment with a resultant increase in habitat diversity. The change relates primarily to flood‐induced channel planform change and moderate levels of fluvial disturbance. The general significance of this change to plant species diversity on the valley floor of the River Tummel and elsewhere is discussed as is possible implications of the upstream impoundment and scenarios for climatically induced changes in flood frequency and magnitude. The overall outcome is the strong possibility that simple changes in river management and land use practices could result in re‐establishment of the nature conservation value of similar river corridors in Europe over the medium term without active restoration efforts. Copyright © 2002 John Wiley & Sons, Ltd.     

Variation in Preen Oil Composition Pertaining to Season,Sex, and Genotype in the Polymorphic White-Throated Sparrow

Evidence for the the ability of birds to detect olfactory signals is now well documented, yet it remains unclear whether birds secrete chemicals that can be used as social cues. A potential source of chemical cues in birds is the secretion from the uropygial gland, or preen gland, which is thought to waterproof, maintain, and protect feathers from ectoparasites. However, it is possible that preen oil also may be used for individual recognition, mate choice, and signalling social/sexual status. If preen oil secretions can be used as socio-olfactory signals, we should be able to identify the volatile components that could make the secretions more detectable, determine the seasonality of these secretions, and determine whether olfactory signals differ among relevant social groups. We examined the seasonal differences in volatile compounds of the preen oil of captive white-throated sparrows, Zonotrichia albicollis. This species is polymorphic and has genetically determined morphs that occur in both sexes. Mating is almost exclusively disassortative with respect to morph, suggesting strong mate choice. By sampling the preen oil from captive birds in breeding and non-breeding conditions, we identified candidate chemical signals that varied according to season, sex, morph, and species. Linear alcohols with a 10–18 carbon chains, as well as methyl ketones and carboxylic acids, were the most abundant volatile compounds. Both the variety and abundances of some of these compounds were different between the sexes and morphs, with one morph secreting more volatile compounds in the non-breeding season than the other. In addition, 12 compounds were seasonally elevated in amount, and were secreted in high amounts in males. Finally, we found that preen oil signatures tended to be species-specific, with white-throated sparrows differing from the closely related Junco in the abundances and/or prevalence of at least three compounds. Our data suggest roles for preen oil secretions and avian olfaction in both non-social as well as social interactions.     

Comparative Analysis of Ozone and Ultrasound Effect on the Elimination of Giardia spp. Cysts from Wastewater

Giardia spp. is a flagellate protozoan that presents two evolution forms, cysts and trophozoites. Cysts are resistant to chlorine, the most employed disinfectant agent in the treatment of water. For this reason, new techniques for the disinfection of waters that contain this parasite are necessary. This work evaluated the efficiency of the disinfection by ozone and ultrasound individually and simultaneously upon wastewater. The data obtained showed that after application, ozone, ultrasound, and combined techniques induced a significant elimination of Giardia spp. cysts. Furthermore, this effect was more accentuated when the two techniques were applied simultaneously.     

Late season nitrogen fertilization of soybeans: effects on leaf senescence, yield and environment

Nitrogen demand from soybean seeds during seed filling is very high and has been proposed as the cause of nitrogen remobilization and leaf senescence. Previous research has not shown consistent effects of late season fertilization on seed yield, while its effects on leaf senescence have not been evaluated. Two field experiments were performed to determine the effects of a late season N fertilization on leaf senescence and fall, seed yield and its components, and residual soil nitrate, and to evaluate the potential risk of groundwater contamination. Two rates of nitrogen (50 and 100 kg N ha^–1) were applied at the R3 and R5 development stages. Nitrogen fertilization, either at R3 or R5, increased soil nitrate availability during the seed-filling period. Seed yield, seed number and protein content were not affected by N fertilization. The addition of 100 kg N ha^–1 produced a small delay of 1–2 days in the leaf fall, and slightly increased seed size (3.6%). Our results suggest that increasing soil N availability during the seed-filling period is not an effective way to delay leaf senescence or to increase seed growth and yield of soybean. Nitrogen fertilization increased the level of residual nitrate in the top soil at one site (the one with lowest seed yield), increasing the risk of nitrate leaching during subsequent fallow.