Population-level modeling to account for multigenerational effects of uranium in Daphnia magna

As part of the ecological risk assessment associated with radionuclides in freshwater ecosystems, toxicity of waterborne uranium was recently investigated in the microcrustacean Daphnia magna over a three-generation exposure (F0, F1, and F2). Toxic effects on daphnid life history and physiology, increasing over generations, were demonstrated at the organism level under controlled laboratory conditions. These effects were modeled using an approach based on the dynamic energy budget (DEB). For each of the three successive generations, DEBtox (dynamic energy budget applied to toxicity data) models were fitted to experimental data. Lethal and sublethal DEBtox outcomes and their uncertainty were projected to the population level using population matrix techniques. To do so, we compared two modeling approaches in which experimental results from F0, F1, and F2 generations were either considered separately (F0-, F1-, and F2-based simulations) or together in the actual succession of F0, F1, and F2 generations (multi-F-based simulation). The first approach showed that considering results from F0 only (equivalent to a standard toxicity test) would lead to a severe underestimation of uranium toxicity at the population level. Results from the second approach showed that combining effects in successive generations cannot generally be simplified to the worst case among F0-, F1-, and F2-based population dynamics.     

Kinetic evaluation of removal of odorous contaminants in a three-stage biological air filter

Biofiltration is a cost-effective technology for removing air contaminants from animal facilities. Kinetic analysis can be helpful in understanding and designing the process but has not been performed on full-scale filters treating complex mixtures. In this study, kinetics was investigated in a full-scale biological filter treating air pollutants from a pig facility. Due to the high air flow rates used in the filter, both a plug flow model and a model based on complete mixing were tested with respect to kinetic order and Michaelis-Menten kinetics. Application of these models only gave poor to moderate agreement with air filter removal data. Two alternative kinetic models (Stover-Kincannon model and Grau second-order model) adopted from wastewater biofiltration process analysis were introduced to analyze contaminant removal in the biological air filter. Data analysis demonstrated the applicability of these two models with a high degree of precision on contaminant removal in the biological air filter. Whereas the Stover-Kincannon model demonstrated that pollutant removal rates were related to the mass loading rates, the Grau second-order kinetic model indicated that the removal efficiencies were dependent on air loading rates. Therefore, the kinetic data can be used for comparing biofilter performances and for design purposes.     

Metabolic and production profiles of dairy cows in response to decreased nutrient density to increase physiological imbalance at different stages of lactation

Physiological imbalance (PI) is a situation in which physiological parameters deviate from the normal, and cows consequently have an increased risk of developing production diseases and reduced production or reproduction. Our objectives were to (1) determine the effect of stage of lactation and milk yield on metabolic and production responses of cows during a nutrient restriction period to experimentally increase PI; (2) identify major metabolites that relate to degree of PI; and (3) identify potential biomarkers in milk for on-farm detection of PI throughout lactation. Forty-seven Holstein cows in early [n=14; 49±22 d in milk (DIM); parity=1.6±0.5], mid (n=15; 159±39 DIM; parity=1.5±0.5), and late (n=18; 273±3 DIM; parity=1.3±0.5) lactation were used. Prior to restriction, all cows were fed the same total mixed ration ad libitum. All cows were then nutrient restricted for 4 d by supplementing the ration with 60% wheat straw to induce PI. After restriction, cows returned to full feed. Daily milk yield was recorded and composite milk samples were analyzed for fat, protein, lactose, citrate, somatic cells, uric acid, alkaline phosphatase, β-hydroxybutyrate (BHBA), and milk urea nitrogen. Blood was collected daily and analyzed for metabolites: nonesterified fatty acids (NEFA), BHBA, glucose, plasma urea nitrogen, and insulin. The revised quantitative insulin sensitivity check index (RQUICKI) was calculated for each cow. Liver biopsies collected before and during restriction were analyzed for triglycerides, glycogen, phospholipids, glucose, and total lipid content. A generalized linear mixed model was used to determine the effect of stage of lactation on responses during restriction. Regression analyses were used to examine the effect of pre-restriction levels on changes during restriction. Similar decreases in milk yield among groups indicate that the capacity of individual responses is dependent on milk yield but the coping strategies used are dependent on stage of lactation. Milk yield was a better predictor of feed intake than DIM. Plasma glucose decreased for all cows, and cows in early lactation had increased plasma BHBA, whereas cows in later lactation had increased NEFA during restriction. Milk citrate had the greatest increase (58%) during restriction for all cows. Results reported here identified metabolites (i.e., glucose, NEFA, BHBA, cholesterol) as predictors of PI and identified milk citrate as a promising biomarker for PI on farm.     

Milk fatty acid composition and production performance of Danish Holstein and Danish Jersey cows fed different amounts of linseed and rapeseed

Fat supplements are used in diets for dairy cows to increase energy intake and milk production and the fatty acid composition of the feed affects milk fatty acid composition. A total of 74 Danish Holstein and 41 Danish Jersey cows were divided into 4 groups and the cows within each group were fed a mixed ration supplemented with 0, 3.5, 6.8, or 10.2% of dry matter of a linseed:rapeseed (1:3) mixture during lactation wk 6 to 30. Milk yield, fat, and lactose contents were not affected by treatments for Danish Holsteins, whereas these parameters increased when increased amounts of oilseeds were fed to Danish Jerseys. For both breeds, milk protein content decreased when increased amounts of oilseeds were fed. The milk fatty acid composition showed higher concentrations of saturated fatty acids and lower concentrations of unsaturated fatty acids in milk fat from Danish Jerseys compared with Danish Holsteins. Increased amounts of oilseeds in feed increased milk fat concentration of all C18 fatty acids except C18:2 n-6, whereas the content of C6 to C14, C11 to C17, and in particular, C16, decreased. This effect was more pronounced for Danish Holsteins than for Danish Jerseys. The apparent recovery of C18:2 n-6 and C18:3 n-3 decreased when increased amounts of oilseeds were fed; however, this was most likely due to increased amounts of fatty acid from feed used for other energy demands than milk production. It was concluded that up to 6.8% of oilseed supplementation can be fed without production problems and, in many cases, with positive production responses, including an improved milk fatty acid profile.     

The effect of crowding stress on bacterial growth and sensory properties of chilled Atlantic salmon fillets

Abstract: Atlantic salmon were subjected to minimal preslaughter crowding stress (Control), short‐term crowding for 20 min (SS‐group), or long‐term crowding for 24 h (LS‐group). The fish were filleted prerigor, cut into 270 g pieces, and packaged in modified atmosphere (60% CO₂ and 40% N₂). Fillet quality analyses were determined during 22 d of storage at 0.3 °C. Bacterial growth and unpleasant sensory properties increased earlier in the LS‐group. The negative effects of long‐term preslaughter stress were more pronounced for raw than cooked samples, and more pronounced for odor than flavor. Sequence analyses of bacterial DNA at the end of storage revealed that 100% of the bacteria were comprised by Photobacterium phosphoreum of the SS‐ and LS‐group, whereas the Control group also contained 21% of Carnobacterium maltaromaticum (lactic acid bacteria, LAB). Counting of LAB, using Man‐Rogosa‐Sharke agar, similarly showed higher numbers of the Control group after 15 d of storage. A total bacterial count of log 6 CFU/g was observed after 15 d of storage of the LS‐group, which was 3 and 7 d earlier compared with the Control and SS‐group, respectively. Fillet color, texture, and liquid losses were not negatively affected by preslaughter crowding stress. From the sensory and bacterial analyses, it is concluded that long‐term crowding stress accelerates bacterial growth and development of unpleasant sensory properties, hence reduces the shelf life of prerigor modified atmosphere packaged (MAP) salmon. Practical Application: Stressful handling of Atlantic salmon before slaughter resulted in faster reduction of fresh taste and smell, faster bacterial growth, and hence shorter shelf life. The deteriorative effects were more pronounced of raw compared to cooked salmon. Therefore, salmon should be handled carefully in connection with slaughter to avoid impaired welfare and fillet quality, in particularly for fish that is consumed raw, such as sushi.     

The diarylprolinol silyl ether system: a general organocatalyst

The past few decades have witnessed some of the most important and revolutionizing advances in the field of asymmetric catalysis. Chemists no longer rely solely on natural sources as the starting point of their synthetic strategy, as in chiral pool or auxiliary-based synthesis. Instead, naturally occurring chiral motifs are selected and, either unchanged or after modification, used in substoichiometric amounts as chiral catalysts or ligands. In this way, they effectively transfer their chirality to prochiral substrates, thereby rapidly amplifying and diversifying the arsenal of useful chiral building blocks available to the synthetic community. A long-standing goal in the pursuit of new catalytic systems is the discovery of general catalysts. Ideally, such catalytic systems should be capable of promoting a large number of enantioselective reactions, via multiple modes of activation, with good substrate tolerance and high stereoselectivity. In this Account, we describe the synthetic usefulness, efficiency, selectivity, and robustness of the diarylprolinol silyl ether system as the catalyst in various reactions of aldehydes. Based on the diarylprolinol silyl ether system, several studies on enamine-mediated transformations of saturated aldehydes have resulted in the introduction of different functionalities into the α-position of aldehydes in a highly stereoselective manner. This HOMO-activation concept was later extended to include α,β-unsaturated aldehydes, which after condensation with the aminocatalyst generate a dienamine species capable of undergoing stereoselective Diels-Alder-type reactions. As a result, the effective functionalization of the γ-position of the aldehyde is achieved. Recently, the activation principle was further developed to include 2,4-dienals, which form trienamine intermediates upon condensation with the aminocatalyst. The trienamines effectively react with carbon-centered dienophiles, forming aldehyde products having up to four contiguous stereocenters. Because of the concerted nature of the reaction and the efficient catalyst shielding of the β-position, the stereoinduction is achieved at the remote ε-position of the original aldehyde. Complementary to the enamine-mediated activations, α,β-unsaturated aldehydes can also be efficiently functionalized by applying the diarylprolinol silyl ether system via conjugate addition through iminium-ion-mediated processes, that is, LUMO-activation. In such reactions, the aminocatalyst not only effectively shields one of the enantiotopic faces of the enal, it also ensures excellent chemoselectivity, affording 1,4-adducts as the only products. Several different carbon and heteroatom nucleophiles can be added in a highly stereoselective fashion. The ability of the catalysts to participate in various enamine- and iminium-ion-mediated processes also makes them ideal for the sequential addition of nucleophiles and electrophiles in a cascade manner. These cascade reactions thereby afford access to products having at least two stereocenters. In the years to come, the diarylprolinol silyl ether catalysts will probably maintain their prominent position as general catalysts in the field of aminocatalysis. Moreover, recent efforts devoted to mechanistic studies might soon engender further advances with this versatile catalytic system, particularly in the areas of activation modes, catalyst loadings, and industrial applications.     

Dietary Supplementation with 22-<Emphasis Type="Italic">S</Emphasis>-Hydroxycholesterol to Rats Reduces Body Weight Gain and the Accumulation of Liver Triacylglycerol

This study explores the pharmacokinetics of 22-S-hydroxycholesterol (22SHC) in vivo in rats. We also carried out a metabolic study to explore whether the beneficial effects observed of 22SHC on glucose and lipid metabolism in vitro could be seen in vivo in rats. In the pharmacokinetic study, rats were given 50 mg/kg of [³H]22-S-hydroxycholesterol before absorption, distribution and excretion were monitored. In the metabolic study, the effect of 22SHC (30 mg/kg/day for 3 weeks) in rats on body weight gain [chow and high-fat diet (HFD)], serum lipids triacylglycerol (TAG) content and gene expression in liver and skeletal muscle were examined. Results showed that 22SHC was well absorbed after oral administration and distributed to most organs and mainly excreted in feces. Rats receiving 22SHC gained less body weight than their controls regardless whether the animals received chow diet or HFD. Moreover, we observed that animals receiving HFD had elevated levels of serum TAG while this was not observed for animals on HFD supplemented with 22SHC. The amount of TAG in liver was reduced after 22SHC treatment in animals receiving either chow diet or HFD. Gene expression analysis revealed that two genes (carnitine palmitoyltransferase 2 and uncoupling protein 3) involved in fatty acid oxidation and energy dissipation were increased in liver. Ucp3 expression (both protein and mRNA level) was increased in skeletal muscle, but insulin-stimulated glucose uptake and TAG content were unchanged. In conclusion, 22SHC seems to be an interesting model substance in the search of treatments for disorders involving aberrations in lipid metabolism.     

Synthesis and characterizations of poly(ethylene-co-vinylalcohol)-grafted-poly(3-hydroxybutyrate-co-hydroxyvalerate) copolymers

Poly(ethylene-co-vinylalcohol)-grafted-poly(3-hydroxybutyrate-co-hydroxyvalerate) (EVOH-g-PHBV) was prepared by a catalyzed grafting of PHBV onto immiscible EVOH. These reactions were performed at high temperature in the molten state. The choices of Tin(II) bis(2-ethylhexanoate) (Sn(Oct)₂) and 1,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD), as catalyst, were justified by a first study in an internal mixer. The catalyst quantity, reaction temperature and reaction time were optimized to apply them in the conditions of a reactive extrusion process with a co-rotating twin screw extruder. High reaction temperature, from 180 °C to 220 °C, associated to intensive mixing led to efficient grafting of PHBV onto EVOH, compatible with short residence times required.Rheological, thermal and morphological analyses were conducted to characterize the obtained copolymers. Molecular weights were determined by SEC. SEM imaging were made on cryo-fractured surfaces of blends extruded with and without catalyst. In most of reaction conditions, a compatible blend was obtained with a fine micro phase separation. Grafted copolymers were only obtained when well defined and controlled conditions are applied.     

Structural and rheological investigation of interphase in polyethylene/polyamide/nanoclay ternary blends

This study aims at investigating and characterizing the interphase in Polyethylene (PE)/Polyamide (PA) blends with nodular morphology, filled with organically modified Montmorillonite (C30B), using structural and rheological experimental techniques. PE/PA/C30B blends have been prepared by simultaneous mixing at a dispersed phase fraction (PE or PA) of 20% and a clay fraction ranging from 1 to 6%. Structural properties of the interphase have been investigated using XRD combined with TEM micrographs. The presence of numerous interphase defects is evidenced, and the effect of interphase disorder is discussed. Linear viscoelastic properties show the contribution of the interphase in PE matrix ternary blends at all clay fractions, whereas interphase effects are masked by the contribution of dispersed nanoclay particles in PA matrix ternary blends.