MCM-41 Heterogenized Chiral Amines as Base Catalysts for Enantioselective Michael Reaction

Cinchonidine and cinchonine have been grafted onto pure silica MCM-41. It has been shown that both supported alkaloids are active catalysts for the Michael addition of ethyl 2-oxocyclopentanecarboxylate and methyl vinyl ketone, anchored cinchonidine being more active and enantioselective than anchored cinchonine. The study of the influence of the polarity of the solvent and reaction temperature on the optical induction shows that there is not a direct correlation between solvent polarity and enantioselectivity, and the maximum optical yield was obtained between 278 and 273 K.     

Distribution of chlorophylls and carotenoids in ripening olives and between oil and alperujo when processed using a two-phase extraction system

The present work has studied the content and type of pigments present in olive fruits and the respective oils and alperujos. The concentration of isochromic pigment fractions—chlorophylls and carotenoids—decreased with fruit ripening, more markedly in the former than in the latter. This implied that the ratio between the two pigment fractions also decreased in parallel in the three products studied. However, the value in the oil was lower than in the fruit, and that in the alperujo was much higher. During the extraction process, the release of acids may have caused pheophytinization reactions in the chlorophyll fraction, increasing pheophytin content in alperujos and oils, whereas the carotenoid fraction was affected only in the alperujo. Chlorophyll b derivatives were destroyed in greater proportion than chlorophyll a derivatives during transfer to the oil. During processing the destruction of lutein was greater than that of β-carotene. The balance of matter between fruit, alperujo, and oil indicated that not all the fruit pigmentation was released from the structures, and most remained occluded in the alperujo. The rest of the pigmentation, and particularly the chlorophyll fraction, was partly destroyed during its transfer to the oil.     

An efficient method for a numerical description of virgin olive oil color with only two absorbance measurements

Four polynomial expressions are obtained that provide a good approximation and an easy, rapid calculation of the chromatic coordinates and the chroma—L ^*, a ^*, b ^*, and C—for the illuminant C and the standard observer, for a virgin or extra virgin olive oil; absorbance is measured at only 480 and 670 nm. These are as follows: L ^*=0.556458(A₄₈₀)²−2.51145A₄₈₀+0.55504(A₆₇₀)²−8.53016A₆₇₀+98.4089; a ^*=0.177372(A₄₈₀)²+2.1363A₄₈₀+1.43254(A₆₇₀)²−0.789231A₆₇₀−13.9246; b ^*=−16.0277(A₄₈₀)²+79.8932A₄₈₀−5.06558(A₆₇₀)²+3.36169A₆₇₀+31.9405; C=−15.8439(A₄₈₀)²+78.9312A₄₈₀−5.26784(A₆₇₀)²+3.56917A₆₇₀+33.3927. These give acceptable results, making the method a practical alternative to the extremely laborious Commission Internationale d’Eclairage (CIE) L ^* a ^* b ^* system, by which 391 absorbance values must be measured individually, nanometer by nanometer, before applying more complex equations. The validity of the proposed method has been confirmed by comparison, using a set of 20 sample oils different from the set of 25 oils used to generate the order of the equations. The variations between the values provided by the proposed and standard methods, respectively, had a mean of 0.00 for each of the chromatic variables—L ^* , a ^* , b ^* , and C; SD were moderate (0.71, 0.52, 1.22, and 1.22, respectively); the root mean square and the R ²-terms also confirmed the validity of the method.     

Molecular Characterization of a Lysophosphatidylcholine Acyltransferase Gene Belonging to the MBOAT Family in Ricinus communis L.

Acyl-CoA:lysophosphatidylcholine acyltransferase (LPCAT, EC 2.3.1.23) catalyzes acylation of lysophosphatidylcholine (lysoPtdCho) to produce phosphatidylcholine (PtdCho), the main phospholipid in cellular membranes. This reaction is a key component of the acyl-editing process, involving recycling of the fatty acids (FA) mainly at the sn-2 position of PtdCho. Growing evidences indicate that the LPCAT reaction controls the direct entry of newly synthesized FA into PtdCho and, at least in some plant species, it has an important impact on the synthesis and composition of triacylglycerols. Here we describe the molecular characterization of the single LPCAT gene found in the genome of Ricinus communis (RcLPCAT) that is homologous to LPCAT genes of the MBOAT family previously described in Arabidopsis and Brassica. RcLPCAT is ubiquitously expressed in all organs of the castor plant. Biochemical properties have been studied by heterologous expression of RcLPCAT in the ale1 yeast mutant, defective in lysophospholipid acyltransferase activity. RcLPCAT preferentially acylates lysoPtdCho against other lysophospholipids (lysoPL) and does not discriminates the acyl chain in the acceptor, displaying a strong activity with alkyl lysoPL. Regarding the acyl-CoA donor, RcLPCAT uses monounsaturated fatty acid thioesters, such as oleoyl-CoA (18:1-CoA), as preferred donors, while it has a low activity with saturated fatty acids and shows a poor utilization of ricinoleoyl-CoA (18:1-OH-CoA). These characteristics are discussed in terms of a possible role of RcLPCAT in regulating the entry of FA into PtdCho and the exclusion from the membranes of the hydroxylated FA.     

Corrosion inhibition of aluminum by organic coatings formulated with calcium exchange silica pigment

One of the first commercial ion-exchange anticorrosive pigments to be developed was Shieldex^® (Si/Ca). Its proposed corrosion protection mechanism, based on the retention of aggressive cations and the subsequent release of calcium cations, has created certain controversy. A number of studies have focused on the anticorrosive behavior of this pigment on carbon steel and galvanized steel to replace chromates (Cr⁶⁺) as inhibitor pigment, but none has considered its performance on aluminum or aluminum alloys. In this research, alkyd coatings have been formulated with Si/Ca pigment at different concentrations and applied on aluminum 1050 (Al 99.5%) specimens. These specimens have then been subjected to accelerated tests (condensing humidity, salt spray, and Kesternich) and natural weathering in atmospheres of different aggressivity. Corrosion performance has been also evaluated in the laboratory by electrochemical impedance spectroscopy. The study has also considered an organic coating with zinc chromate anticorrosive pigment for comparative purposes. The results obtained with organic coatings formulated with Si/Ca pigments confirm that they provide corrosion protection of the underlying aluminum substrate, even improving the behavior of the reference zinc chromate in some environmental conditions.     

Evidences of the Cerium Oxide-Catalysed DPF Regeneration in a Real Diesel Engine Exhaust

The active phase Ce_0.5Pr_0.5O₂ has been loaded on commercial substrates (SiC DPF and cordierite honeycomb monolith) to perform DPF regeneration experiments in the exhaust of a diesel engine. Also, a powder sample has been prepared to carry out soot combustion experiments at laboratory. Experiments performed in the real diesel exhaust demonstrated the catalytic activity of the Ce–Pr mixed oxide for the combustion of soot, lowering the DPF regeneration temperature with regard to a counterpart catalyst-free DPF. The temperature for active regeneration of the Ce_0.5Pr_0.5O₂-containing DPF when the soot content is low is in the range of 500–550 °C. When the Ce_0.5Pr_0.5O₂-containing DPF is saturated with a high amount of soot, pressure drop and soot load at the filter reach equilibrium at around 360 °C under steady state engine operation due to passive regeneration. The uncoated DPF reached this equilibrium at around 440 °C. Comparing results at real exhaust with those at laboratory allow concluding that the Ce_0.5Pr_0.5O₂-catalysed soot combustion in the real exhaust is not based on the NO₂-assisted mechanism but is most likely occurring by the active oxygen-based mechanism.     

Synthesis and characterization of polyurethane/titanium dioxide nanocomposites obtained by in situ polymerization

The development of new polymeric and polymeric based materials is fundamental to meet the market demands. This work aims the synthesis and characterization of polyurethane/titanium dioxide nanocomposite, using low cost commercial raw materials. Nanocomposites were synthesized by in situ polymerization reactions in which titanium dioxide were added in the following proportions, by weight, in relation to the mass obtained from the pure polymer: 0.5, 1.0, 2.0, 3.0, 5.0, 7.0, and 10.0 %. These reactions were based in poli (ε-caprolactone) and 1,6-diisocyanatohexane. The materials were characterized by infrared spectroscopy Fourier transform, scanning electron microscopy, differential scanning calorimetry analysis, thermogravimetric analysis, dynamic mechanical thermal analysis, and UV–Vis spectroscopy. Based on the obtained results it was concluded that the nanocomposites synthesized by in situ polymerization presented, in general, thermal properties (degradation temperature) and mechanical properties higher than the pure polymer.     

Volatile Organic Compounds of Conspecific-Damaged Eucalyptus benthamii Influence Responses of Mated Females of Thaumastocoris peregrinus

Plants respond to herbivory by synthesizing and releasing novel blends of volatile organic compounds (VOCs). Natural enemies are attracted to these VOCs, but little is known about the effects of these chemicals on the herbivores themselves. We studied the effect of Thaumastocoris peregrinus herbivory on VOCs released by Eucalyptus benthamii plants and the responses of this herbivore to the VOCs. In total, 12 compounds released by E. benthamii were identified. Five compounds (β-pinene, linalool, 9-epi-(E)-caryophyllene, viridiflorol, and one unidentified compound) emitted after herbivore and mechanical damage were not detected in collections from undamaged plants. The three most abundant VOCs, α-pinene, aromadendrene, and globulol, were released in greater quantities from herbivore-damaged plants compared to plants with mechanical damage, which, in turn, released greater amounts than undamaged (control) plants. The VOCs emitted after herbivore damage did not differ during the photophase and scotophase in either quantity or quality. In an olfactometer, mated female T. peregrinus showed a preference for undamaged plants over herbivore-damaged plants, and also for hexane over α-pinene at an amount equivalent to that released by a herbivore-damaged plant. In the olfactometer, virgin females did not exhibit any preference between conspecific-damaged or undamaged plants.     

Biosynthesis and Site of Production of Sex Pheromone Components of the Cerambycid Beetle, Hedypathes betulinus

We determined the site of pheromone production tissues and a partial route for the biosynthesis of the sex pheromone in Hedypathes betulinus (Coleoptera: Cerambycidae: Lamiinae), Brazil’s main green maté pest. Pheromone was found predominantly in the prothorax of males, suggesting that this is the region of production of pheromones in this insect. Scanning electron microscopy revealed small pores that may be associated with pheromone release in males; these pores also were observed in females. A deuterium-labeled putative precursor (geranyl acetone-D₅) of the sex pheromone of H. betulinus was synthesized. When applied to the prothorax of males, label from the precursor was incorporated into the pheromone components, confirming that pheromone production occurs in the prothorax and that the pheromone components are biosynthesized from geranyl acetone.