This work reports the reduction of a large variety of aldehydes and ketones with the system PhSiH3/CpRu(PPh3)2Cl in good to excellent yields and high chemoselectivity. The catalyst CpRu(PPh3)2Cl can ...be used in at least 12 catalytic cycles with excellent catalytic activity and several substrates were reduced under solvent free conditions.
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•CpRu(PPh3)2Cl is highly efficient catalyst for the reduction of carbonyl compounds.•The reductions can be performed under solvent free conditions.•The catalyst CpRu(PPh3)2Cl can be use in 12 catalytic cycles with excellent activity.
In vitro batch incubations were used to study the rumen biohydrogenation of unsaturated fatty acids. An earlier study using increasing supplementation levels of stearidonic acid (18:4n-3), revealed ...that the rumen microbial population extensively biohydrogenates 18:4n-3 after 72 h of in vitro incubation, though several intermediates formed were not completely characterized. Therefore, in the present study, samples were reanalyzed in order to identify the 18:2, 18:3 and 18:4 biohydrogenation intermediates of 18:4n-3. Gas–liquid chromatography coupled to mass spectrometry was used to characterize these intermediates. The acetonitrile chemical ionization mass spectrometry of the fatty acid methyl esters derivatives enabled the discrimination of fatty acids as non-conjugated or conjugated biohydrogenation intermediates. In addition, the acetonitrile covalent adduct chemical ionization tandem mass spectrometry yielded prominent ions indicative of the double bond position of the major 18:3 isomers, i.e. Δ5,11,15 18:3. Furthermore, the 4,4-dimethyloxazoline derivatives prepared from the fatty acid methyl esters enabled the structure of novel 18:2, 18:3 and 18:4 biohydrogenation intermediates to be elucidated. The intermediates accumulated in the fermentation media after 72 h of incubation of 18:4n-3 suggest that similar to the biohydrogenation pathways of linoleic (18:2n-6) and α-linolenic (18:3n-3) acids, the pathway of the 18:4n-3 also proceeds with the formation of conjugated fatty acids followed by hydrogenation, although no conjugated dienes were found. The formation of the novel biohydrogenation intermediates of 18:4n-3 seems to follow an uncommon isomerization pattern with distinct double bond migrations.
•In both sampling sites, quality traits and residual contaminant levels in gonads varied seasonally.•Gonads were nutritionally richer, more firm and yellowish, but with less minerals during fall ...season.•Major contaminants in gonads and seawater were at trace levels, not constituting a health risk.•Fall is the best period to harvest high quality and safe gonads in the NW Portuguese coast.
Paracentrotus lividus gonads are gastronomic delicacies widely appreciated in Europe. Two commercially exploited populations of sea urchins were characterized, for the first time, in terms of gonad quality (market-related traits such as colour, texture and nutritional value) and safety (contaminants levels) to define the best season for harvesting this valuable resource. Spawning occurred between spring-summer, yet gonad index peaked only in one population during winter. In both populations, the strongest yellow colouration and highest gonad firmness, protein, lipid, polyunsaturated fatty acids and carotenoid contents as well as the lowest contents of mineral were registered in fall. Inorganic and organic contaminants levels were, in general, similar among sites and seasons, being found at trace levels in seawater and gonads, with low risk for consumers. For these populations, high-quality gonads can be harvested during fall, despite being safe for human consumption all year round.
This paper introduces a new method for a one-step determination of ammonia nitrogen (NH3) in high complex solid and liquid samples from the agricultural and livestock sectors. To this end, we ...developed a simultaneous extraction and fluorimetric labeling of NH3, using gas diffusion microextraction (GDME), followed by the fluorescence measurement under 96-well microplate format. The GDME ensured a selective diffusion of NH3 through a commercial hydrophobic membrane, and confined the acceptor solution, which included the fluorimetric labeling reagent o-phthalaldehyde (OPA). The OPA-NH3 labeling reaction was optimized resorting to a full factorial experimental design, which showed that the reducing agent (Na2SO3) concentration was critical to achieve the highest sensitivity. A similar optimization approach for GDME showed that time and temperature significantly influenced the sensitivity of the assay, and also that the modifications in these two factors could be used to adjust the sensitivity according to the concentrations present in the samples. In our final conditions, it was possible to quantify NH3 in the range between 0.38 and 6.27mgL−1 using a 10min extraction at 25°C in different samples (e.g., corn and grass silages, feces, urine). The developed method showed a high repeatability and reproducibility (intraday and interday relative standard deviations values of 4.5% and 9.5%, respectively) and an adequate limit of detection (0.22mgL−1). This new methodology also highlighted the simplicity and versatility of GDME for the determination of volatile components of high-complex matrices, which will certainly drive future developments in the analysis of environmental and biological samples.
•A new methodology for ammonia-N determination in complex samples is presented.•Gas-diffusion microextraction and fluorimetric derivatization in a single step.•Labeling reaction and extraction parameters were optimized by an experimental design.•The method allowed the application in routine analyses of solid and liquid samples.
•The influence of ultrasound in the activity of amyloglucosidase was evaluated.•Six commercially-available amyloglucosidases were tested.•A Box-Behnken response surface methodology established the ...optimum conditions for each enzyme.•The role of US in the amlyloglucosidase-assisted hydrolysis of pure starch (corn, rice, potato, wheat) was investigated.
The present report studied the role of ultrasound (US) energy in the amyloglucosidase-based starch hydrolysis using two complementary approaches: (i) in the activity of six commercially-available amyloglucosidases (using soluble starch as substrate), and (ii) in the hydrolysis of four pure starches from different botanical sources. This corresponds to the first systematic evaluation of the role of US in starch hydrolysis mediated by amyloglucosidase, being a consequence of our previous report that assessed the effect of US in the activity of alpha-amylase (LWT – Food Science and Technology 84 (2017) 674–685). Regarding amlyloglucosidases, three enzymes obtained from Aspergillus niger (AN1-AN3), and Spirizyme Achieve (SPA), Spirizyme Fuel (SPF) and Spirizyme Ultra (SPU) were submitted to a Box-Behnken experimental design in order to establish the optimum conditions for their maximum activity. In the presence of US, we found both inactivation and activation, ranging from -88% (AN3) to 699% (SPA). The US promoted the enzyme activity when combined with lower temperatures (40–60 °C), with a marked effect in Spirizyme enzymes. Based on the optimum conditions established by the experimental design, we also evaluated the role of US in the glucose yield resulting from the hydrolysis of pure starches (corn, rice, potato, wheat). In this case, US led to higher glucose yields in all conditions tested. The enhancement factors observed ranged from 1.2 (AN1, rice starch) to 65 (SPA, potato starch) times. We compared these findings with previous reports, which highlighted the role of US in intensifying amyloglucosidase-based saccharification in mild conditions, by simultaneously influencing both enzyme and substrate. Hence, US power has to be fine-tuned for each particular enzyme in order to maximize process intensification.
The effects of increasing levels of solvent-extracted palm kernel meal (SPKM) and corn distillers dried grains (CDG) in corn silage-based diets on feed intake and milk production were examined in 2 ...experiments. In Experiment 1, 20 Holstein cows averaging 100 d in milk (DIM) (SD=61.5) at the start of the experiment were utilized in an 11-wk randomized complete block design with 4 treatments in 5 blocks to study effects of increasing levels of SPKM in the diet. During a 3-wk preliminary period, cows were fed a standard diet. At the end of the preliminary period, cows were blocked by 4% fat-corrected milk yield, parity number (primiparous and multiparous), and DIM, and were assigned randomly to 1 of 4 experimental diets. The total mixed ration (TMR) consisted of (dry matter basis) 40% corn silage, 5% coarsely chopped wheat straw, and 55% concentrate. The increasing dietary levels of SPKM were achieved by replacing protein sources and citrus pulp with SPKM and urea (0, 5, 10, and 15% SPKM and 0.06, 0.22, 0.38, and 0.55% urea for SPKM0, SPKM5, SPKM10, and SPKM15, respectively). In Experiment 2, 18 Holstein cows averaging 93 DIM (SD=49.1) at the start of the experiment were utilized in an 11-wk randomized complete block design with 3 treatments in 6 blocks to study effects of increasing levels of CDG in the diet. The preliminary period lasted for 2 wk. Assignment of cows to treatments was the same as in Experiment 1. The TMR consisted of (dry matter basis) 40% corn silage, 5% coarsely chopped wheat straw, and 55% concentrate. The increasing dietary levels of CDG were achieved by replacing soybean meal and citrus pulp with CDG and urea (0, 7, and 14% CDG and 0, 0.22, and 0.49% urea for CDG0, CDG7, and CDG14, respectively). There were no significant treatment effects on dry matter intake, milk yield, or milk composition in Experiment 1. Inclusion of SPKM tended to increase protein and lactose contents of milk. The SPKM0 diet promoted body weight loss. There were no treatment effects in Experiment 2, except for milk protein content, which was decreased by CDG. Plasma Lys concentration tended to be affected by SPKM and CDG inclusions. Plasma concentrations of 3-methylhistidine and Leu seemed to be related to body protein degradation/synthesis. The feeding of SPKM up to 15% in the diet decreased feed costs without detrimental effects on productive responses and tended to increase milk protein content. The inclusion of CDG in diets based on corn silage and corn byproducts might decrease milk protein content due to an unbalanced supply of AA, particularly Lys.
Two Latin square design experiments investigated the relationship between hydrogen sulphide concentration in the rumen headspace gas of dairy cows and the early stages of protein degradation in the ...rumen. In Expt 1, three protein sources differing in rumen N (nitrogen) degradability (maize gluten feed (MGF); sunflower meal (SFM); and soyabean meal (SBM)) were used, whereas in Expt 2 four different batches of the same feed (MGF) differing in colour (CIE L*, a*, b* (CIELAB) scale) were used. After allowing the concentration of hydrogen sulphide in rumen gas to decline close to zero, a fixed amount of protein sources was offered to cows and the concentrations of hydrogen sulphide were recorded in rumen headspace gas at 30-min intervals. In Expt 1, the concentration of hydrogen sulphide showed considerable variation between protein sources, with MGF having the highest concentration followed by SFM and SBM resulting in very low concentrations. The N wash losses (zero time measurements with nylon bags) ranked the feeds in the same way, from MGF (highest; 61%) to SBM (lowest; 26%). There were marked differences in the degradation of cystine and methionine between protein sources, although the degradation of cystine was always higher than for methionine. MGF (Expt 2) led to increased concentrations of hydrogen sulphide, with peak concentrations achieved between 1 and 2 h after feeding. The concentrations of hydrogen sulphide were higher for MGF1, intermediate for MGF2 and lower for MGF3 and MGF4, agreeing with colour scale. Differences in the early stages of dietary sulphur degradation corresponded with differences in hydrogen sulphide concentrations in rumen gas. The results suggest that hydrogen sulphide concentrations in the rumen headspace gas could be useful to evaluate nutritional parameters not measured by the in sacco technique, contributing to a better understanding of the response of dairy cows to different protein supplements.
The fatty acid (FA) analysis of grass and maize silages was studied by application of a direct transesterification method (DT) followed by purification by solid-phase extraction (SPE). The choice of ...the internal standard (IS) for quantification of FA by gas−liquid chromatography (GLC) was also studied. The acidic DT method applied to grass silage samples produced a high amount of non-fatty acid methyl ester compounds (non-FAME) compared with those formed in maize silages. The application of the SPE cleanup step reduced significantly the amount of non-FAME compounds in both samples. Five FAs were tested as IS; among them, 3 were naturally present in all silages, however their use as IS did not affect quantification of total FA composition. Nevertheless, some minor FAs present in silages were significantly affected by the IS used. Additionally, application of corrections to the GLC peak areas did not significantly influence quantification of total FA composition of silages.
The identification of crops that simultaneously contribute to the global protein supply and mitigate the effects of climate change is an urgent matter. Lupins are well adapted to nutrient-poor or ...contaminated soils, tolerate various abiotic stresses, and present relevant traits for acting as ecosystem engineers. Lupins are best studied for their seeds, but their full foraging potential needs further evaluation. This study evaluated the effects of location and sowing date on forage production, proximate composition, and the detailed mineral and alkaloid profiles of three species of Lupinus (L. albus cv. Estoril, L. angustifolius cv. Tango, and L. luteus cv. Cardiga). Sowing date and location and their interaction with the plant species significantly affected the vast majority of measured parameters, emphasizing the effects of climate and soil conditions on these crops. The relatively high crude protein and in vitro digestibility support the potential of the lupin species studied as sustainable forage protein sources in diets for ruminant animals. The content of individual essential macro and trace elements was below the maximum tolerable levels for cattle and sheep. Lupanine, smipine, and sparteine were the most abundant quinolizidine alkaloids in L. albus cv. Estoril, lupanine, and sparteine in L. angustifolius cv. Tango, and lupinine, gramine, ammodendrine, and sparteine in L. luteus cv. Cardiga. Based on the maximum tolerable levels of total quinolizidine alkaloid intake, the dietary inclusion of forages of L. albus cv. Estoril and L. angustifolius cv. Tango does not pose a risk to the animals, but the high alkaloid content of L. luteus cv. Cardiga may compromise its utilization at high levels in the diet. Overall, the results reveal a high potential for lupins as protein forage sources well adapted to temperate regions and soils with lower fertility, with a relevant impact on livestock sustainability in a climate change era.
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