Hydrogenation of vegetable oil using highly dispersed Pt/γ-Al2O3 catalyst: Effects of key operating parameters and deactivation study

In the present work, Pt/γ-Al₂O₃ catalysts with high metal dispersion were prepared and characterized using chloroplatinic acid and platinum acetylacetonate as metal precursors. The activity and selectivity of the catalysts were evaluated in the hydrogenation of sunflower oil. A comprehensive analysis of the effects of key operational parameters on catalytic performance was carried out. The experimental variables were hydrogen pressure (275.8–551.6 kPa), temperature (160–200°C), and catalyst loading (0.005–0.015 kg Pt_exp/m³_oil). Platinum catalysts were active, with a double bond conversion of 28% at 2 h. The metal precursor affected catalyst selectivity. The catalyst prepared with chloroplatinic acid exhibited a lower formation of trans-isomers compared with Pt acetylacetonate. The γ-Al₂O₃ supported platinum catalyst with a metal loading of 0.51 wt.% and a metal dispersion of 98% maintained its initial catalyst activity and selectivity after 10 consecutive uses (1200 min accumulate operation time), without changes in its catalytic properties. The obtained results suggested that Pt catalysts are an attractive alternative to conventional nickel catalysts for the hydrogenation of vegetable oil.     

Analysis of polyolefin compositions through near infrared spectroscopy

In this work, NIRS is employed to provide compositions of α‐olefin copolymers, allowing for evaluation of the effects of certain key process variables on the final NIR spectral responses of obtained polymer materials. This work also introduces a new temperature programmed analytical technique, which combines NIRS measurements with partial fractionation of α‐olefin copolymers. The new proposed technique can be used for evaluation of polyolefin compositions, as presented here for poly(propene/1‐butene) copolymers. Besides, preliminary results obtained from thermal fractionation experiments indicate that this new proposed experimental technique can be employed for characterization of comonomer sequence distributions of α‐olefin copolymers. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40127.     

The Barley Chloroplast Mutator (cpm) Mutant: All Roads Lead to the Msh1 Gene

The barley chloroplast mutator (cpm) is a nuclear gene mutant that induces a wide spectrum of cytoplasmically inherited chlorophyll deficiencies. Plastome instability of cpm seedlings was determined by identification of a particular landscape of polymorphisms that suggests failures in a plastome mismatch repair (MMR) protein. In Arabidopsis, MSH genes encode proteins that are in charge of mismatch repair and have anti-recombination activity. In this work, barley homologs of these genes were identified, and their sequences were analyzed in control and cpm mutant seedlings. A substitution, leading to a premature stop codon and a truncated MSH1 protein, was identified in the Msh1 gene of cpm plants. The relationship between this mutation and the presence of chlorophyll deficiencies was established in progenies from crosses and backcrosses. These results strongly suggest that the mutation identified in the Msh1 gene of the cpm mutant is responsible for the observed plastome instabilities. Interestingly, comparison of mutant phenotypes and molecular changes induced by the barley cpm mutant with those of Arabidopsis MSH1 mutants revealed marked differences.     

On the Acetylation of Phenanthrene and 9-chlorophenanthrene

Friedel-Crafts acetylation of phenanthrene ( 1a ) in sym-tetrachloroethane yields mixtures of 2-, 3- and 9-acetylphenanthrenes ( 2a, 3a, 4 ). The distribution of isomers is found to depend strongly upon the method of mixing the reagents. Acetylation of 9-chlorophenanthrene ( 1b ), performed by a variety of methods and solvents, led mainly to 3-acetyl-9-chlorophenanthrene ( 3b ) (≥85%). Previously unreported 2-acetyl-9-chlorophenanthrene ( 2b ) was found to form up to a maximum 11% in nitrobenzene.     

Seasonal variations in total fatty acid composition of muscles and eye sockets of tucunaré (Cichla sp.) from the Brazilian Amazon area

Seasonal variations in total fatty acid compositions of tucunaré, Cichla sp. in the Janauacá Lake of the Amazon basin were determined by GC. Saturated fatty acids (SFAs) were found to be at higher concentrations than monounsaturated fatty acids (MUFAs) and polyunsaturated fatty acids (PUFAs) in two seasonal periods. Major fatty acids were palmitic (16:0, 48.5–51.6% of total SFA), oleic (18:1ω9, 43.9–50.2% of total MUFA), docosahexaenoic (DHA, 22:6ω3, 13.5–27.9% of total PUFA) and arachidonic acid (AA, 20:4ω6, 16.0–19.6% of total PUFA). Polyunsaturated fatty acids were the most abundant in muscle during the flood period, and more especially fatty acids 22:6ω3 (10%) and 20:4ω6 (7%). There were no significant variations amongst total lipid SFA, MUFA, and PUFA from eye sockets. The ω6 fatty acid percentages were always higher than the ω3 fatty acid percentages in tucunaré, with ω6/ω3 ratios varying between 1.02 and 1.6 in the flood and drought periods.     

Enzymatic de-glycosylation of rutin improves its antioxidant and antiproliferative activities

Bioavailability and biological properties of flavonoid glycosides can be improved after the enzymatic hydrolysis of specific glycosyl groups. In this study, we evaluate the antioxidant and antiproliferative potential of rutin after enzymatic hydrolysis performed by α-l-rhamnosidases (hesperidinase from Penicillium sp. and naringinase from Penicillium decumbens) previously heated at 70 °C for 30 min to inactivate the undesirable β-d-glucosidase activity. The highest in vitro antioxidant activity determined by DPPH radical scavenging was achieved with rutin hydrolyzed by hesperidinase. Rutin was predominantly bioconverted into quercetin-3-glucoside. There was no statistical difference between xanthine oxidase inhibition by rutin before and after hydrolysis. However, in vitro inhibitory activity against ten human tumor cell lines showed that hydrolyzed rutin exerted a more potent antiproliferative effect than quercetin and rutin on various cancer cell lines, specially glioma, and ovarian and breast adenocarcinomas. These results indicate that quercetin-3-glucoside could be a promising functional derivative obtained by rutin hydrolysis.     

Biobased surfactant-like molecules from organic wastes: the effect of waste composition and composting process on surfactant properties and on the ability to solubilize Tetrachloroethene (PCE)

In this work, four surfactant-like humic acids (HAs) obtained from garden lignocellulose wastes and kitchen food wastes mixed with garden-lignocellulose wastes, both before and after composting, were tested for surfactant properties and the ability to solubilize tetrachloroethene (PCE). The waste-derived HAs showed good surfactant properties, lowering the water surface tension from 74 mN m(-1) to 45.4 +/- 4.4 mN m(-1), with a critical micelle concentration (CMC) of 1.54 +/- 1.68 g L(-1), which is lower than many synthetic ionic surfactants. CMC was affected by both waste origin and composting processes. The addition of food waste and composting reduced CMC by adding alkyl-C (measured by CP MAS 13C NMR) and N- and S-HA contents (amide molecules), so that a multistep regression was found [CMC = 24.6 - 0.189 alkyl C - 2.64 (N + S); R2 = 0.77, P < 0.10, n = 6]. The four HAs solubilized PCE at the rate of 0.18-0.47 g PCE/g aqueous biosurfactant. These results were much higher than those reported in the literature for a commercial HA (0.026 g/g), but they were in line with those measured in this work for nonionic surfactants such as Tween-80 (0.69 g/g) and Triton X-100 (1.08 g/g).     

Microalgae biomass interaction in biopolymer gelled systems

Microalgae are an enormous biological resource, representing one of the most promising sources for the development of new food products and applications. Pea protein/κ-carrageenan/starch gels, interesting vegetarian alternatives to dairy desserts, served as model systems to study the addition of microalgal biomass, its effect, and subsequent rheological behaviour. Spirulina and Haematococcus gels presented a markedly different rheological behaviour compared to the control mixed biopolymer gelled system. The present goal is to clarify how these microalgae affect the gelation and interact with each biopolymer present in the complex mixed gel system. Hence, the aim of the present work is to study the effect of Spirulina and Haematococcus microalgal biomass addition on the rheological behaviour of pea protein, κ-carrageenan and starch simple gels, as well as in pea protein/κ-carrageenan and pea protein/starch systems. The gelation process was monitored in-situ through dynamic oscillatory measurements (temperature, time and frequency sweep tests) for a 24 h maturation period, and rheological results were supported with fluorescence optical microscopy observations. The addition of Spirulina and Haematococcus to biopolymer gelled systems induced significant changes in the gels’ rheological behaviour and microstructure. In general, it was observed that the gelling mechanism is ruled by the biopolymers, while microalgae seem to be embedded in the gel network acting as active particle fillers. The addition of Haematococcus resulted in more structured gels in comparison to the control and Spirulina systems. In the case of κ-carrageenan gels, both microalgae induced a large increase in the rheological parameters, which should be related to the high ionic content of microalgal biomass. Spirulina addition on starch systems promoted a decrease in the gels’ rheological parameters. This should be related to the starch gelatinization process, probably by competing for water binding zones during the granules’ hydration process.