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Sample records for acid unsaturation numbers

  1. Iridium-catalyzed enantioselective hydrogenation of unsaturated heterocyclic acids.

    PubMed

    Song, Song; Zhu, Shou-Fei; Pu, Liu-Yang; Zhou, Qi-Lin

    2013-06-01

    Spiral binding: A highly enantioselective hydrogenation of unsaturated heterocyclic acids has been developed by using chiral iridium/spirophosphino oxazoline catalysts (see scheme; BArF(-) =tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, Boc=tert-butoxycarbonyl). This reaction provided an efficient method for the preparation of optically active heterocyclic acids with excellent enantioselectivities. PMID:23610004

  2. Preparation of .alpha.,.beta.-unsaturated carboxylic acids and esters

    DOEpatents

    Gogate, Makarand Ratnakar; Spivey, James Jerry; Zoeller, Joseph Robert

    1998-01-01

    Disclosed is a process for the preparation of .alpha.,.beta.-unsaturated carboxylic acids and esters thereof which comprises contacting formaldehyde or a source of formaldehyde with a carboxylic acid, ester or anhydride in the presence of a catalyst comprising an oxide of niobium.

  3. Preparation of {alpha},{beta}-unsaturated carboxylic acids and esters

    DOEpatents

    Gogate, M.R.; Spivey, J.J.; Zoeller, J.R.

    1998-09-15

    Disclosed is a process for the preparation of {alpha},{beta}-unsaturated carboxylic acids and esters thereof which comprises contacting formaldehyde or a source of formaldehyde with a carboxylic acid, ester or anhydride in the presence of a catalyst comprising an oxide of niobium.

  4. Bio-olefins from unsaturated fatty acids via tandem catalysis

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A new catalytic route to bio-olefins from unsaturated fatty acids will be described. At the heart of the process, the catalyst apparently functions in a tandem mode by both dynamically isomerizing the positions of double bonds in an aliphatic chain and, subsequently, decarboxylating specific isomers...

  5. Preparation of {alpha}, {beta}-unsaturated carboxylic acids and anhydrides

    DOEpatents

    Spivey, J.J.; Gogate, M.R.; Zoeller, J.R.; Tustin, G.C.

    1998-01-20

    Disclosed is a process for the preparation of {alpha},{beta}-unsaturated carboxylic acids and anhydrides thereof which comprises contacting formaldehyde or a source of formaldehyde with a carboxylic anhydride in the presence of a catalyst comprising mixed oxides of vanadium, phosphorus and, optionally, a third component selected from titanium, aluminum or, preferably silicon.

  6. Preparation of .alpha., .beta.-unsaturated carboxylic acids and anhydrides

    DOEpatents

    Spivey, James Jerry; Gogate, Makarand Ratnakav; Zoeller, Joseph Robert; Tustin, Gerald Charles

    1998-01-01

    Disclosed is a process for the preparation of .alpha.,.beta.-unsaturated carboxylic acids and anhydrides thereof which comprises contacting formaldehyde or a source of formaldehyde with a carboxylic anhydride in the presence of a catalyst comprising mixed oxides of vanadium, phosphorus and, optionally, a third component selected from titanium, aluminum or, preferably silicon.

  7. Stereoselective synthesis of unsaturated α-amino acids.

    PubMed

    Fanelli, Roberto; Jeanne-Julien, Louis; René, Adeline; Martinez, Jean; Cavelier, Florine

    2015-06-01

    Stereoselective synthesis of unsaturated α-amino acids was performed by asymmetric alkylation. Two methods were investigated and their enantiomeric excess measured and compared. The first route consisted of an enantioselective approach induced by the Corey-Lygo catalyst under chiral phase transfer conditions while the second one involved the hydroxypinanone chiral auxiliary, both implicating Schiff bases as substrate. In all cases, the use of a prochiral Schiff base gave higher enantiomeric excess and yield in the final desired amino acid. PMID:25715756

  8. Comparative Adsorption of Saturated and Unsaturated Fatty Acids at the Iron Oxide/Oil Interface.

    PubMed

    Wood, Mary H; Casford, M T; Steitz, R; Zarbakhsh, A; Welbourn, R J L; Clarke, Stuart M

    2016-01-19

    A detailed comparison of the adsorption behavior of long straight chain saturated and unsaturated fatty acids at the iron oxide/oil interface has been considered using a combination of surface study techniques. Both depletion isotherms and polarized neutron reflectometry (PNR) show that the extent of adsorption decreases as the number of double bonds in the alkyl chains increases. Sum frequency generation spectroscopic measurements demonstrate that there is also an increase in chain disorder within the adsorbed layer as the unsaturation increases. However, for the unsaturated analogues, a decrease in peak intensity is seen for the double bond peak upon heating, which is thought to arise from isomerization in the surface-bound layer. The PNR study of oleic acid adsorption indicates chemisorbed monolayer adsorption, with a further diffuse reversible adsorbed layer formed at higher concentrations. PMID:26707597

  9. Growth of group IV mycobacteria on medium containing various saturated and unsaturated fatty acids.

    PubMed Central

    Saito, H; Tomioka, H; Yoneyama, T

    1984-01-01

    Seventy-one strains of 15 species of rapidly growing mycobacteria were studied for their susceptibilities to fatty acids with 2 to 20 carbons by the agar dilution method at pH 7.0. Most mycobacteria other than potential pathogens (Mycobacterium fortuitum and Mycobacterium chelonei) were resistant to saturated fatty acids, except for lauric acid (C12:0) (MIC, 6.25 to 25 micrograms/ml) and capric acid (C10:0) (MIC, 50 to 100 micrograms#ml). M. fortuitum and M. chelonei were substantially insusceptible to these fatty acids. Unsaturated fatty acids with 16 to 20 carbons, except for C20:5, were highly toxic to group IV mycobacteria other than M. fortuitum, M. chelonei, Mycobacterium smegmatis, and Mycobacterium phlei, these being highly resistant to all the unsaturated acids, except for C16:1, C18:3, and C20:5. Introduction of double bonds to C16 to C20 fatty acids caused a marked increase in their activities that depended on the increase in the number of double bonds, at least up to three or four. M. fortuitum and M. chelonei were more resistant to the unsaturated fatty acids (particularly to C20:3 and C20:4) than the other group IV mycobacteria. PMID:6486760

  10. Modulatory effects of unsaturated fatty acids on the binding of glucocorticoids to rat liver glucocorticoid receptors.

    PubMed

    Vallette, G; Vanet, A; Sumida, C; Nunez, E A

    1991-09-01

    Binding of the synthetic glucocorticoid dexamethasone to the rat liver cytosol glucocorticoid receptor was inhibited by physiological concentrations of nonesterified fatty acids as a function of increasing dose, degree of unsaturation, and chain length of the fatty acid. Polyunsaturated fatty acids were the most potent inhibitors. Scatchard analysis and Line-weaver-Burk plots of the binding data revealed that both the association constants and number of binding sites decreased and that polyunsaturated fatty acids inhibition was of a mixed non-competitive type. The dissociation rate constant of [3H]dexamethasone from glucocorticoid receptors was increased by up to 10 times in the presence of docosahexaenoic acid, whereas a competitive inhibitor like the glucocorticoid antagonist RU 38486 had no effect. Moreover, sucrose density gradient analysis showed that docosahexaenoic acid inhibited the binding of [3H] dexamethasone to both the 8.8S and 4S forms. The results strongly suggest that unsaturated fatty acids are interacting at a site on the receptor different from the hormone binding site and the heat shock protein and that by binding to a second site unsaturated fatty acids greatly change the conformation of the hormone binding site to reduce its affinity for the hormone, either partially or completely depending on the concentration and the class of the fatty acid. PMID:1874175

  11. Metabolic Fate of Unsaturated Glucuronic/Iduronic Acids from Glycosaminoglycans

    PubMed Central

    Maruyama, Yukie; Oiki, Sayoko; Takase, Ryuichi; Mikami, Bunzo; Murata, Kousaku; Hashimoto, Wataru

    2015-01-01

    Glycosaminoglycans in mammalian extracellular matrices are degraded to their constituents, unsaturated uronic (glucuronic/iduronic) acids and amino sugars, through successive reactions of bacterial polysaccharide lyase and unsaturated glucuronyl hydrolase. Genes coding for glycosaminoglycan-acting lyase, unsaturated glucuronyl hydrolase, and the phosphotransferase system are assembled into a cluster in the genome of pathogenic bacteria, such as streptococci and clostridia. Here, we studied the streptococcal metabolic pathway of unsaturated uronic acids and the structure/function relationship of its relevant isomerase and dehydrogenase. Two proteins (gbs1892 and gbs1891) of Streptococcus agalactiae strain NEM316 were overexpressed in Escherichia coli, purified, and characterized. 4-Deoxy-l-threo-5-hexosulose-uronate (Dhu) nonenzymatically generated from unsaturated uronic acids was converted to 2-keto-3-deoxy-d-gluconate via 3-deoxy-d-glycero-2,5-hexodiulosonate through successive reactions of gbs1892 isomerase (DhuI) and gbs1891 NADH-dependent reductase/dehydrogenase (DhuD). DhuI and DhuD enzymatically corresponded to 4-deoxy-l-threo-5-hexosulose-uronate ketol-isomerase (KduI) and 2-keto-3-deoxy-d-gluconate dehydrogenase (KduD), respectively, involved in pectin metabolism, although no or low sequence identity was observed between DhuI and KduI or between DhuD and KduD, respectively. Genes for DhuI and DhuD were found to be included in the streptococcal genetic cluster, whereas KduI and KduD are encoded in clostridia. Tertiary and quaternary structures of DhuI and DhuD were determined by x-ray crystallography. Distinct from KduI β-barrels, DhuI adopts an α/β/α-barrel structure as a basic scaffold similar to that of ribose 5-phosphate isomerase. The structure of DhuD is unable to accommodate the substrate/cofactor, suggesting that conformational changes are essential to trigger enzyme catalysis. This is the first report on the bacterial metabolism of

  12. Effects of high pressure on unsaturated fatty acids

    NASA Astrophysics Data System (ADS)

    Povedano, Isabel; Guignon, Bérengère; Montoro, Óscar R.; Sanz, Pedro D.; Taravillo, Mercedes; Baonza, Valentín G.

    2014-10-01

    The objective of this study is to investigate the effects of high pressure processing on the molecular structure of some unsaturated fatty acids. Samples of elaidic acid, linoleic acid, ZE and EE conjugated linoleic acid are treated at 293 or 333 K at pressures up to 700 MPa. It is observed that the adiabatic heat generated from compression is able to bring the sample temperature above 373 K after 700 MPa. These relatively extreme conditions are of great interest for food sterilization, but they may induce undesirable change in fatty acid quality characteristics. To check for structural changes, Raman spectra of the samples are analysed after treatments. The comparison with Raman spectra of samples kept at atmospheric pressure shows that pressure induces some conformational changes at the hydrocarbon skeleton in solid samples, while the liquid ones remain unchanged. No cis/trans isomerization occurs, but gauche conformers are likely to be present.

  13. Unsaturated fatty acids supplementation reduces blood lead level in rats.

    PubMed

    Skoczyńska, Anna; Wojakowska, Anna; Nowacki, Dorian; Bobak, Łukasz; Turczyn, Barbara; Smyk, Beata; Szuba, Andrzej; Trziszka, Tadeusz

    2015-01-01

    Some dietary factors could inhibit lead toxicity. The aim of this study was to evaluate the effect of dietary compounds rich in unsaturated fatty acids (FA) on blood lead level, lipid metabolism, and vascular reactivity in rats. Serum metallothionein and organs' lead level were evaluated with the aim of assessing the possible mechanism of unsaturated FA impact on blood lead level. For three months, male Wistar rats that were receiving drinking water with (100 ppm Pb) or without lead acetate were supplemented per os daily with virgin olive oil or linseed oil (0.2 mL/kg b.w.) or egg derived lecithin fraction: "super lecithin" (50 g/kg b.w.). Mesenteric artery was stimulated ex vivo by norepinephrine (NE) administered at six different doses. Lecithin supplementation slightly reduced pressor responses of artery to NE. Lead administered to rats attenuated the beneficial effect of unsaturated FA on lipid metabolism and vascular reactivity to adrenergic stimulation. On the other hand, the super lecithin and linseed oil that were characterized by low omega-6 to omega-3 ratio (about 1) reduced the blood lead concentration. This effect was observed in lead poisoned rats (p < 0.0001) and also in rats nonpoisoned with lead (p < 0.05). PMID:26075218

  14. Unsaturated Fatty Acids Supplementation Reduces Blood Lead Level in Rats

    PubMed Central

    Skoczyńska, Anna; Wojakowska, Anna; Nowacki, Dorian; Bobak, Łukasz; Turczyn, Barbara; Smyk, Beata; Szuba, Andrzej; Trziszka, Tadeusz

    2015-01-01

    Some dietary factors could inhibit lead toxicity. The aim of this study was to evaluate the effect of dietary compounds rich in unsaturated fatty acids (FA) on blood lead level, lipid metabolism, and vascular reactivity in rats. Serum metallothionein and organs' lead level were evaluated with the aim of assessing the possible mechanism of unsaturated FA impact on blood lead level. For three months, male Wistar rats that were receiving drinking water with (100 ppm Pb) or without lead acetate were supplemented per os daily with virgin olive oil or linseed oil (0.2 mL/kg b.w.) or egg derived lecithin fraction: “super lecithin” (50 g/kg b.w.). Mesenteric artery was stimulated ex vivo by norepinephrine (NE) administered at six different doses. Lecithin supplementation slightly reduced pressor responses of artery to NE. Lead administered to rats attenuated the beneficial effect of unsaturated FA on lipid metabolism and vascular reactivity to adrenergic stimulation. On the other hand, the super lecithin and linseed oil that were characterized by low omega-6 to omega-3 ratio (about 1) reduced the blood lead concentration. This effect was observed in lead poisoned rats (p < 0.0001) and also in rats nonpoisoned with lead (p < 0.05). PMID:26075218

  15. Distinctive roles of unsaturated and saturated fatty acids in hyperlipidemic pancreatitis

    PubMed Central

    Chang, Yu-Ting; Chang, Ming-Chu; Tung, Chien-Chih; Wei, Shu-Chen; Wong, Jau-Min

    2015-01-01

    AIM: To investigate how the saturated and unsaturated fatty acid composition influences the susceptibility of developing acute pancreatitis. METHODS: Primary pancreatic acinar cells were treated with low and high concentrations of different saturated and unsaturated fatty acids, and changes in the cytosolic Ca2+ signal and the expression of protein kinase C (PKC) were measured after treatment. RESULTS: Unsaturated fatty acids at high concentrations, including oleic acid, linoleic acid, palmitoleic acid, docosahexaenoic acid, and arachidonic acid, induced a persistent rise in cytosolic Ca2+ concentrations in acinar cells. Unsaturated fatty acids at low concentrations and saturated fatty acids, including palmitic acid, stearic acid, and triglycerides, at low and high concentrations were unable to induce a rise in Ca2+ concentrations in acinar cells. Unsaturated fatty acids at high concentrations but not saturated fatty acids induced intra-acinar cell trypsin activation and cell damage and increased PKC expression. CONCLUSION: At sufficiently high concentrations, unsaturated fatty acids were able to induce acinar cells injury and promote the development of pancreatitis. Unsaturated fatty acids may play a distinctive role in the pathogenesis of pancreatitis through the activation of PKC family members. PMID:26327761

  16. Two Dimensional Polyamides Prepared From Unsaturated Carboxylic Acids And Amines.

    DOEpatents

    McDonald, William F.; Huang, Zhi Heng; Wright, Stacy C.; Danzig, Morris; Taylor, Andrew C.

    2002-07-17

    A polyamide and a process for preparing the polyamide are disclosed. The process comprises reacting in a reaction mixture a monomer selected from unsaturated carboxylic acids, esters of unsaturated carboxylic acids, anhydrides of unsaturated carboxylic acids, and mixtures thereof, and a first amine to form an intermediate reaction product in the reaction mixture, wherein the first amine is selected from RR.sub.1 NH, RNH.sub.2, RR.sub.1 NH.sub.2.sup.+, RNH.sub.3.sup.+ and mixtures thereof, wherein R and R.sub.1 can be the same or different and each contain between about 1 and 50 carbon atoms and are optionally substituted with heteroatoms oxygen, nitrogen, sulfur, and phosphorus and combinations thereof, and reacting the intermediate reaction product and a second amine to form a polyamide, wherein the second amine is selected from R.sub.2 R.sub.3 NH, R.sub.2 NH.sub.2, R.sub.2 R.sub.3 NH.sub.2.sup.+, R.sub.2 NH.sub.3.sup.+ and mixtures thereof wherein R.sub.2 and R.sub.3 can be the same or different and each contain between about 1 and 50 carbon atoms and are optionally substituted with heteroatoms oxygen, nitrogen, sulfur, and phosphorus and combinations thereof, wherein multiple of the R, R.sub.1, R.sub.2, and R.sub.3 are in vertically aligned spaced relationship along a backbone formed by the polyamide. In one version of the invention, the monomer is selected from maleic anhydride, maleic acid esters, and mixtures thereof. In another version of the invention, the first amine is an alkylamine, such as tetradecylamine, and the second amine is a polyalkylene polyamine, such as pentaethylenehexamine. In yet another version of the invention, the first amine and the second amine are olefinic or acetylenic amines, such as the reaction products of an alkyldiamine and an acetylenic carboxylic acid. The first amine and the second amine may be the same or different depending on the desired polyamide polymer structure.

  17. Effect of fatty acids on phase behavior of hydrated dipalmitoylphosphatidylcholine bilayer: saturated versus unsaturated fatty acids.

    PubMed

    Inoue, T; Yanagihara, S; Misono, Y; Suzuki, M

    2001-02-01

    The effect of some fatty acids on the phase behavior of hydrated dipalmitoylphosphatidylcholine (DPPC) bilayer was investigated with special interest in possible difference between saturated and unsaturated fatty acids. The phase behavior of hydrated DPPC bilayer was followed by a differential scanning calorimetry and a Fourier transform infrared spectroscopy. The addition of palmitic acid (PA) increased the bilayer phase transition temperature with the increase of the PA content in the mixture. In addition, DPPC molecules in gel phase bilayer became more rigid in the presence of PA compared with those in the absence of PA. This effect of PA on the phase behavior of hydrated DPPC bilayer is common to other saturated fatty acids, stearic acid, myristic acid, and also to unsaturated fatty acid with trans double bond, elaidic acid. Contrary to these fatty acids, oleic acid (OA), the unsaturated fatty acid with cis double bond in the acyl chain, exhibited quite different behavior. The effect of OA on the bilayer phase transition temperature was rather small, although a slight decrease in the temperature was appreciable. Furthermore, the IR spectral results demonstrated that the perturbing effect of OA on the gel phase bilayer of DPPC was quite small. These results mean that OA does not disturb the hydrated DPPC bilayer significantly. PMID:11269932

  18. Dietary unsaturated fatty acids differently affect catecholamine handling by adrenal chromaffin cells.

    PubMed

    Gomes, Andreia; Correia, Gustavo; Coelho, Marisa; Araújo, João Ricardo; Pinho, Maria João; Teixeira, Ana Luisa; Medeiros, Rui; Ribeiro, Laura

    2015-05-01

    Catecholamines (CA) play an important role in cardiovascular (CDV) disease risk. Namely, noradrenaline (NA) levels positively correlate whereas adrenaline (AD) levels negatively correlate with obesity and/or CDV disease. Western diets, which are tipically rich in Ω-6 fatty acids (FAs) and deficient in Ω-3 FAs, may contribute to the development of obesity, type 2 diabetes and/or coronary artery disease. Taking this into consideration and the fact that our group has already described that saturated FAs affect catecholamine handling by adrenal chromaffin cells, this work aimed to investigate the effect of unsaturated FAs upon catecholamine handling in the same model. Our results showed that chronic exposure to unsaturated FAs differently modulated CA cellular content and release, regardless of both FA series and number of carbon atoms. Namely, the Ω-6 arachidonic and linoleic acids, based on their effect on CA release and cellular content, seemed to impair NA and AD vesicular transport, whereas γ-linolenic acid selectively impaired AD synthesis and release. Within the Ω-9 FAs, oleic acid was devoid of effect, and elaidic acid behaved similarly to γ-linolenic acid. Eicosapentaenoic and docosahexaenoic acids (Ω-3 series) impaired the synthesis and release of both NA and AD. These results deserve attention and future development, namely, in what concerns the mechanisms involved and correlative effects in vivo. PMID:25727966

  19. C18-unsaturated branched-chain fatty acid isomers: characterization and physical properties

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Iso-oleic acid is a mixture of C18-unsaturated branched-chain fatty acid isomers with a methyl group on various positions of the alkyl chain, which is the product of the skeletal isomerization reaction of oleic acid and is the intermediate used to make isostearic acid (C18-saturated branched-chain f...

  20. Effect of Surfactants on Production of Oxygenated Unsaturated Fatty Acids by Bacillus megaterium ALA2

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Bacillus megaterium ALA2 (NRRL B-21660) produces many oxygenated unsaturated fatty acids from linoleic acid. Its major product, 12,13,17-trihydroxy-9(Z)-octadecenoic acid (12,13,17-THOA), inhibits the growth of some plant pathogenic fungi. Because hydrophobic fatty acids need to be evenly disperse...

  1. Sophorolipid-derived unsaturated and epoxy fatty acid estolides as plasticizers for poly(3-hydroxybutyrate)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Unsaturated and epoxy fatty acid estolides were synthesized from the omega and omega-1 hydroxy fatty acids derived from sophorolipids (SLs) prepared by fermentation from glucose:soybean oil and glucose:oleic acid, respectively. These estolides were utilized as additives in solution-cast poly(3-hydro...

  2. Impairment of NFkappaB activity by unsaturated fatty acids.

    PubMed

    Schumann, Julia; Fuhrmann, Herbert

    2010-08-01

    Using a luciferase reporter gene assay, we identified polyunsaturated fatty acids (PUFA) to impair NF kappaB signaling. Furthermore, we could demonstrate the PUFA ability to derogate NF kappaB activity to be independent from the family the fatty acid belongs to. Instead, we found a relation between the number of bis-allyl-methylene positions of the PUFA added and the NF kappaB activity of stimulated, long-term supplemented cells. The data presented provide new insights into the biological mechanisms PUFA exert their anti-inflammatory effects. Since suppression of NF kappaB activity could be of benefit in a number of inflammatory diseases as well as cancer, our findings are of clinical implication. According to our data dietary supplementation with PUFA-containing oils is likely to provide an at least palliative therapy for disorders linked to inappropriate NF kappaB signaling. PMID:20580946

  3. Residual mitochondrial transmembrane potential decreases unsaturated fatty acid level in sake yeast during alcoholic fermentation

    PubMed Central

    Sawada, Kazutaka

    2016-01-01

    Oxygen, a key nutrient in alcoholic fermentation, is rapidly depleted during this process. Several pathways of oxygen utilization have been reported in the yeast Saccharomyces cerevisiae during alcoholic fermentation, namely synthesis of unsaturated fatty acid, sterols and heme, and the mitochondrial electron transport chain. However, the interaction between these pathways has not been investigated. In this study, we showed that the major proportion of unsaturated fatty acids of ester-linked lipids in sake fermentation mash is derived from the sake yeast rather than from rice or koji (rice fermented with Aspergillus). Additionally, during alcoholic fermentation, inhibition of the residual mitochondrial activity of sake yeast increases the levels of unsaturated fatty acids of ester-linked lipids. These findings indicate that the residual activity of the mitochondrial electron transport chain reduces molecular oxygen levels and decreases the synthesis of unsaturated fatty acids, thereby increasing the synthesis of estery flavors by sake yeast. This is the first report of a novel link between residual mitochondrial transmembrane potential and the synthesis of unsaturated fatty acids by the brewery yeast during alcoholic fermentation. PMID:26839744

  4. Residual mitochondrial transmembrane potential decreases unsaturated fatty acid level in sake yeast during alcoholic fermentation.

    PubMed

    Sawada, Kazutaka; Kitagaki, Hiroshi

    2016-01-01

    Oxygen, a key nutrient in alcoholic fermentation, is rapidly depleted during this process. Several pathways of oxygen utilization have been reported in the yeast Saccharomyces cerevisiae during alcoholic fermentation, namely synthesis of unsaturated fatty acid, sterols and heme, and the mitochondrial electron transport chain. However, the interaction between these pathways has not been investigated. In this study, we showed that the major proportion of unsaturated fatty acids of ester-linked lipids in sake fermentation mash is derived from the sake yeast rather than from rice or koji (rice fermented with Aspergillus). Additionally, during alcoholic fermentation, inhibition of the residual mitochondrial activity of sake yeast increases the levels of unsaturated fatty acids of ester-linked lipids. These findings indicate that the residual activity of the mitochondrial electron transport chain reduces molecular oxygen levels and decreases the synthesis of unsaturated fatty acids, thereby increasing the synthesis of estery flavors by sake yeast. This is the first report of a novel link between residual mitochondrial transmembrane potential and the synthesis of unsaturated fatty acids by the brewery yeast during alcoholic fermentation. PMID:26839744

  5. α,β-Unsaturated monoterpene acid glucose esters: structural diversity, bioactivities and functional roles.

    PubMed

    Goodger, Jason Q D; Woodrow, Ian E

    2011-12-01

    The glycosylation of lipophilic small molecules produces many important plant secondary metabolites. The majority of these are O-glycosides with relatively fewer occurring as glucose esters of aromatic or aliphatic acids. In particular, monoterpene acid glucose esters have much lower structural diversity and distribution compared to monoterpene glycosides. Nevertheless, there have been over 20 monoterpene acid glucose esters described from trees in the genus Eucalyptus (Myrtaceae) in recent years, all based on oleuropeic acid, menthiafolic acid or both. Here we review all of the glucose esters containing these monoterpenoids identified in plants to date. Many of the compounds contain phenolic aglycones and all contain at least one α,β-unsaturated carbonyl, affording a number of important potential therapeutic reactivities such as anti-tumor promotion, carcinogenesis suppression, and anti-oxidant and anti-inflammatory activities. Additional properties such as cytotoxicity, bitterness, and repellency are suggestive of a role in plant defence, but we also discuss their localization to the exterior of foliar secretory cavity lumina, and suggest they may also protect secretory cells from toxic terpenes housed within these structures. Finally we discuss how the use of a recently developed protocol to isolate secretory cavities in a functional state could be used in conjunction with systems biology approaches to help characterize their biosynthesis and roles in plants. PMID:21945720

  6. Preparation of Saturated and Unsaturated Fatty Acid Hydrazides and Long Chain C-glycoside Ketohydrazones

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A method is described to prepare both saturated and unsaturated fatty acid acyl hydrazides using lipase as a catalyst. Hydrazides were generated from fatty acid methyl esters as well as directly from vegetable oils, and an organic co-solvent was not needed to maintain the integrity of the unsaturat...

  7. LIPID CLASS DISTRIBUTION OF HIGHLY UNSATURATED LONG CHAIN FATTY ACIDS IN MARINE DINOFLAGELLATES.

    EPA Science Inventory

    The very long chain highly unsaturated C28 fatty acids, octacosaheptaenoic [28:7(n-6)] and octacosaoctaenoic acid [28:8(n-3)], were found to be associated with phospholipids, obtained by fractionation of total lipid extracts into distinct lipid classes, in 4 and 6, respectively, ...

  8. Physicochemical aspects of inhibition of acid corrosion of metals by unsaturated organic compounds

    NASA Astrophysics Data System (ADS)

    Avdeev, Ya G.; Kuznetsov, Yurii I.

    2012-12-01

    The state-of-the-art in the development and improvement of methods for protecting metals from corrosion in mineral acid solutions using unsaturated organic compounds is considered. Characteristic features of the mechanism of their protective action on metal corrosion in acidic media are discussed. The bibliography includes 203 references.

  9. Aedes aegypti (Diptera: culicidae) biting deterrence: structure-activity relationship of saturated and unsaturated fatty acids

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In this study we systematically evaluated for the first time the biting deterrent effects of a series of saturated and unsaturated fatty acids against Aedes aegypti [yellow fever mosquito (Diptera: Culicidae)] using the K & D bioassay system (Klun et al 2005). The saturated fatty acids (C6:0 to C16...

  10. Phosphate limitation promotes unsaturated fatty acids and arachidonic acid biosynthesis by microalgae Porphyridium purpureum.

    PubMed

    Su, Gaomin; Jiao, Kailin; Li, Zheng; Guo, Xiaoyi; Chang, Jingyu; Ndikubwimana, Theoneste; Sun, Yong; Zeng, Xianhai; Lu, Yinghua; Lin, Lu

    2016-07-01

    Polyunsaturated fatty acids (PUFAs) are highly appreciated on their nutritive value for human health and aquaculture. P. purpureum, one of the red microalgae acknowledged as a promising accumulator of ARA, was chosen as the target algae in the present research. Effects of sodium bicarbonate (0.04-1.2 g/L), temperature (25, 30 and 33 °C) and phosphate (0.00-0.14 g/L) on biomass yield, total fatty acids (TFA) and arachidonic acid (ARA) accumulation were investigated systemically. NaHCO3 dose of 0.8 g/L and moderate temperature of 30 °C were preferred. In addition, TFA and ARA production were significantly enhanced by an appropriate concentration of phosphate, and the highest TFA yield of 666.38 mg/L and ARA yield of 159.74 mg/L were obtained at a phosphate concentration of 0.035 g/L. Interestingly, with phosphate concentration continuing to fall, UFA/TFA and ARA/EPA ratios were increased accordingly, suggesting that phosphate limitation promoted unsaturated fatty acids and arachidonic acid biosynthesis. Low concentration of phosphate may be favored to increase the enzymatic activities of ∆6-desaturase, which played a key role in catalyzing the conversion of C16:0 to C18:2, and thus the selectivity of UFA increased. Meanwhile, the increase of ARA selectivity could be attributed to ω6 pathway promotion and ∆17-desaturase activity inhibition with phosphate limitation. Phosphate limitation strategy enhanced unsaturated fatty acids and ARA biosynthesis in P. purpureum, and can be applied in commercial scale manufacturing and commercialization of ARA. PMID:27004948

  11. Stereoselective synthesis of (E)-trisubstituted alpha,beta-unsaturated amides and acids.

    PubMed

    Feuillet, Fred J P; Cheeseman, Matt; Mahon, Mary F; Bull, Steven D

    2005-08-21

    Potassium alkoxides of N-acyl-oxazolidin-2-one-syn-aldols undergo stereoselective elimination reactions to afford a range of trisubstituted (E)-alpha,beta-unsaturated amides in >95% de, that may be subsequently converted into their corresponding (E)-alpha,beta-unsaturated acids or (E)-alpha,beta-unsaturated oxazolines in good yield. syn-Aldols derived from alpha,beta-unsaturated aldehydes gave their corresponding trisubstituted (E)-alpha,beta-unsaturated-amides with poorer levels of diastereocontrol, whilst there was a similar loss in (E)-selectivity during elimination of syn-aldols derived from chiral aldehydes. These elimination reactions proceed via rearrangement of the potassium alkoxide of the syn-aldol to a 1,3-oxazinane-2,4-dione enolate intermediate that subsequently eliminates carbon dioxide to afford a trisubstituted (E)-alpha,beta-unsaturated amide. The (E)-selectivity observed during the E1cB-type elimination step has been rationalised using a simple conformational model that employs a chair-like transition state to explain the observed stereocontrol. PMID:16186928

  12. Differential roles of unsaturated and saturated fatty acids on autophagy and apoptosis in hepatocytes.

    PubMed

    Mei, Shuang; Ni, Hong-Min; Manley, Sharon; Bockus, Abigail; Kassel, Karen M; Luyendyk, James P; Copple, Bryan L; Ding, Wen-Xing

    2011-11-01

    Fatty acid-induced lipotoxicity plays a critical role in the pathogenesis of nonalcoholic liver disease. Saturated fatty acids and unsaturated fatty acids have differential effects on cell death and steatosis, but the mechanisms responsible for these differences are not known. Using cultured HepG2 cells and primary mouse hepatocytes, we found that unsaturated and saturated fatty acids differentially regulate autophagy and apoptosis. The unsaturated fatty acid, oleic acid, promoted the formation of triglyceride-enriched lipid droplets and induced autophagy but had a minimal effect on apoptosis. In contrast, the saturated fatty acid, palmitic acid, was poorly converted into triglyceride-enriched lipid droplets, suppressed autophagy, and significantly induced apoptosis. Subsequent studies revealed that palmitic acid-induced apoptosis suppressed autophagy by inducing caspase-dependent Beclin 1 cleavage, indicating cross-talk between apoptosis and autophagy. Moreover, our data suggest that the formation of triglyceride-enriched lipid droplets and induction of autophagy are protective mechanisms against fatty acid-induced lipotoxicity. In line with our in vitro findings, we found that high-fat diet-induced hepatic steatosis was associated with autophagy in the mouse liver. Potential modulation of autophagy may be a novel approach that has therapeutic benefits for obesity-induced steatosis and liver injury. PMID:21856859

  13. Redox-dependent anti-inflammatory signaling actions of unsaturated fatty acids.

    PubMed

    Delmastro-Greenwood, Meghan; Freeman, Bruce A; Wendell, Stacy Gelhaus

    2014-01-01

    Unsaturated fatty acids are metabolized to reactive products that can act as pro- or anti-inflammatory signaling mediators. Electrophilic fatty acid species, including nitro- and oxo-containing fatty acids, display salutary anti-inflammatory and metabolic actions. Electrophilicity can be conferred by both enzymatic and oxidative reactions, via the homolytic addition of nitrogen dioxide to a double bond or via the formation of α,β-unsaturated carbonyl and epoxide substituents. The endogenous formation of electrophilic fatty acids is significant and influenced by diet, metabolic, and inflammatory reactions. Transcriptional regulatory proteins and enzymes can sense the redox status of the surrounding environment upon electrophilic fatty acid adduction of functionally significant, nucleophilic cysteines. Through this covalent and often reversible posttranslational modification, gene expression and metabolic responses are induced. At low concentrations, the pleiotropic signaling actions that are regulated by these protein targets suggest that some classes of electrophilic lipids may be useful for treating metabolic and inflammatory diseases. PMID:24161076

  14. Redox-Dependent Anti-Inflammatory Signaling Actions of Unsaturated Fatty Acids

    PubMed Central

    Delmastro-Greenwood, Meghan; Freeman, Bruce A.; Wendell, Stacy Gelhaus

    2014-01-01

    Unsaturated fatty acids are metabolized to reactive products that can act as pro- or anti-inflammatory signaling mediators. Electrophilic fatty acid species, including nitro- and oxo-containing fatty acids, display salutary anti-inflammatory and metabolic actions. Electrophilicity can be conferred by both enzymatic and oxidative reactions, via the homolytic addition of nitrogen dioxide to a double bond or via the formation of α,β-unsaturated carbonyl and epoxide substituents. The endogenous formation of electrophilic fatty acids is significant and influenced by diet, metabolic, and inflammatory reactions. Transcriptional regulatory proteins and enzymes can sense the redox status of the surrounding environment upon electrophilic fatty acid adduction of functionally significant, nucleophilic cysteines. Through this covalent and often reversible posttranslational modification, gene expression and metabolic responses are induced. At low concentrations, the pleiotropic signaling actions that are regulated by these protein targets suggest that some classes of electrophilic lipids may be useful for treating metabolic and inflammatory diseases. PMID:24161076

  15. 4-(Dimethylamino)pyridine-catalysed iodolactonisation of γ,δ-unsaturated carboxylic acids.

    PubMed

    Meng, Chuisong; Liu, Zhihui; Liu, Yuxiu; Wang, Qingmin

    2015-06-28

    4-(Dimethylamino)pyridine functioned as an excellent catalyst for iodolactonisation reactions of γ,δ-unsaturated carboxylic acids, affording γ-lactones, δ-lactones, or both under neutral conditions at room temperature. The effects of substrate structures on the iodolactonisation were investigated, and a catalytic mechanism is proposed. PMID:26009007

  16. Conjugate hydrotrifluoromethylation of α,β-unsaturated acyl-oxazolidinones: synthesis of chiral fluorinated amino acids.

    PubMed

    Erdbrink, Holger; Peuser, Ilona; Gerling, Ulla I M; Lentz, Dieter; Koksch, Beate; Czekelius, Constantin

    2012-11-21

    A novel conjugate hydrofluoroalkylation of α,β-unsaturated acyl-oxazolidinones is described. Using this method, enantiomerically pure β-trifluoromethylated amino acids were prepared. Trifluorovaline and trifluoroisoleucine were incorporated into peptides and found to show extremely low α-helix propensities. PMID:23042408

  17. Regulation of the expression of key genes involved in HDL metabolism by unsaturated fatty acids

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The aim of this study was to determine the effects, and possible mechanisms of action, of unsaturated fatty acids on the expression of genes involved in HDL metabolism in HepG2 cells. The mRNA concentration of target genes was assessed by real time PCR. Protein concentrations were determined by wes...

  18. Higher Intakes of Antioxidants and Unsaturated Fatty Acid Reduce the Cardiac Autonomic Effects of Particles

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Higher intakes of antioxidants (vitamins C and E, carotene) found in foods such as cruciferous vegetables, and unsaturated fatty acids, including omega-3 from fish and monounsaturated fats from nuts and seeds, may prevent cardiovascular disease. We examined whether higher intake of such antioxidants...

  19. Organocatalytic enantioselective γ-aminoalkylation of unsaturated ester: access to pipecolic acid derivatives.

    PubMed

    Xu, Jianfeng; Jin, Zhichao; Chi, Yonggui Robin

    2013-10-01

    The direct γ-carbon functionalization of α,β-unsaturated esters via N-Heterocyclic Carbene (NHC) catalysis is disclosed. This catalytically generated nucleophilic γ-carbon undergoes highly enantioselective additions to hydrazones. The resulting δ-lactam products can be readily transformed to optically enriched pipecolic acid derivatives. PMID:24067098

  20. Terpolymers of ethyl acrylate/methacrylic acid/unsaturated acid ester of alcohols and acids as anti-settling agents in coal water slurries

    SciTech Connect

    Savoly, A.; Villa, J.L.; Grinstein, R.H.; Nachfolger, S.J.

    1988-05-17

    This patent describes a pumpable stabilized coal water slurry, having a coal content of at least about 50% by weight wherein at least 80% of the coal particles are about 200 mesh or finer, containing from about 0.01% to about 1% by weight of the slurry of a water soluble terpolymer of ethylacrylate (A), metacrylic acid (B) and a third monomer (C) selected from the group consisting of an unsaturated carboxylic acid ester of an alcohol and an ethoxylated carboxylic acid. The unsaturated carboxylic acid is a mono- or di- basic unsaturated carboxylic acid of 3 to 10 carbon atoms selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and maleic acid.

  1. Skin-Specific Unsaturated Fatty Acids Boost the Staphylococcus aureus Innate Immune Response

    PubMed Central

    Nguyen, Minh Thu; Hanzelmann, Dennis; Härtner, Thomas; Peschel, Andreas

    2015-01-01

    Antimicrobial fatty acids (AFAs) protect the human epidermis against invasion by pathogenic bacteria. In this study, we questioned whether human skin fatty acids (FAs) can be incorporated into the lipid moiety of lipoproteins and whether such incorporation would have an impact on innate immune stimulation in the model organism Staphylococcus aureus USA300 JE2. This organism synthesized only saturated FAs. However, when feeding USA300 with unsaturated FAs present on human skin (C16:1, C18:1, or C18:2), those were taken up, elongated stepwise by two carbon units, and finally found in the bacterial (phospho)lipid fraction. They were also observed in the lipid moiety of lipoproteins. When USA300 JE2 was fed with the unsaturated FAs, the cells and cell lysates showed an increased innate immune activation with various immune cells and peripheral blood mononuclear cells (PBMCs). Immune activation was highest with linoleic acid (C18:2). There are several pieces of evidence that the enhanced immune stimulating effect was due to the incorporation of unsaturated FAs in lipoproteins. First, the enhanced stimulation was dependent on Toll-like receptor 2 (TLR2). Second, an lgt mutant, unable to carry out lipidation of prolipoproteins, was unable to carry out immune stimulation when fed with unsaturated FAs. Third, the supplied FAs did not significantly affect growth, protein release, or expression of the model lipoprotein Lpl1. Although S. aureus is unable to synthesize unsaturated FAs, it incorporates long-chain unsaturated FAs into its lipoproteins, with the effect that the cells are better recognized by the innate immune system. This is an additional mechanism how our skin controls bacterial colonization and infection. PMID:26502910

  2. Skin-Specific Unsaturated Fatty Acids Boost the Staphylococcus aureus Innate Immune Response.

    PubMed

    Nguyen, Minh Thu; Hanzelmann, Dennis; Härtner, Thomas; Peschel, Andreas; Götz, Friedrich

    2016-01-01

    Antimicrobial fatty acids (AFAs) protect the human epidermis against invasion by pathogenic bacteria. In this study, we questioned whether human skin fatty acids (FAs) can be incorporated into the lipid moiety of lipoproteins and whether such incorporation would have an impact on innate immune stimulation in the model organism Staphylococcus aureus USA300 JE2. This organism synthesized only saturated FAs. However, when feeding USA300 with unsaturated FAs present on human skin (C16:1, C18:1, or C18:2), those were taken up, elongated stepwise by two carbon units, and finally found in the bacterial (phospho)lipid fraction. They were also observed in the lipid moiety of lipoproteins. When USA300 JE2 was fed with the unsaturated FAs, the cells and cell lysates showed an increased innate immune activation with various immune cells and peripheral blood mononuclear cells (PBMCs). Immune activation was highest with linoleic acid (C18:2). There are several pieces of evidence that the enhanced immune stimulating effect was due to the incorporation of unsaturated FAs in lipoproteins. First, the enhanced stimulation was dependent on Toll-like receptor 2 (TLR2). Second, an lgt mutant, unable to carry out lipidation of prolipoproteins, was unable to carry out immune stimulation when fed with unsaturated FAs. Third, the supplied FAs did not significantly affect growth, protein release, or expression of the model lipoprotein Lpl1. Although S. aureus is unable to synthesize unsaturated FAs, it incorporates long-chain unsaturated FAs into its lipoproteins, with the effect that the cells are better recognized by the innate immune system. This is an additional mechanism how our skin controls bacterial colonization and infection. PMID:26502910

  3. Functions of the Clostridium acetobutylicium FabF and FabZ proteins in unsaturated fatty acid biosynthesis

    PubMed Central

    2009-01-01

    Background The original anaerobic unsaturated fatty acid biosynthesis pathway proposed by Goldfine and Bloch was based on in vivo labeling studies in Clostridium butyricum ATCC 6015 (now C. beijerinckii) but to date no dedicated unsaturated fatty acid biosynthetic enzyme has been identified in Clostridia. C. acetobutylicium synthesizes the same species of unsaturated fatty acids as E. coli, but lacks all of the known unsaturated fatty acid synthetic genes identified in E. coli and other bacteria. A possible explanation was that two enzymes of saturated fatty acid synthesis of C. acetobutylicium, FabZ and FabF might also function in the unsaturated arm of the pathway (a FabZ homologue is known to be an unsaturated fatty acid synthetic enzyme in enterococci). Results We report that the FabF homologue located within the fatty acid biosynthetic gene cluster of C. acetobutylicium functions in synthesis of both unsaturated fatty acids and saturated fatty acids. Expression of this protein in E. coli functionally replaced both the FabB and FabF proteins of the host in vivo and replaced E. coli FabB in a defined in vitro fatty acid synthesis system. In contrast the single C. acetobutylicium FabZ homologue, although able to functionally replace E. coli FabZ in vivo and in vitro, was unable to replace FabA, the key dehydratase-isomerase of E. coli unsaturated fatty acid biosynthesis in vivo and lacked isomerase activity in vitro. Conclusion Thus, C. acetobutylicium introduces the double of unsaturated fatty acids by use of a novel and unknown enzyme. PMID:19493359

  4. The ratio of unsaturated fatty acids in biosurfactants affects the efficiency of gene transfection.

    PubMed

    Inoh, Yoshikazu; Furuno, Tadahide; Hirashima, Naohide; Kitamoto, Dai; Nakanishi, Mamoru

    2010-10-15

    An unsaturated hydrocarbon chain in phospholipid was reported to affect a phase transition and a fusogenic activity after mixing membranes, and consequently to achieve a high DNA transfection efficiency. We previously showed that a biosurfactant mannosylerythritol lipid-A (MEL-A) enhances the gene transfection efficiency of cationic liposomes. Here, we have studied the effects of unsaturated fatty acid ratio of MEL-A on the physicochemical properties and gene delivery into cells of cationic liposomes using MEL-A with three different unsaturated fatty acid ratios (9.1%, 21.5%, and 46.3%). The gene transfer efficiency of cationic liposomes containing MEL-A (21.5%) was much higher than that of those containing MEL-A (9.1%) and MEL-A (46.3%). MEL-A (21.5%)-containing cationic liposomes induced highly efficient membrane fusion after addition of anionic liposomes and led to subsequent DNA release. Imaging analysis revealed that MEL-A (21.5%)-containing liposomes fused with the plasma membrane and delivered DNA into the nucleus of NIH-3T3 cells, MEL-A (46.3%)-containing liposomes fused with the plasma membrane did not deliver DNA into the nucleus, and MEL-A (9.1%)-containing liposomes neither fused with the plasma membrane nor delivered DNA into the nucleus. Thus, it is understandable that the unsaturated fatty acid ratio of MEL-A strongly influences the gene transfection efficiency of cationic liposomes. PMID:20674726

  5. Reaction of /alpha/,/beta/-unsaturated acyl isothiocyanates with salts of dithiocarbamic acids

    SciTech Connect

    Krus, K.; Masias, A.; Beletskaya, I.P.

    1989-01-10

    The reaction of unsaturated isothiocyanates with the sodium and calcium salts of N-alkyl- and N,N-dialkyldithiocarbamic acids was studied. Depending on the structure of the dithiocarbamate, the reaction products are thiazines or acyl dithiocarbamates. For the salts of methyldithiocarbamic acid the effect of the concentration and the nature of the metal on the relative yields of 6-phenyl-3-methylpropiorhodanine and 6-phenylpropiorhodanine was studied. A method is proposed for the synthesis of 3-substituted propiorhodanines.

  6. A non-canonical caleosin from Arabidopsis efficiently epoxidizes physiological unsaturated fatty acids with complete stereoselectivity.

    PubMed

    Blée, Elizabeth; Flenet, Martine; Boachon, Benoît; Fauconnier, Marie-Laure

    2012-10-01

    In plants, epoxygenated fatty acids (EFAs) are constituents of oil seeds as well as defence molecules and components of biopolymers (cutin, suberin). While the pleiotropic biological activities of mammalian EFAs have been well documented, there is a paucity of information on the physiological relevance of plant EFAs and their biosynthesis. Potential candidates for EFA formation are caleosin-type peroxygenases which catalyze the epoxidation of unsaturated fatty acids in the presence of hydroperoxides as co-oxidants. However, the caleosins characterized so far, which are mostly localized in seeds, are poor epoxidases. In sharp contrast, quantitative RT-PCR analysis revealed that PXG4, a class II caleosin gene, is expressed in roots, stems, leaves and flowers of Arabidopsis. Expressed in yeast, PXG4 encodes a calcium-dependent membrane-associated hemoprotein able to catalyze typical peroxygenase reactions. Moreover, we show here that purified recombinant PXG4 is an efficient fatty acid epoxygenase, catalyzing the oxidation of cis double bonds of unsaturated fatty acids. Physiological linoleic and linolenic acids proved to be the preferred substrates for PXG4; they are oxidized into the different positional isomers of the monoepoxides and into diepoxides. An important regioselectivity was observed; the C-12,13 double bond of these unsaturated fatty acids being the least favored unsaturation epoxidized by PXG4, linolenic acid preferentially yielded the 9,10-15,16-diepoxide. Remarkably, PXG4 catalyzes exclusively the formation of (R),(S)-epoxide enantiomers, which is the absolute stereochemistry of the epoxides found in planta. These findings pave the way for the study of the functional role of EFAs and caleosins in plants. PMID:22913587

  7. Mechanism of biosynthesis of unsaturated fatty acids in Pseudomonas sp. strain E-3, a psychrotrophic bacterium

    SciTech Connect

    Wada, M.; Fukunaga, N.; Sasaki, S. )

    1989-08-01

    Biosynthesis of palmitic, palmitoleic, and cis-vaccenic acids in Pseudomonas sp. strain E-3 was investigated with in vitro and in vivo systems. (1-{sup 14}C)palmitic acid was aerobically converted to palmitoleate and cis-vaccenate, and the radioactivities on their carboxyl carbons were 100 and 43%, respectively, of the total radioactivity in the fatty acids. Palmitoyl coenzyme A desaturase activity was found in the membrane fraction. (1-{sup 14}C)stearic acid was converted to octadecenoate and C16 fatty acids. The octadecenoate contained oleate and cis-vaccenate, but only oleate was produced in the presence of cerulenin. (1-{sup 14}C)lauric acid was aerobically converted to palmitate, palmitoleate, and cis-vaccenate. Under anaerobic conditions, palmitate (62%), palmitoleate (4%), and cis-vaccenate (34%) were produced from (1-{sup 14}C)acetic acid, while they amounted to 48, 39, and 14%, respectively, under aerobic conditions. In these incorporation experiments, 3 to 19% of the added radioactivity was detected in released {sup 14}CO{sub 2}, indicating that part of the added fatty acids were oxidatively decomposed. Partially purified fatty acid synthetase produced saturated and unsaturated fatty acids with chain lengths of C10 to C18. These results indicated that both aerobic and anaerobic mechanisms for the synthesis of unsaturated fatty acid are operating in this bacterium.

  8. Growth of and mineral deposition in young rats fed saturated and unsaturated fatty acids

    SciTech Connect

    Magee, A.; D'Souza, D. John Hopkins Univ., Baltimore, MD )

    1991-03-15

    Male weanling rats were used in 4 week experiments to study effects of saturated and unsaturated fatty acids on growth and mineral deposition in several organs (bone, kidneys, liver, spleen, testes). Minerals evaluated were calcium, copper, iron, magnesium, manganese, phosphorus, and zinc, and levels of these minerals in tests diets were appropriate for growing rats. Two levels of dietary fat were used, and fatty acids included in the study were butyric/capronic, palmitic/stearic, oleic, and linoleic/linolenic acids. Decreased weight gains were observed in rats fed saturated fatty acids or 10% fat, while increases in weight gains were associated with increases in polyunsaturated/saturated (P/S) ratios. Copper, iron, or zinc levels tended to be higher in organs of rats fed saturated fatty acids. P/S ratios had no effect on copper or zinc deposition, but decreases in liver iron and increases in spleen iron were observed in rats fed the higher P/S ratios. Manganese levels were generally unaffected by fatty acid types, fat level, or P/S ratio, although liver manganese levels were higher in rats fed unsaturated fatty acids. Dietary fatty acids, fat level, or P/S ratios had no apparent effects on calcium, magnesium, phosphorus, or zinc deposition in femurs and tibias of rats.

  9. Expression of genes controlling unsaturated fatty acids biosynthesis and oil deposition in developing seeds of Sacha inchi (Plukenetia volubilis L.).

    PubMed

    Wang, Xiaojuan; Liu, Aizhong

    2014-10-01

    Sacha inchi (Plukenetia volubilis L., Euphorbiaceae) seed oil is rich in α-linolenic acid, a kind of n-3 fatty acids with many health benefits. To discover the mechanism underlying α-linolenic acid accumulation in sacha inchi seeds, preliminary research on sacha inchi seed development was carried out from one week after fertilization until maturity, focusing on phenology, oil content, and lipid profiles. The results suggested that the development of sacha inchi seeds from pollination to mature seed could be divided into three periods. In addition, investigations on the effect of temperature on sacha inchi seeds showed that total oil content decreased in the cool season, while unsaturated fatty acid and linolenic acid concentrations increased. In parallel, expression profiles of 17 unsaturated fatty acid related genes were characterized during seed development and the relationships between gene expression and lipid/unsaturated fatty acid accumulation were discussed. PMID:25119487

  10. Partial Hydrothermal Oxidation of High Molecular Weight Unsaturated Carboxylic Acids for Upgrading of Biodiesel Fuel

    NASA Astrophysics Data System (ADS)

    Kawasaki, K.; Jin, F.; Kishita, A.; Tohji, K.; Enomoto, H.

    2007-03-01

    With increasing environmental awareness and crude oil price, biodiesel fuel (BDF) is gaining recognition as a renewable fuel which may be used as an alternative diesel fuel without any modification to the engine. The cold flow and viscosity of BDF, however, is a major drawback that limited its use in cold area. In this study, therefore, we investigated that partial oxidation of high molecular weight unsaturated carboxylic acids in subcritical water, which major compositions in BDF, to upgrade biodiesel fuel. Oleic acid, (HOOC(CH2)7CH=CH(CH2)7CH3), was selected as a model compound of high molecular weight unsaturated carboxylic acids. All experiments were performed with a batch reactor made of SUS 316 with an internal volume of 5.7 cm3. Oleic acid was oxidized at 300 °C with oxygen supply varying from 1-10 %. Results showed that a large amount of carboxylic acids and aldehydes having 8-9 carbon atoms were formed. These experimental results suggest that the hydrothermal oxidative cleavage may mainly occur at double bonds and the cleavage of double bonds could improve the cold flow and viscosity of BDF.

  11. Identification of a Binding Site for Unsaturated Fatty Acids in the Orphan Nuclear Receptor Nurr1.

    PubMed

    de Vera, Ian Mitchelle S; Giri, Pankaj K; Munoz-Tello, Paola; Brust, Richard; Fuhrmann, Jakob; Matta-Camacho, Edna; Shang, Jinsai; Campbell, Sean; Wilson, Henry D; Granados, Juan; Gardner, William J; Creamer, Trevor P; Solt, Laura A; Kojetin, Douglas J

    2016-07-15

    Nurr1/NR4A2 is an orphan nuclear receptor, and currently there are no known natural ligands that bind Nurr1. A recent metabolomics study identified unsaturated fatty acids, including arachidonic acid and docosahexaenoic acid (DHA), that interact with the ligand-binding domain (LBD) of a related orphan receptor, Nur77/NR4A1. However, the binding location and whether these ligands bind other NR4A receptors were not defined. Here, we show that unsaturated fatty acids also interact with the Nurr1 LBD, and solution NMR spectroscopy reveals the binding epitope of DHA at its putative ligand-binding pocket. Biochemical assays reveal that DHA-bound Nurr1 interacts with high affinity with a peptide derived from PIASγ, a protein that interacts with Nurr1 in cellular extracts, and DHA also affects cellular Nurr1 transactivation. This work is the first structural report of a natural ligand binding to a canonical NR4A ligand-binding pocket and indicates a natural ligand can bind and affect Nurr1 function. PMID:27128111

  12. Effect of low temperature on highly unsaturated fatty acid biosynthesis in activated sludge.

    PubMed

    He, Su; Ding, Li-Li; Xu, Ke; Geng, Jin-Ju; Ren, Hong-Qiang

    2016-07-01

    Low temperature is a limiting factor for the microbial activity of activated sludge for sewage treatment plant in winter. Highly unsaturated fatty acid (UFA) biosynthesis, phospholipid fatty acid (PLFA) constituents and microbial structure in activated sludge at low temperature were investigated. Over 12 gigabases of metagenomic sequence data were generated with the Illumina HiSeq 2000 platform. The result showed 43.11% of phospholipid fatty acid (PLFA) in the activated sludge participated in UFA biosynthesis, and γ-Linolenic could be converted to Arachidonic acid at low temperature. The highly UFA biosynthesis in activated sludge was n-6 highly UFA biosynthesis, rather than n-3 highly UFA biosynthesis. The microbial community structures of activated sludge were analyzed by PLFA and high-throughput sequencing (HiSeq) simultaneously. Acidovorax, Pseudomonas, Flavobacterium and Polaromonas occupied higher percentage at 5°C, and genetic changes of highly UFA biosynthesis derived from microbial community structures change. PMID:27035483

  13. Biodegradation, sorption, and transport of 2,4-dichlorophenoxyacetic acid in saturated and unsaturated soils.

    PubMed Central

    Estrella, M R; Brusseau, M L; Maier, R S; Pepper, I L; Wierenga, P J; Miller, R M

    1993-01-01

    The fate of an organic contaminant in soil depends on many factors, including sorption, biodegradation, and transport. The herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) was used as a model compound to illustrate the impact of these interacting factors on the fate of an organic contaminant. Batch and column experiments performed with a sandy loam soil mixture under saturated and unsaturated conditions were used to determine the effects of sorption and biodegradation on the fate and transport of 2,4-D. Sorption of 2,4-D was found to have a slight but significant effect on transport of 2,4-D under saturated conditions (retardation factor, 1.8) and unsaturated conditions (retardation factor, 3.4). Biodegradation of 2,4-D was extensive under both batch and column conditions and was found to have a significant impact on 2,4-D transport in column experiments. In batch experiments, complete mineralization of 2,4-D (100 mg kg-1) occurred over a 4-day period following a 3-day lag phase under both saturated and unsaturated conditions. The biodegradation rate parameters calculated for batch experiments were found to be significantly different from those estimated for column experiments. PMID:8285717

  14. Retention behaviour of unsaturated fatty acid methyl esters on porous graphitic carbon.

    PubMed

    Gaudin, Karen; Chaminade, Pierre; Baillet, Arlette

    2004-01-01

    The eluotropic strength of binary mobile phases was calculated for three homologous series of cis, trans, and cis-cis unsaturated fatty acid methyl esters (FAMEs). Binary mobile phases with chloroform, dichloromethane, or tetrahydrofuran as strong solvent and methanol or acetonitrile as weak solvent were tested. The volume fraction of strong solvent in the binary phases was between 0.3 and 0.8. Curves of eluotropic strength versus volume fraction of strong solvents showed similar trends to previously published results for saturated homologues. Correlation coefficients of the plots of eluotropic strength values for saturated versus unsaturated FAMEs were close to 1.0. Therefore these similarities validate the model of eluotropic strength previously established with saturated FAMEs as relevant for unsaturated FAMEs. The separation factors between cis and trans homologues always showed elution of the cis before the trans homologue. The difference in retention is due primarily to the geometry of the molecule. The retention is lowered more by the addition of a first carbon double bond than by the addition of a second one, independently of the mobile phase composition. PMID:15335056

  15. Aedes aegypti (Diptera: Culicidae) biting deterrence: structure-activity relationship of saturated and unsaturated fatty acids.

    PubMed

    Ali, Abbas; Cantrell, Charles L; Bernier, Ulrich R; Duke, Stephen O; Schneider, John C; Agramonte, Natasha M; Khan, Ikhlas

    2012-11-01

    In this study we evaluated the biting deterrent effects of a series of saturated and unsaturated fatty acids against Aedes aegypti (L), yellow fever mosquito (Diptera: Culicidae) using the K & Dbioassay module system. Saturated (C6:0 to C16:0 and C18:0) and unsaturated fatty acids (C11:1 to C14:1, C16:1, C18:1, and C18:2) showed biting deterrence index (BDI) values significantly greater than ethanol, the negative control. Among the saturated fatty acids, mid chain length acids (C10:0 to C13:0) showed higher biting deterrence than short (C6:0 to C9:0) and long chain length acids (C14:0 to C18:0), except for C8:0 and C16:0 that were more active than the other short and long chain acids. The BDI values of mid chain length acids (C10:0 to C13:0) were not significantly less than N, N-diethyl-meta-toluamide (DEET), the positive control. Among the unsaturated fatty acids, C11:1 showed the highest activity (BDI = 1.05) and C18:2 had the lowest activity (BDI = 0.7). In C11:1, C12:1, and C14:1 BDI values were not significantly less than DEET. After the preliminary observations, residual activity bioassays were performed on C11:0, C12:0, C11:1, and C12:1 over a 24-h period. All the fatty acids (C11:0, C12:0, C11:1, and C12:1) and DEET showed significantly higher activity at all test intervals than the solvent control. At treatment and 1-h posttreatment, all fatty acids showed proportion not biting (PNB) values not significantly less than DEET. At 3-, 6-, and 12-h posttreatment, all fatty acids showed PNB values significantly greater than DEET. At 24-h posttreatment, only the PNB value for C12:0 was significantly higher than DEET. The dose-responses of C12:0 and DEET were determined at concentrations of 5-25 nmol/cm2. As in the residual activity bioassays, the PNB values for C12:0 and DEET at 25 nmol/cm(2) were not significantly different. However, at lower concentrations, the PNB values for C12:0 were significantly greater than DEET. These results clearly indicate that mid

  16. Synthesis of α,β-unsaturated esters via a chemo-enzymatic chain elongation approach by combining carboxylic acid reduction and Wittig reaction

    PubMed Central

    Duan, Yitao; Yao, Peiyuan; Du, Yuncheng; Feng, Jinhui

    2015-01-01

    Summary α,β-Unsaturated esters are versatile building blocks for organic synthesis and of significant importance for industrial applications. A great variety of synthetic methods have been developed, and quite a number of them use aldehydes as precursors. Herein we report a chemo-enzymatic chain elongation approach to access α,β-unsaturated esters by combining an enzymatic carboxylic acid reduction and Wittig reaction. Recently, we have found that Mycobacterium sp. was able to reduce phenylacetic acid (1a) to 2-phenyl-1-ethanol (1c) and two sequences in the Mycobacterium sp. genome had high identity with the carboxylic acid reductase (CAR) gene from Nocardia iowensis. These two putative CAR genes were cloned, overexpressed in E. coli and one of two proteins could reduce 1a. The recombinant CAR was purified and characterized. The enzyme exhibited high activity toward a variety of aromatic and aliphatic carboxylic acids, including ibuprofen. The Mycobacterium CAR catalyzed carboxylic acid reduction to give aldehydes, followed by a Wittig reaction to afford the products α,β-unsaturated esters with extension of two carbon atoms, demonstrating a new chemo-enzymatic method for the synthesis of these important compounds. PMID:26664647

  17. Isolation, identification and quantification of unsaturated fatty acids, amides, phenolic compounds and glycoalkaloids from potato peel.

    PubMed

    Wu, Zhi-Gang; Xu, Hai-Yan; Ma, Qiong; Cao, Ye; Ma, Jian-Nan; Ma, Chao-Mei

    2012-12-15

    Eleven compounds were isolated from potato peels and identified. Their structures were determined by interpretation of UV, MS, 1D, and 2D NMR spectral data and by comparison with reported data. The main components of the potato peels were found to be chlorogenic acid and other phenolic compounds, accompanied by 2 glycoalkaloids, 3 low-molecular-weight amide compounds, and 2 unsaturated fatty acids, including an omega-3 fatty acid. The potato peels showed more potent radical scavenging activity than the flesh. The quantification of the 11 components indicated that the potato peels contained a higher amount of phenolic compounds than the flesh. These results suggest that peel waste from the industry of potato chips and fries may be a source of useful compounds for human health. PMID:22980823

  18. Formation of cloud condensation nuclei by oxidative processing: Unsaturated fatty acids

    NASA Astrophysics Data System (ADS)

    Broekhuizen, Keith E.; Thornberry, Troy; Kumar, P. Pradeep; Abbatt, Jonathan P. D.

    2004-12-01

    The ability of submicron oleic acid and linoleic acid particles, or condensation nuclei (CN), to act as cloud condensation nuclei (CCN) has been investigated using a tandem differential mobility analyzer (TDMA) coupled to a flow tube reactor and a thermal gradient diffusion chamber (TGDC). The size change and CCN properties of pure oleic acid, mixed oleic acid/methanol, and pure linoleic acid particles have been investigated as a function of exposure to ozone. Pure oleic and linoleic acid particles were CCN inactive for all particle diameters (≤300 nm) and supersaturations (≤1%) studied. The mixed oleic acid/methanol particles, however, had a critical activation diameter of 188 nm for an experimental water supersaturation of 0.6%. Under low ozone exposures (<1 × 10-4 atm s), both the oleic acid and linoleic acid particles decreased in size. In particular, oleic acid particles lost 25% of their initial volume, consistent with the loss of nonanal, a volatile reaction product. However, no increase in CCN activity was observed at these exposures. Under conditions of much higher ozone exposure, e.g., 0.42 atm s, the pure oleic acid particles became CCN active, with a critical activation diameter of 161 nm at 0.6% supersaturation. CCN activity for the linoleic acid particles was never observed, even under these high ozone exposures not typically observed in the atmosphere. By contrast, the mixed oleic acid/methanol particles showed enhanced activation under atmospherically relevant ozone exposures (<1 × 10-4 atm s). These results suggest that the products of the ozone plus unsaturated fatty acid reaction do promote the CCN activity of the particles; however, the degree of activity is dependent on both the level of ozone exposure and the chemical nature of the particle. These results are the first to demonstrate that the CCN properties of pure organic aerosols can be modified through oxidative processing.

  19. Growth behavior of gold nanoparticles synthesized in unsaturated fatty acids by vacuum evaporation methods.

    PubMed

    Fujita, Akito; Matsumoto, Yusuke; Takeuchi, Mitsuaki; Ryuto, Hiromichi; Takaoka, Gikan H

    2016-02-21

    Physical vapor evaporation of metals on low vapor pressure liquids is a simple and clean method to synthesize nanoparticles and thin films, though only little work has been conducted so far. Here, gold nanoparticles were synthesized by vacuum evaporation (VE) methods in ricinoleic acid and oleic acid, two typical unsaturated fatty acids (UFAs). The two solvents formed black aggregates after deposition and then shrunk and finally disappeared with the progress of time. By transmission electron microscopy (TEM) images, nanoparticles in ricinoleic acids formed aggregates and then dispersed by time, while in oleic acid big aggregates were not observed in all timescales. From TEM images and small angle X-ray scattering (SAXS) measurements, the mean size of the nanoparticles was about 4 nm in both ricinoleic and oleic acids. UV-Vis spectra were also taken as a function of time and the results were consistent with the growth behavior presumed by TEM images. Air exposure had an influence on the behavior of the sample triggering the nanoparticle formation in both solvents. From control experiments, we discovered that oxygen gas triggered the phenomenon and nanoparticles function as a catalyst for the oxidation of the UFAs. It stimulates the phenomenon and in ricinoleic acid, specifically, electrons are transferred from riconleic acid to the gold nanoparticles, enhancing the surface potential of the nanoparticles and the repulsive force between their electronic double layers. PMID:26821883

  20. 40 CFR 180.1284 - Ammonium salts of higher fatty acids (C8-C18 saturated; C8-C12 unsaturated); exemption from the...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 24 2011-07-01 2011-07-01 false Ammonium salts of higher fatty acids... Ammonium salts of higher fatty acids (C8-C18 saturated; C8-C12 unsaturated); exemption from the requirement of a tolerance. Ammonium salts of C8-C18 saturated and C8-C12 unsaturated higher fatty acids...

  1. 40 CFR 180.1284 - Ammonium salts of higher fatty acids (C8-C18 saturated; C8-C12 unsaturated); exemption from the...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 23 2010-07-01 2010-07-01 false Ammonium salts of higher fatty acids... Ammonium salts of higher fatty acids (C8-C18 saturated; C8-C12 unsaturated); exemption from the requirement of a tolerance. Ammonium salts of C8-C18 saturated and C8-C12 unsaturated higher fatty acids...

  2. Reaction Products of Unsaturated Polycarboxylic Acids and Sodium Hypophosphite for Improved Flame Resistance of Cotton-Containing Materials

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Reaction products of unsaturated polycarboxylic acids and sodium hypophosite were found to improve flame resistance of cellulosic materials as determined by the 45 degree flammability test for apparel textiles. The most effective product was that from the reaction of maleic acid with sodium hypopho...

  3. Anaerobic biosynthesis of unsaturated fatty acids in the cyanobacterium, Oscillatoria limnetica

    NASA Technical Reports Server (NTRS)

    Jahnke, L. L.; Lee, B.; Sweeney, M. J.; Klein, H. P.

    1989-01-01

    The mechanism for synthesis of monounsaturated fatty acids under aerobic and anaerobic conditions was studied in the facultative anaerobic cyanobacterium, Oscillatoria limnetica. The hexadecenoic acid (C16:1) of aerobically grown O. limnetica was shown to contain both the delta 7 (79%) and delta 9 (21%) isomers, while the octadecenoic (C18:1) acid was entirely the delta 9 acid. Incorporation of [2-14C] acetate into the fatty acids under aerobic conditions resulted in synthesis of the delta 7 and delta 9 C16:1 and the delta 9 C18:1. Synthesis of unsaturated fatty acids in the presence of DCMU required sulfide. Anaerobic incubations in the presence of DCMU and sulfide (less than 0.003% atmospheric oxygen) resulted in a two-fold increase in monounsaturated fatty acids of both delta 7 and delta 9 C16:1 and delta 9 and delta 11 C18:1. The synthesis of these is characteristic of a bacterial-type, anaerobic pathway.

  4. Process for the generation of .alpha., .beta.-unsaturated carboxylic acids and esters using niobium catalyst

    DOEpatents

    Gogate, Makarand Ratnakav; Spivey, James Jerome; Zoeller, Joseph Robert

    1999-01-01

    A process using a niobium catalyst includes the step of reacting an ester or carboxylic acid with oxygen and an alcohol in the presence a niobium catalyst to respectively produce an .alpha.,.beta.-unsaturated ester or carboxylic acid. Methanol may be used as the alcohol, and the ester or carboxylic acid may be passed over the niobium catalyst in a vapor stream containing oxygen and methanol. Alternatively, the process using a niobium catalyst may involve the step of reacting an ester and oxygen in the presence the niobium catalyst to produce an .alpha.,.beta.-unsaturated carboxylic acid. In this case the ester may be a methyl ester. In either case, niobium oxide may be used as the niobium catalyst with the niobium oxide being present on a support. The support may be an oxide selected from the group consisting of silicon oxide, aluminum oxide, titanium oxide and mixtures thereof. The catalyst may be formed by reacting niobium fluoride with the oxide serving as the support. The niobium catalyst may contain elemental niobium within the range of 1 wt % to 70 wt %, and more preferably within the range of 10 wt % to 30 wt %. The process may be operated at a temperature from 150 to 450.degree. C. and preferably from 250 to 350.degree. C. The process may be operated at a pressure from 0.1 to 15 atm. absolute and preferably from 0.5-5 atm. absolute. The flow rate of reactants may be from 10 to 10,000 L/kg.sub.(cat) /h, and preferably from 100 to 1,000 L/kg.sub.(cat) /h.

  5. Iodine-Catalyzed Decarboxylative Amidation of β,γ-Unsaturated Carboxylic Acids with Chloramine Salts Leading to Allylic Amides.

    PubMed

    Kiyokawa, Kensuke; Kojima, Takumi; Hishikawa, Yusuke; Minakata, Satoshi

    2015-10-26

    The iodine-catalyzed decarboxylative amidation of β,γ-unsaturated carboxylic acids with chloramine salts is described. This method enables the regioselective synthesis of allylic amides from various types of β,γ-unsaturated carboxylic acids containing substituents at the α- and β-positions. In the reaction, N-iodo-N-chloroamides, generated by the reaction of a chloramine salt with I2 , function as a key active species. The reaction provides an attractive alternative to existing methods for the synthesis of useful secondary allylic amine derivatives. PMID:26493878

  6. Global Metabolomic Profiling Reveals an Association of Metal Fume Exposure and Plasma Unsaturated Fatty Acids

    PubMed Central

    Chang, Chiung-yu; Fan, Tianteng; Su, Li; Chen, Feng; Christiani, David C.

    2013-01-01

    Background Welding-associated air pollutants negatively affect the health of exposed workers; however, their molecular mechanisms in causing disease remain largely unclear. Few studies have systematically investigated the systemic toxic effects of welding fumes on humans. Objectives To explore the effects of welding fumes on the plasma metabolome, and to identify biomarkers for risk assessment of welding fume exposure. Methods The two-stage, self-controlled exploratory study included 11 boilermakers from a 2011 discovery panel and 8 boilermakers from a 2012 validation panel. Plasma samples were collected pre- and post-welding fume exposure and analyzed by chromatography/mass spectrometry. Results Eicosapentaenoic or docosapentaenoic acid metabolic changes post-welding were significantly associated with particulate (PM2.5) exposure (p<0.05). The combined analysis by linear mixed-effects model showed that exposure was associated with a statistically significant decline in metabolite change of eicosapentaenoic acid [(95% CI) = −0.013(−0.022∼−0.004); p = 0.005], docosapentaenoic acid n3 [(95% CI) = −0.010(−0.018∼−0.002); p = 0.017], and docosapentaenoic acid n6 [(95% CI) = −0.007(−0.013∼−0.001); p = 0.021]. Pathway analysis identified an association of the unsaturated fatty acid pathway with exposure (pStudy−2011 = 0.025; pStudy−2012 = 0.021; pCombined = 0.009). The functional network built by these fatty acids and their interactive genes contained significant enrichment of genes associated with various diseases, including neoplasms, cardiovascular diseases, and lipid metabolism disorders. Conclusions High-dose exposure of metal welding fumes decreases unsaturated fatty acids with an exposure-response relationship. This alteration in fatty acids is a potential biological mediator and biomarker for exposure-related health disorders. PMID:24143234

  7. The Staphylococcus aureus Response to Unsaturated Long Chain Free Fatty Acids: Survival Mechanisms and Virulence Implications

    PubMed Central

    Kenny, John G.; Ward, Deborah; Josefsson, Elisabet; Jonsson, Ing-Marie; Hinds, Jason; Rees, Huw H.; Lindsay, Jodi A.; Tarkowski, Andrej; Horsburgh, Malcolm J.

    2009-01-01

    Staphylococcus aureus is an important human commensal and opportunistic pathogen responsible for a wide range of infections. Long chain unsaturated free fatty acids represent a barrier to colonisation and infection by S. aureus and act as an antimicrobial component of the innate immune system where they are found on epithelial surfaces and in abscesses. Despite many contradictory reports, the precise anti-staphylococcal mode of action of free fatty acids remains undetermined. In this study, transcriptional (microarrays and qRT-PCR) and translational (proteomics) analyses were applied to ascertain the response of S. aureus to a range of free fatty acids. An increase in expression of the σB and CtsR stress response regulons was observed. This included increased expression of genes associated with staphyloxanthin synthesis, which has been linked to membrane stabilisation. Similarly, up-regulation of genes involved in capsule formation was recorded as were significant changes in the expression of genes associated with peptidoglycan synthesis and regulation. Overall, alterations were recorded predominantly in pathways involved in cellular energetics. In addition, sensitivity to linoleic acid of a range of defined (sigB, arcA, sasF, sarA, agr, crtM) and transposon-derived mutants (vraE, SAR2632) was determined. Taken together, these data indicate a common mode of action for long chain unsaturated fatty acids that involves disruption of the cell membrane, leading to interference with energy production within the bacterial cell. Contrary to data reported for other strains, the clinically important EMRSA-16 strain MRSA252 used in this study showed an increase in expression of the important virulence regulator RNAIII following all of the treatment conditions tested. An adaptive response by S. aureus of reducing cell surface hydrophobicity was also observed. Two fatty acid sensitive mutants created during this study were also shown to diplay altered pathogenesis as assessed

  8. Temperature-Sensitive Mutants of Escherichia coli Requiring Saturated and Unsaturated Fatty Acids for Growth: Isolation and Properties

    PubMed Central

    Harder, Mark E.; Beacham, Ifor R.; Cronan, John E.; Beacham, Kathryn; Honegger, Joy L.; Silbert, David F.

    1972-01-01

    A procedure is described for selection of temperature-sensitive mutants affecting fatty-acid synthesis based upon radiation suicide of wild-type organisms by tritiated acetate selectively incorporated into fatty acids. At 37°, two of the mutants extensively incorporate fatty-acid supplements provided in the medium, and grow for extended periods only when a trans-unsaturated or a combination of saturated and cis-unsaturated fatty acids is available. In vivo fatty-acid synthesis, measured by [14C]acetate incorporation, is temperature-sensitive in these strains relative to protein synthesis and other non-lipid macromolecular syntheses using acetate. The biochemical nature of these mutations has not been identified. PMID:4564200

  9. Effects of Diets High in Unsaturated Fatty Acids on Socially Induced Stress Responses in Guinea Pigs

    PubMed Central

    Nemeth, Matthias; Millesi, Eva; Wagner, Karl-Heinz; Wallner, Bernard

    2014-01-01

    Unsaturated fatty acids (UFAs), such as omega-3 and omega-6 poly- and omega-9 monounsaturated fatty acids are important nutrients and major components of neuronal cell membranes. They play a major role in modulating brain functions and physiology and may therefore diminish behavioral and physiological stress reactions in corroboration with decreased cortisol concentrations. Functionally, cortisol itself can modulate several behaviors and also the fatty acid metabolism in the long term. But only little is known about the behavioral and physiological influences of dietary UFAs in a social group, where individuals are regularly exposed to stressful situations. Therefore, the aim of this study was to determine the effects of dietary UFAs on saliva cortisol concentrations and behavioral responses in socially confronted guinea pigs. Three groups of animals were additionally supplemented with 500 mg chia seeds (high in omega-3), walnuts (high in omega-6), or peanuts (high in omega-9) per kg bodyweight each day and compared to a control group. During social confrontation saliva cortisol concentrations significantly increased in all groups, which was accompanied by a loss in bodyweight. However, cortisol levels remained lower in the chia and walnut groups compared to controls. Additionally, the walnut group displayed significantly increased locomotion, while no differences between groups were detected in socio-positive, sexual, or aggressive behaviors. Total plasma omega-3, omega-6, and omega-9 fatty acids were significantly increased in the corresponding groups, due to the dietary supplementations. However, a significant decrease in plasma omega-3 and an increase in plasma n-6 fatty acids were detected in the chia group when comparing the measurements before and after social confrontation. We conclude that both omega-3 and omega-6 polyunsaturated fatty acids can diminish behavioral and physiological stress responses to the social environment, enabling individuals to cope

  10. Effects of diets high in unsaturated Fatty acids on socially induced stress responses in Guinea pigs.

    PubMed

    Nemeth, Matthias; Millesi, Eva; Wagner, Karl-Heinz; Wallner, Bernard

    2014-01-01

    Unsaturated fatty acids (UFAs), such as omega-3 and omega-6 poly- and omega-9 monounsaturated fatty acids are important nutrients and major components of neuronal cell membranes. They play a major role in modulating brain functions and physiology and may therefore diminish behavioral and physiological stress reactions in corroboration with decreased cortisol concentrations. Functionally, cortisol itself can modulate several behaviors and also the fatty acid metabolism in the long term. But only little is known about the behavioral and physiological influences of dietary UFAs in a social group, where individuals are regularly exposed to stressful situations. Therefore, the aim of this study was to determine the effects of dietary UFAs on saliva cortisol concentrations and behavioral responses in socially confronted guinea pigs. Three groups of animals were additionally supplemented with 500 mg chia seeds (high in omega-3), walnuts (high in omega-6), or peanuts (high in omega-9) per kg bodyweight each day and compared to a control group. During social confrontation saliva cortisol concentrations significantly increased in all groups, which was accompanied by a loss in bodyweight. However, cortisol levels remained lower in the chia and walnut groups compared to controls. Additionally, the walnut group displayed significantly increased locomotion, while no differences between groups were detected in socio-positive, sexual, or aggressive behaviors. Total plasma omega-3, omega-6, and omega-9 fatty acids were significantly increased in the corresponding groups, due to the dietary supplementations. However, a significant decrease in plasma omega-3 and an increase in plasma n-6 fatty acids were detected in the chia group when comparing the measurements before and after social confrontation. We conclude that both omega-3 and omega-6 polyunsaturated fatty acids can diminish behavioral and physiological stress responses to the social environment, enabling individuals to cope

  11. Tandem isomerization-decarboxylation of unsaturated fatty acids to olefins via ruthenium metal-as-ligand catalysts

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A new facile Ru-catalyzed route to bio-olefins3 from unsaturated fatty acids via readily accessible metal-as-ligand type catalyst precursors, [Ru(CO)2RCO2]n and Ru3(CO)12, will be described. The catalyst apparently functions in a tandem mode by dynamically isomerizing the positions of double bonds i...

  12. Copper-Catalyzed Carboxylation of Alkenylzirconocenes with Carbon Dioxide Leading to α,β-Unsaturated Carboxylic Acids.

    PubMed

    Wang, Sheng; Shao, Peng; Chen, Chao; Xi, Chanjuan

    2015-10-16

    A variety of alkenylzirconocenes were efficiently carboxylated by CO2 utilizing the (IMes)CuCl catalyst yielding the corresponding α,β-unsaturated carboxylic acids in good yields. This reaction could be carried out in a one-pot operation via sequential carbozirconation of alkynes and carboxylation using CO2 as starting materials under room temperature. PMID:26406296

  13. Selective Nickel- and Manganese-Catalyzed Decarboxylative Cross Coupling of Some α,β-Unsaturated Carboxylic Acids with Cyclic Ethers

    PubMed Central

    Zhang, Jia-Xiang; Wang, Yan-Jing; Zhang, Wei; Wang, Nai-Xing; Bai, Cui-Bing; Xing, Ya-Lan; Li, Yi-He; Wen, Jia-Long

    2014-01-01

    A nickel- and manganese-catalyzed decarboxylative cross coupling of α, β-unsaturated carboxylic acids with cyclic ethers such as tetrahydrofuran and 1, 4-dioxane was developed. Oxyalkylation was achieved when nickel acetate was used as catalyst, while manganese acetate promoted the reaction of alkenylation. PMID:25502282

  14. Alkaline battery containing a separator of a cross-linked copolymer of vinyl alcohol and unsaturated carboxylic acid

    NASA Technical Reports Server (NTRS)

    Hsu, L. C.; Philipp, W. H.; Sheibley, D. W.; Gonzalez-Sanabria, O. D. (Inventor)

    1985-01-01

    A battery separator for an alkaline battery is described. The separator comprises a cross linked copolymer of vinyl alcohol units and unsaturated carboxylic acid units. The cross linked copolymer is insoluble in water, has excellent zincate diffusion and oxygen gas barrier properties and a low electrical resistivity. Cross linking with a polyaldehyde cross linking agent is preferred.

  15. Unsaturated fatty acids prevent activation of NLRP3 inflammasome in human monocytes/macrophages[S

    PubMed Central

    L'homme, Laurent; Esser, Nathalie; Riva, Laura; Scheen, André; Paquot, Nicolas; Piette, Jacques; Legrand-Poels, Sylvie

    2013-01-01

    The NLRP3 inflammasome is involved in many obesity-associated diseases, such as type 2 diabetes, atherosclerosis, and gouty arthritis, through its ability to induce interleukin (IL)-1β release. The molecular link between obesity and inflammasome activation is still unclear, but free fatty acids have been proposed as one triggering event. Here we reported opposite effects of saturated fatty acids (SFAs) compared with unsaturated fatty acids (UFAs) on NLRP3 inflammasome in human monocytes/macrophages. Palmitate and stearate, both SFAs, triggered IL-1β secretion in a caspase-1/ASC/NLRP3-dependent pathway. Unlike SFAs, the UFAs oleate and linoleate did not lead to IL-1β secretion. In addition, they totally prevented the IL-1β release induced by SFAs and, with less efficiency, by a broad range of NLRP3 inducers, including nigericin, alum, and monosodium urate. UFAs did not affect the transcriptional effect of SFAs, suggesting a specific effect on the NLRP3 activation. These results provide a new anti-inflammatory mechanism of UFAs by preventing the activation of the NLRP3 inflammasome and, therefore, IL-1β processing. By this way, UFAs might play a protective role in NLRP3-associated diseases. PMID:24006511

  16. From microalgae oil to produce novel structured triacylglycerols enriched with unsaturated fatty acids.

    PubMed

    Wang, Jun; Wang, Xu-Dong; Zhao, Xing-Yu; Liu, Xi; Dong, Tao; Wu, Fu-An

    2015-05-01

    Novel structured triacylglycerols (STAGs) enriched with unsaturated fatty acids (UFAs) and low palmitic acid (PA) content were firstly synthesized from Schizochytrium sp. oil and oleic acid (OA) via solvent-free acidolysis catalyzed by Lipozyme RM IM. The results indicated that, the PA content decreased from 24.49% to 6.95%, while the UFAs content increased from 70.20% to 90.9% at the sn-1,3 positions in the STAGs under the optimal condition (i.e., lipase load of 7%, molar ratio of microalgae oil TAGs to OA of 1:3, and temperature of 65 °C). The lipase Lipozyme RM IM could be reused 16 times without significant loss of activity. The improved plastic and storage ranges of STAGs are useful for infant formula formulations, by which a possible method is blending of this product and 1,3-dioleoyl-2-palmitoylglycerol enriched fats and minor lipids based on the corresponding chemical compositions of human milk fat. PMID:25451776

  17. The Effect of Temperature on the Level and Biosynthesis of Unsaturated Fatty Acids in Diacylglycerols of Brassica napus Leaves 1

    PubMed Central

    Williams, John P.; Khan, Mobashsher U.; Mitchell, Kirk; Johnson, Geoff

    1988-01-01

    Experiments on the effects of temperature on the levels of unsaturated fatty acids and their rates of desaturation in Brassica napus leaf lipids have shown that significant differences occur in the composition of all diacylglycerols in the leaf between plants grown at high and low temperatures. In the major thylakoid diacylglycerols, monogalactosyl-diacylglycerol and digalactosyldiacylglycerol, not only is there an increase in the level of unsaturation at low temperatures, but there is a change in the balance between molecular species of chloroplastic origin (16/18C) and cytosolic origin (18/18C). Radioactivity tracer data indicate that at low temperatures there are two distinct phases of desaturation in the fatty acids of the major diacylglycerols of these leaves. A rapid phase, which appears in plants grown at low temperatures and results in the desaturation of palmitic acid to hexadecadienoic acid and oleic acid to linoleic acid may explain the high levels of unsaturated fatty acids found in the leaf diacylglycerols from plants grown at low temperatures. The appearance of this rapid phase is controlled by the temperature at which the plant is grown and is not subject to rapid variations in environmental temperature. PMID:16666243

  18. Modification of the Technical Properties of Lactobacillus johnsonii NCC 533 by Supplementing the Growth Medium with Unsaturated Fatty Acids

    PubMed Central

    Muller, J. A.; Ross, R. P.; Sybesma, W. F. H.; Fitzgerald, G. F.; Stanton, C.

    2011-01-01

    The aim of this study was to investigate the influence of supplementing growth medium with unsaturated fatty acids on the technical properties of the probiotic strain Lactobacillus johnsonii NCC 533, such as heat and acid tolerance, and inhibition of Salmonella enterica serovar Typhimurium infection. Our results showed that the membrane composition and morphology of L. johnsonii NCC 533 were significantly changed by supplementing a minimal Lactobacillus medium with oleic, linoleic, and linolenic acids. The ratio of saturated to unsaturated plus cyclic fatty acids in the bacterial membrane decreased by almost 2-fold when minimal medium was supplemented with unsaturated fatty acids (10 μg/ml). The subsequent acid and heat tolerance of L. johnsonii decreased by 6- and 20-fold when the strain was grown in the presence of linoleic and linolenic acids, respectively, compared with growth in oleic acid (all at 10 μg/ml). Following acid exposure, significantly higher (P < 0.05) oleic acid content was detected in the membrane when growth medium was supplemented with linoleic or linolenic acid, indicating that saturation of the membrane fatty acids occurred during acid stress. Cell integrity was determined in real time during stressed conditions using a fluorescent viability kit in combination with flow cytometric analysis. Following heat shock (at 62.5°C for 5 min), L. johnsonii was unable to form colonies; however, 60% of the bacteria showed no cell integrity loss, which could indicate that the elevated heat inactivated vital processes within the cell, rendering it incapable of replication. Furthermore, L. johnsonii grown in fatty acid-enriched minimal medium had different adhesion properties and caused a 2-fold decrease in S. enterica serovar Typhimurium UK1-lux invasion of HT-29 epithelial cells compared with bacteria grown in minimal medium alone. This could be related to changes in the hydrophobicity and fluidity of the membrane. Our study shows that technical

  19. Uptake and incorporation of saturated and unsaturated fatty acids into macrophage lipids and their effect upon macrophage adhesion and phagocytosis.

    PubMed Central

    Calder, P C; Bond, J A; Harvey, D J; Gordon, S; Newsholme, E A

    1990-01-01

    Murine thioglycollate-elicited peritoneal macrophages were cultured in the presence of a variety of fatty acids added as complexes with bovine serum albumin. All fatty acids tested were taken up readily by the cells and both neutral and phospholipid fractions were enriched with the fatty acid provided in the medium. This generated a range of cells enriched in saturated, monounsaturated or polyunsaturated fatty acids, including n-3 acids of fish oil origin. Saturated fatty acid enrichment enhanced macrophage adhesion to both tissue culture plastic and bacterial plastic compared with enrichment with polyunsaturated fatty acids. Macrophages enriched with the saturated fatty acids myristate or palmitate showed decreases of 28% and 21% respectively in their ability to phagocytose unopsonized zymosan particles. Those enriched with polyunsaturated fatty acids showed 25-55% enhancement of phagocytic capacity. The greatest rate of uptake was with arachidonate-enriched cells. Phagocytic rate was highly correlated with the saturated/unsaturated fatty acid ratio, percentage of polyunsaturated fatty acid and index of unsaturation, except for macrophages enriched with fish-oil-derived fatty acids; they showed lower phagocytic activity than expected on the basis of their degree of unsaturation. These results suggest that membrane fluidity is important in determining macrophage adhesion and phagocytic activity. However, in the case of phagocytosis, this effect may be partially overcome if the cells are enriched with fish-oil-derived fatty acids. Thus it may be possible to modulate the activity of cells of the immune system, and so an immune response, by dietary lipid manipulation. PMID:2117922

  20. Combusting vegetable oils in diesel engines: the impact of unsaturated fatty acids on particle emissions and mutagenic effects of the exhaust.

    PubMed

    Bünger, Jürgen; Bünger, Jörn F; Krahl, Jürgen; Munack, Axel; Schröder, Olaf; Brüning, Thomas; Hallier, Ernst; Westphal, Götz A

    2016-06-01

    High particle emissions and strong mutagenic effects were observed after combustion of vegetable oil in diesel engines. This study tested the hypothesis that these results are affected by the amount of unsaturated or polyunsaturated fatty acids of vegetable oils. Four different vegetable oils (coconut oil, CO; linseed oil, LO; palm tree oil, PO; and rapeseed oil, RO) and common diesel fuel (DF) were combusted in a heavy-duty diesel engine. The exhausts were investigated for particle emissions and mutagenic effects in direct comparison with emissions of DF. The engine was operated using the European Stationary Cycle. Particle masses were measured gravimetrically while mutagenicity was determined using the bacterial reverse mutation assay with tester strains TA98 and TA100. Combustion of LO caused the largest amount of total particulate matter (TPM). In comparison with DF, it particularly raised the soluble organic fraction (SOF). RO presented second highest TPM and SOF, followed by CO and PO, which were scarcely above DF. RO revealed the highest number of mutations of the vegetable oils closely followed by LO. PO was less mutagenic, but still induced stronger effects than DF. While TPM and SOF were strongly correlated with the content of polyunsaturated fatty acids in the vegetable oils, mutagenicity had a significant correlation with the amount of total unsaturated fatty acids. This study supports the hypothesis that numbers of double bounds in unsaturated fatty acids of vegetable oils combusted in diesel engines influence the amount of emitted particles and the mutagenicity of the exhaust. Further investigations have to elucidate the causal relationship. PMID:26126632

  1. Shallow hypothermia depends on the level of fatty acid unsaturation in adipose and liver tissues in a tropical heterothermic primate.

    PubMed

    Vuarin, Pauline; Henry, Pierre-Yves; Guesnet, Philippe; Alessandri, Jean-Marc; Aujard, Fabienne; Perret, Martine; Pifferi, Fabien

    2014-07-01

    Optimal levels of unsaturated fatty acids have positive impacts on the use of prolonged bouts of hypothermia in mammalian hibernators, which generally have to face low winter ambient temperatures. Unsaturated fatty acids can maintain the fluidity of fat and membrane phospholipids at low body temperatures. However, less attention has been paid to their role in the regulation of shallow hypothermia, and in tropical species, which may be challenged more by seasonal energetic and/or water shortages than by low temperatures. The present study assessed the relationship between the fatty acids content of white adipose and liver tissues and the expression of shallow hypothermia in a tropical heterothermic primate, the gray mouse lemur (Microcebus murinus). The adipose tissue is the main tissue for fat storage and the liver is involved in lipid metabolism, so both tissues were expected to influence hypothermia dependence on fatty acids. As mouse lemurs largely avoid deep hypothermia (i.e. torpor) use under standard captive conditions, the expression of hypothermia was triggered by food-restricting experimental animals. Hypothermia depth increased with time, with a stronger increase for individuals that exhibited higher contents of unsaturated fatty acids suggesting that they were more flexible in their use of hypothermia. However these same animals delayed the use of long hypothermia bouts relative to individuals with a higher level of saturated fatty acids. This study evidences for the first time that body fatty acids unsaturation levels influence the regulation of body temperature not only in cold-exposed hibernators but also in tropical, facultative heterotherms. PMID:24956961

  2. Unsaturated amino acids derived from isoleucine trigger early membrane effects on plant cells.

    PubMed

    Roblin, Gabriel; Laduranty, Joëlle; Bonmort, Janine; Aidene, Mohand; Chollet, Jean-François

    2016-10-01

    Unsaturated amino acids (UnsAA) have been shown to affect the activity of various biological processes. However, their mode of action has been investigated poorly thus far. We show in this work that 2-amino-3-methyl-4-pentenoic acid (C2) and 2-amino-3-methyl-4-pentynoic acid (C3) structurally derived from isoleucine (Ile) exhibited a multisite action on plant cells. For one, C2 and C3 induced early modifications at the plasma membrane level, as shown by the hyperpolarization monitored by microelectrode implantation in the pulvinar cells of Mimosa pudica, indicating that these compounds are able to modify ionic fluxes. In particular, proton (H(+)) fluxes were modified, as shown by the pH rise monitored in the bathing medium of pulvinar tissues. A component of this effect may be linked to the inhibitory effect observed on the proton pumping and the vanadate-sensitive activity of the plasma membrane H(+)-ATPase monitored in plasma membrane vesicles (PMVs) purified from pulvinar tissues of M. pudica and leaf tissues of Beta vulgaris. This effect may explain, in part, the inhibitory effect of the compounds on the uptake capacity of sucrose and valine by B. vulgaris leaf tissues. In contrast, an unexpected action was observed in cell reactions, implicating ion fluxes and water movement. Indeed, the osmocontractile reactions of pulvini induced either by a mechanical shock in M. pudica or by dark and light signals in Cassia fasciculata were increased, indicating that, compared to Ile, these compounds may modify in a specific way the plasma membrane permeability to water and ions. PMID:27254795

  3. The effect of supplementing rumen undegradable unsaturated fatty acids on marbling in early-weaned steers.

    PubMed

    Mangrum, K S; Tuttle, G; Duckett, S K; Sell, G S; Krehbiel, C R; Long, N M

    2016-02-01

    The objective of this study was to determine if supplementation with a rumen undegradable unsaturated fatty acids (FA) source improved marbling deposition in early-weaned steers. All steers (Angus, = 23; Angus × Hereford, = 24) were weaned at 150 ± 5 d of age. Steers were blocked by BW and breed and then randomly assigned to either control (CON; average 1.5 kg of corn gluten feed [CGF], = 23) or isocaloric supplementation containing a rumen undegradable fat source (RUF; 200 g of Megalac-R added to an average of 1.06 kg of CGF, = 24) offered 5 d/wk for 110 d. All steers had ad libitum access to pastures throughout treatment and received supplements individually. Steer BW and blood samples were collected at 0, 55, and 110 d of supplementation, and real-time ultrasound measurements were collected at d 110. Following treatment, steers were transported to Oklahoma State University for finishing and subsequent harvesting at a commercial plant. All data were analyzed using the PROC MIXED procedure of SAS either as repeated measures or ANOVA depending on parameters. There were no significant changes in BW from the beginning of treatment to harvest due to treatment. Ultrasound data showed that RUF steers tended ( = 0.08) to have more i.m. fat than CON at d 110. Serum concentrations of FA showed a treatment × day interaction ( < 0.02) for 16:0, 18:0, 18:1-9, 18:2, 20:4, and total FA. These specific FA concentrations slightly increased in CON steers, but there was a more pronounced increase in the concentration of these FA across the supplementation period in RUF steers. Serum triglyceride and cholesterol concentrations were increased ( < 0.01) on d 55 and 110 in RUF steers compared with those in CON steers. Serum leptin concentration in RUF steers was greater ( < 0.01) than CON steers at d 110. After harvest, RUF carcasses had greater ( = 0.01) marbling scores than those of CON carcasses. All other carcass measures were similar between treatments. The percentage of total

  4. Influence of the degree of unsaturation of the acyl side chain upon the interaction of analogues of 1-arachidonoylglycerol with monoacylglycerol lipase and fatty acid amide hydrolase

    SciTech Connect

    Vandevoorde, Severine; Saha, Bijali; Mahadevan, Anu; Razdan, Raj K.; Pertwee, Roger G.; Martin, Billy R.; Fowler, Christopher J. . E-mail: cf@pharm.umu.se

    2005-11-11

    Little is known as to the structural requirements of the acyl side chain for interaction of acylglycerols with monoacylglycerol lipase (MAGL), the enzyme chiefly responsible for the metabolism of the endocannabinoid 2-arachidonoylglycerol (2-AG) in the brain. In the present study, a series of twelve analogues of 1-AG (the more stable regioisomer of 2-AG) were investigated with respect to their ability to inhibit the metabolism of 2-oleoylglycerol by cytosolic and membrane-bound MAGL. In addition, the ability of the compounds to inhibit the hydrolysis of anandamide by fatty acid amide hydrolase (FAAH) was investigated. For cytosolic MAGL, compounds with 20 carbon atoms in the acyl chain and 2-5 unsaturated bonds inhibited the hydrolysis of 2-oleoylglycerol with similar potencies (IC{sub 50} values in the range 5.1-8.2 {mu}M), whereas the two compounds with a single unsaturated bond were less potent (IC{sub 50} values 19 and 21 {mu}M). The fully saturated analogue 1-monoarachidin did not inhibit the enzyme, whereas the lower side chain analogues 1-monopalmitin and 1-monomyristin inhibited the enzyme with IC{sub 50} values of 12 and 32 {mu}M, respectively. The 22-carbon chain analogue of 1-AG was also potent (IC{sub 50} value 4.5 {mu}M). Introduction of an {alpha}-methyl group for the C20:4, C20:3, and C22:4 compounds did not affect potency in a consistent manner. For the FAAH and the membrane-bound MAGL, there was no obvious relationship between the degree of unsaturation of the acyl side chain and the ability to inhibit the enzymes. It is concluded that increasing the number of unsaturated bonds on the acyl side chain of 1-AG from 1 to 5 has little effect on the affinity of acylglycerols for cytosolic MAGL.

  5. Prebiotic oligomerization of amino acids inside lipid vesicles of unsaturated and saturated fatty acids in hydrothermal environments

    NASA Astrophysics Data System (ADS)

    Imai, E.; Furuuchi, R.; Nemoto, A.; Hatori, K.; Honda, H.; Matsuno, K.

    We have already attempted an experimental model simulating seawater circulation in the vicinity of hydrothermal vents in the primitive ocean. We used a flow reactor that was constructed for simulating the pressure and temperature conditions of the hydrothermal vents. In the flow reactor, a high-temperature high-pressure fluid at 125˜ 250°C and at 20MPa was injected into a low temperature (0˜ 40°C ) chamber that was maintained at about the same high pressure as the fluid. We then experimentally examined a possibility of oligomerizing amino acids on or inside lipid vesicles. We compared three different kinds of lipid vesicles made of unsaturated fatty acids (oleic acid), saturated fatty acids (decanoic acid) and phospholipids (DPPC). Identification of the oligomeric products was made with the aid of an HPLC analysis. The oligomeric yields from glycine increased significantly in the presence of lipid vesicles compared to the case of their absence. On the other hand, there was found no significant difference in the yields of oligomers between in the presence of lipid vesicles dissolved by surfactant and in their absence. The possibility of lipid molecules serving as catalysts for oligomerization may be dismissed. The diameters of those lipid vesicles observed under a phase contrast microscope were about 10 micrometer or less. The total volume shared by oleic acid vesicles was about 5 % of the total volume of the suspension. Oligomerization of glycine inside oleic acid vesicles was enhanced more than 15 times compared to that proceeding in their outside. Enhancement of oligomerization of glycine in the presence of lipid vesicles was repeated as the reactants revisited the interface zone between the hot and cold regions. Even those lipid vesicles made of saturated fatty acid such as decanoic acid could have been functional in enhancing the oligomerization of monomers in their inside in the primitive ocean. References E. Imai, et al. (1999) Science 283, 831-833. H

  6. The metabolic profile of growing lambs fed diets rich in unsaturated fatty acids.

    PubMed

    Steppa, R; Szkudelska, K; Wójtowski, J; Stanisz, M; Szumacher-Strabel, M; Czyżak-Runowska, G; Cieślak, A; Markiewicz-Kęszycka, M; Pietrzak, M

    2014-10-01

    The effect of two diets enriched with unsaturated fatty acids--one containing the addition of dried distillers grains with solubles (DGS) and the other the addition of false flax--Camelina sativa cake (CS)--on some metabolic parameters and hormone concentration in growing lambs was determined in this experiment. A total of 21 ram lambs of the Polish Whiteheaded mutton sheep were divided into three groups (the control, receiving DGS and CS). The diets were administered to animals for 6 weeks. During the experiment, peripheral blood was collected. Glucose (GL), total cholesterol (CH), triglycerides (TG), free fatty acids (FFA), insulin (IN), leptin (LE), triiodothyronine (T3) and thyroxine (T4) were assayed in serum. The age-dependent reduction in CH and TG limited by both experimental diets were observed. A significant increase in FFA concentration was observed in samples collected in the last, that is, third, time period. This was most probably caused by a 12-h pre-slaughter fasting period. A significantly lower dynamic of FFA increase in that experimental period was found in animals receiving the experimental feed. Insulin concentration in DGS-receiving lambs was increased, in contrast to the CS-receiving lambs, in which it was lower when compared to the control. LE concentration was decreased by both experimental diets, more markedly in the DGS-receiving animals. No differences between the experimental groups and the control were observed in T3 and T4 concentrations. The effect of 12-h pre-slaughter fasting was statistically highly significant for the levels of examined blood markers and hormones, except for TG and IN in the group of lambs receiving the experimental diet with CS. PMID:24387699

  7. [Effect of the B-group vitamin complex on the blood content of saturated and unsaturated fatty acids in patients with ischemic heart disease and hypertension].

    PubMed

    Vodoevich, V P; Buko, V U

    1986-01-01

    Gas-liquid chromatography was used to study the blood content of saturated and unsaturated fatty acids, under the influence of the functionally-associated vitamin-B complex, in 45 patients with coronary heart disease and essential hypertension. The vitamins were given daily in the following doses: thiamine diphosphate 50 mg, riboflavine 40 mg, calcium pantothenate 200 mg, nicotinic acid 200 mg and lipoic acid 50 mg. Favourable shifts leading to positive clinical effects were recorded in the fatty acid metabolism after 10-day taking the vitamin-B complex: the content of unsaturated (linoleic and arachidonic) fatty acids increased while that of saturated (stearic and palmitic) fatty acids decreased. PMID:3705551

  8. Radical formation in the FMN-photosensitized reactions of unsaturated fatty acids bearing double bonds at different positions.

    PubMed

    Nishihama, Nao; Iwahashi, Hideo

    2016-08-15

    Although the reaction mechanisms through which flavin mononucleotide works as an endogenous photosensitizer have been investigated (Baier et al., 2006; Edwards and Silva, 2001; Pajares et al., 2001; Criado et al., 2003; Massad et al., 2008) [23-27], few studies have been performed for the reactions of flavin mononucleotide with unsaturated fatty acids. To examine the reactions of flavin mononucleotide with unsaturated fatty acids bearing a double bond at different positions, an electron spin resonance, a high performance liquid chromatography-electron spin resonance and a high performance liquid chromatography-electron spin resonance-mass spectrometry were employed. The control reaction mixtures contained 25μmolL(-1) of flavin mononucleotide, 1.0mmolL(-1) of FeSO4(NH4)2SO4, 10mmolL(-1) of cholic acid, 30mmolL(-1) of phosphate buffer (pH 7.4) and 0.1molL(-1) of α-(4-pyridyl-1-oxide)-N-tert-butylnitrone in deuterium oxide. In addition, it also contained 4.3mmolL(-1) of one of the following: (z)-11-octadecenoic acid, (z)-6-octadecenoic acid, (z)-9-octadecenoic acid or (z, z)-9, 12-octadecadienoic acid. The control reaction mixtures without FeSO4(NH4)2SO4 and α-(4-pyridyl-1-oxide)-N-tert-butylnitrone were exposed to the visible light at 436nm (7.8Jcm(-2)). After the irradiation, α-(4-pyridyl-1-oxide)-N-tert-butylnitrone was added. The reactions started from adding FeSO4(NH4)2SO4 and performed at 25°C for 1min. Electron spin resonance measurements of the control reaction mixtures showed prominent signals (α(N)=1.58mT and α(Hβ)=0.26mT). High performance liquid chromatography-electron spin resonance analyses of the control reaction mixtures showed prominent peaks at the retention times of 31.1min {(z)-6-octadecenoic acid}, 39.6min {(z)-9-octadecenoic acid}, 44.9min {(z)-11-octadecenoic acid} and 40.2min {(z, z)-9, 12-octadecadienoic acid}. High performance liquid chromatography-electron spin resonance-mass analyses of the control reaction mixtures showed that 4

  9. Sex-Specific Effects of Diets High in Unsaturated Fatty Acids on Spatial Learning and Memory in Guinea Pigs

    PubMed Central

    Nemeth, Matthias; Millesi, Eva; Wagner, Karl-Heinz; Wallner, Bernard

    2015-01-01

    Unsaturated fatty acids (UFAs), including omega-3, omega-6 polyunsaturated and omega-9 monounsaturated fatty acids, are essential components and modulators of neuromembranes and may affect various aspects of physiology and cognition. UFAs are suggested to positively affect spatial learning and memory and also to diminish the negative consequences of physiological stress on cognitive abilities. Due to pronounced sex differences in neurophysiological functions, we hypothesize that these UFA-related effects might differ between male and female individuals. We therefore determined the effects of dietary UFAs on cognitive performances in a radial-Y-maze in male and female guinea pigs in relation to saliva cortisol concentrations, a marker for physiological stress. Animals were assigned to four treatment groups and maintained on diets enriched in either chia seeds (omega-3), walnuts (omega-6), or peanuts (omega-9), or a control diet. Female learning abilities throughout a three-day learning phase were positively affected by omega-3 and omega-9, as determined by a decreasing latency to pass the test and the number of conducted errors, while males generally showed distinct learning abilities, irrespective of the diet. A sex difference in learning performances was found in the control group, with males outperforming females, which was not detected in the UFA-supplemented groups. This was paralleled by significantly increased saliva cortisol concentrations in males throughout the cognition test compared to females. Three days after this learning phase, UFA-supplemented males and all females showed unchanged performances, while control males showed an increased latency and therefore an impaired performance. These results were corroborated by pronounced differences in the plasma UFA-status, corresponding to the different dietary treatments. Our findings indicate sex-specific effects of dietary UFAs, apparently enhancing spatial learning abilities only in females and protecting

  10. Sex-Specific Effects of Diets High in Unsaturated Fatty Acids on Spatial Learning and Memory in Guinea Pigs.

    PubMed

    Nemeth, Matthias; Millesi, Eva; Wagner, Karl-Heinz; Wallner, Bernard

    2015-01-01

    Unsaturated fatty acids (UFAs), including omega-3, omega-6 polyunsaturated and omega-9 monounsaturated fatty acids, are essential components and modulators of neuromembranes and may affect various aspects of physiology and cognition. UFAs are suggested to positively affect spatial learning and memory and also to diminish the negative consequences of physiological stress on cognitive abilities. Due to pronounced sex differences in neurophysiological functions, we hypothesize that these UFA-related effects might differ between male and female individuals. We therefore determined the effects of dietary UFAs on cognitive performances in a radial-Y-maze in male and female guinea pigs in relation to saliva cortisol concentrations, a marker for physiological stress. Animals were assigned to four treatment groups and maintained on diets enriched in either chia seeds (omega-3), walnuts (omega-6), or peanuts (omega-9), or a control diet. Female learning abilities throughout a three-day learning phase were positively affected by omega-3 and omega-9, as determined by a decreasing latency to pass the test and the number of conducted errors, while males generally showed distinct learning abilities, irrespective of the diet. A sex difference in learning performances was found in the control group, with males outperforming females, which was not detected in the UFA-supplemented groups. This was paralleled by significantly increased saliva cortisol concentrations in males throughout the cognition test compared to females. Three days after this learning phase, UFA-supplemented males and all females showed unchanged performances, while control males showed an increased latency and therefore an impaired performance. These results were corroborated by pronounced differences in the plasma UFA-status, corresponding to the different dietary treatments. Our findings indicate sex-specific effects of dietary UFAs, apparently enhancing spatial learning abilities only in females and protecting

  11. The effects of trans-fatty acids on TAG regulation in mice depend on dietary unsaturated fatty acids.

    PubMed

    Saín, Juliana; González, Marcela Aída; Lavandera, Jimena Verónica; Scalerandi, María Victoria; Bernal, Claudio Adrián

    2016-08-01

    The aim of this study was to investigate the effects of trans-fatty acids (TFA) on liver and serum TAG regulation in mice fed diets containing different proportions of n-3, n-6 and n-9 unsaturated fatty acids (UFA) from olive (O), maize (C) or rapeseed (R) oils partially substituted or not with TFA (Ot, Ct and Rt, respectively). Male CF1 mice were fed (30 d) one of these diets. The effects of the partial substitution (1 %, w/w) of different UFA with TFA on the activity and expression of hepatic enzymes involved in lipogenesis and fatty acids oxidation were evaluated, as well as their transcription factor expressions. Some of the mechanisms involved in the serum TAG regulation, hepatic VLDL rich in TAG (VLDL-TAG) secretion rate and lipoprotein lipase (LPL) activity were assessed. In liver, TFA induced an increase in TAG content in the Ot and Rt groups, and this effect was associated with an imbalance between lipogenesis and β-oxidation. In the Ot group, exacerbated lipogenesis may be one of the mechanisms responsible for the liver steatosis induced by TFA, whereas in Rt it has been related to a decreased β-oxidation, compared with their respective controls. The enhanced hepatic VLDL-TAG secretion in the Ot and Rt groups was compensated with a differential removal of TAG by LPL enzyme in extrahepatic tissues, leading to unchanged serum TAG levels. In brief, the effects of low levels of TFA on liver and serum TAG regulation in mice depend on the dietary proportions of n-3, n-6 and n-9 UFA. PMID:27464460

  12. The Role of Highly Unsaturated Fatty Acids in Aquatic Food Webs

    NASA Astrophysics Data System (ADS)

    Perhar, G.; Arhonditsis, G. B.

    2009-05-01

    Highly unsaturated fatty acids (HUFAs) are important molecules transferred across the plant-animal interface in aquatic food webs. Defined here as carbon chains of length 18 (carbons) or more, with a double bond in the third (Omega 3) or sixth (Omega 6) bond from the methyl end, HUFAs are formed in primary producers (phytoplankton). With limited abilities to synthesize de novo, consumers and higher trophic organisms are required to obtain their HUFAs primarily from diet. Bioconversion of HUFAs from one form to another is in theory possible, as is synthesis via elongation and the transformation of a saturated to highly saturated fatty acid, but the enzymes required for these processes are absent in most species. HUFAs are hypothesized to be somatic growth limiting compounds for herbivorous zooplankton and have been shown to be critical for juvenile fish growth and wellbeing. Zooplankton tend to vary their fatty acid concentrations, collection strategies and utilization methods based on taxonomy, and various mechanisms have been suggested to account for these differences i.e., seasonal and nervous system hypotheses. Considering also the facts that copepods overwinter in an active state while daphnids overwinter as resting eggs, and that copepods tend to accumulate Docosahexaenoic acid (DHA) through collection and bioconversion, while daphnids focus on Eicosapentaenoic acid (EPA), one can link high DHA concentrations to active overwintering; but both EPA and DHA have similar melting points, putting DHA's cold weather adaptation abilities into question. Another characteristic setting copepods apart from daphnids is nervous system complexity: copepod axons are coated in thick myelin sheaths, permitting rapid neural processing, such as rapid prey attack and intelligent predator avoidance; DHA may be required for the proper functioning of copepod neurons. Recent modeling results have suggested food webs with high quality primary producers (species high in HUFAs, i

  13. Genetic variants of the unsaturated fatty acid receptor GPR120 relating to obesity in dogs

    PubMed Central

    MIYABE, Masahiro; GIN, Azusa; ONOZAWA, Eri; DAIMON, Mana; YAMADA, Hana; ODA, Hitomi; MORI, Akihiro; MOMOTA, Yutaka; AZAKAMI, Daigo; YAMAMOTO, Ichiro; MOCHIZUKI, Mariko; SAKO, Toshinori; TAMURA, Katsutoshi; ISHIOKA, Katsumi

    2015-01-01

    G protein-coupled receptor (GPR) 120 is an unsaturated fatty acid receptor, which is associated with various physiological functions. It is reported that the genetic variant of GPR120, p.Arg270His, is detected more in obese people, and this genetic variation functionally relates to obesity in humans. Obesity is a common nutritional disorder also in dogs, but the genetic factors have not ever been identified in dogs. In this study, we investigated the molecular structure of canine GPR120 and searched for candidate genetic variants which may relate to obesity in dogs. Canine GPR120 was highly homologous to those of other species, and seven transmembrane domains and two N-glycosylation sites were conserved. GPR120 mRNA was expressed in lung, jejunum, ileum, colon, hypothalamus, hippocampus, spinal cord, bone marrow, dermis and white adipose tissues in dogs, as those in mice and humans. Genetic variants of GPR120 were explored in client-owned 141 dogs, resulting in that 5 synonymous and 4 non-synonymous variants were found. The variant c.595C>A (p.Pro199Thr) was found in 40 dogs, and the gene frequency was significantly higher in dogs with higher body condition scores, i.e. 0.320 in BCS4–5 dogs, 0.175 in BCS3 dogs and 0.000 in BCS2 dogs. We conclude that c.595C>A (p.Pro199Thr) is a candidate variant relating to obesity, which may be helpful for nutritional management of dogs. PMID:25960032

  14. Organosulfate Formation through the Heterogeneous Reaction of Sulfur Dioxide with Unsaturated Fatty Acids and Long-Chain Alkenes.

    PubMed

    Passananti, Monica; Kong, Lingdong; Shang, Jing; Dupart, Yoan; Perrier, Sébastien; Chen, Jianmin; Donaldson, D James; George, Christian

    2016-08-22

    The heterogeneous reaction between SO2 and unsaturated compounds results in the efficient production of organosulfates for several fatty acids and long-chain alkenes. The presence of an acid group, the physical state of the reactants (solid or liquid), the nature of the double bond (cis, trans, terminal), and the use of light irradiation all have an impact on the reaction rate. The reaction was investigated using different set-ups (coated flow tube, aerosol flow tube, and diffuse reflectance infrared Fourier transform cell). The reaction products were identified by high-resolution mass spectrometry and the impact of this reaction on organosulfate formation in the atmosphere is discussed. PMID:27458109

  15. Chiral Integrated Catalysts Composed of Bifunctional Thiourea and Arylboronic Acid: Asymmetric Aza-Michael Addition of α,β-Unsaturated Carboxylic Acids.

    PubMed

    Hayama, Noboru; Azuma, Takumi; Kobayashi, Yusuke; Takemoto, Yoshiji

    2016-01-01

    The first intermolecular asymmetric Michael addition of nitrogen-nucleophiles to α,β-unsaturated carboxylic acids was achieved through a new type of arylboronic acid equipped with chiral aminothiourea. The use of BnONH2 as a nucleophile gives a range of enantioenriched β-(benzyloxy)amino acid derivatives in good yields and with high enantioselectivity (up to 90% yield, 97% enantiomeric excess (ee)). The obtained products are efficiently converted to optically active β-amino acid and 1,2-diamine derivatives. PMID:27373626

  16. De Novo Transcriptome Analysis of Warburgia ugandensis to Identify Genes Involved in Terpenoids and Unsaturated Fatty Acids Biosynthesis

    PubMed Central

    Wang, Xin; Zhou, Chen; Yang, Xianpeng; Miao, Di; Zhang, Yansheng

    2015-01-01

    The bark of Warburgia ugandensis (Canellaceae family) has been used as a medicinal source for a long history in many African countries. The presence of diverse terpenoids and abundant polyunsaturated fatty acids (PUFAs) in this organ contributes to its broad range of pharmacological properties. Despite its medicinal and economic importance, the knowledge on the biosynthesis of terpenoid and unsaturated fatty acid in W. ugandensis bark remains largely unknown. Therefore, it is necessary to construct a genomic and/or transcriptomic database for the functional genomics study on W. ugandensis. The chemical profiles of terpenoids and fatty acids between the bark and leaves of W. ugandensis were compared by gas chromatography-mass spectrometry (GC-MS) analysis. Meanwhile, the transcriptome database derived from both tissues was created using Illumina sequencing technology. In total, about 17.1 G clean nucleotides were obtained, and de novo assembled into 72,591 unigenes, of which about 38.06% can be aligned to the NCBI non-redundant protein database. Many candidate genes in the biosynthetic pathways of terpenoids and unsaturated fatty acids were identified, including 14 unigenes for terpene synthases. Furthermore, 2,324 unigenes were discovered to be differentially expressed between both tissues; the functions of those differentially expressed genes (DEGs) were predicted by gene ontology enrichment and metabolic pathway enrichment analyses. In addition, the expression of 12 DEGs with putative roles in terpenoid and unsaturated fatty acid metabolic pathways was confirmed by qRT-PCRs, which was consistent with the data of the RNA-sequencing. In conclusion, we constructed a comprehensive transcriptome dataset derived from the bark and leaf of W. ugandensis, which forms the basis for functional genomics studies on this plant species. Particularly, the comparative analysis of the transcriptome data between the bark and leaf will provide critical clues to reveal the regulatory

  17. Genetic decrease in fatty acid unsaturation of phosphatidylglycerol increased photoinhibition of photosystem I at low temperature in tobacco leaves.

    PubMed

    Ivanov, A G; Allakhverdiev, S I; Huner, N P A; Murata, N

    2012-08-01

    Leaves of transgenic tobacco plants with decreased levels of fatty acid unsaturation in phosphatidylglycerol (PG) exhibited a slightly lower level of the steady state oxidation of the photosystem I (PSI) reaction center P700 (P700(+)) than wild-type plants. The PSI photochemistry of wild-type plants was only marginally affected by high light treatments. Surprisingly, all plants of transgenic lines exhibited much higher susceptibility to photoinhibition of PSI than wild-type plants. This was accompanied by a 2.5-fold faster re-reduction rate of P700(+) in the dark, indicating a higher capacity for cyclic electron flow around PSI in high light treated transgenic leaves. This was associated with a much higher intersystem electron pool size suggesting over-reduction of the PQ pool in tobacco transgenic lines with altered PG unsaturation compared to wild-type plants. The physiological role of PG unsaturation in PSI down-regulation and modulation of the capacity of PSI-dependent cyclic electron flows and distribution of excitation light energy in tobacco plants under photoinhibitory conditions at low temperatures is discussed. This article is part of a Special Issue entitled: Photosynthesis Research for Sustainability: from Natural to Artificial. PMID:22445720

  18. Gas chromatography-mass spectrometry profile of urinary organic acids of Wistar rats orally treated with ozonized unsaturated triglycerides and ozonized sunflower oil.

    PubMed

    Jardines, Daniel; Correa, Teresa; Ledea, Oscar; Zamora, Zullyt; Rosado, Aristides; Molerio, Jesús

    2003-01-15

    The main products in the ozonolysis of unsaturated triglycerides or vegetable oils are peroxides, aldehydes, Criegee ozonides and carboxylic acids. Some of these compounds are present in different concentrations in the biological fluids. The aim of this work is to study, using gas chromatography-mass spectrometry (GC-MS), the organic acid excretion in urine of rats orally treated with ozonized sunflower oil (OSO), ozonized triolein or ozonized trilinolein. Oral administration of OSO to Wistar rats has produced changes in the urinary content of dicarboxylic organic acids. Among others heptanedioic (pimelic acid) and nonanedioic acids (azelaic acid) were the major increased dicarboxylic acids found. The urinary dicarboxylic acid profiles of rats which received ozonized triolein only showed an increase in heptanedioic and nonanedioic acids. However, when ozonized trilinolein is applied, the profile is similar to that obtained when OSO is administered. A biochemical mechanism is proposed to explain the formation of dicarboxylic acids from ozonated unsaturated triglycerides. PMID:12482495

  19. Stabilized unsaturated polyesters

    NASA Technical Reports Server (NTRS)

    Vogl, O.; Borsig, E. (Inventor)

    1985-01-01

    An unsaturated polyester, such as propylene glycolmaleic acid phthalic acid prepolymer dissolved in styrene is interpolymerized with an ultraviolet absorber and/or an antioxidant. The unsaturated chain may be filled with H or lower alkyl such as methyl and tertiary alkyl such as tertiary butyl. A polymer stable to exposure to the outdoors without degradation by ultraviolet radiation, thermal and/or photooxidation is formed.

  20. Peripancreatic fat necrosis worsens acute pancreatitis independent of pancreatic necrosis via unsaturated fatty acids increased in human pancreatic necrosis collections

    PubMed Central

    Noel, Pawan; Patel, Krutika; Durgampudi, Chandra; Trivedi, Ram N; de Oliveira, Cristiane; Crowell, Michael D; Pannala, Rahul; Lee, Kenneth; Brand, Randall; Chennat, Jennifer; Slivka, Adam; Papachristou, Georgios I; Khalid, Asif; Whitcomb, David C; DeLany, James P; Cline, Rachel A; Acharya, Chathur; Jaligama, Deepthi; Murad, Faris M; Yadav, Dhiraj; Navina, Sarah; Singh, Vijay P

    2016-01-01

    Background and aims Peripancreatic fat necrosis occurs frequently in necrotising pancreatitis. Distinguishing markers from mediators of severe acute pancreatitis (SAP) is important since targeting mediators may improve outcomes. We evaluated potential agents in human pancreatic necrotic collections (NCs), pseudocysts (PCs) and pancreatic cystic neoplasms and used pancreatic acini, peripheral blood mononuclear cells (PBMC) and an acute pancreatitis (AP) model to determine SAP mediators. Methods We measured acinar and PBMC injury induced by agents increased in NCs and PCs. Outcomes of caerulein pancreatitis were studied in lean rats coadministered interleukin (IL)-1β and keratinocyte chemoattractant/growth-regulated oncogene, triolein alone or with the lipase inhibitor orlistat. Results NCs had higher fatty acids, IL-8 and IL-1β versus other fluids. Lipolysis of unsaturated triglyceride and resulting unsaturated fatty acids (UFA) oleic and linoleic acids induced necro-apoptosis at less than half the concentration in NCs but other agents did not do so at more than two times these concentrations. Cytokine coadministration resulted in higher pancreatic and lung inflammation than caerulein alone, but only triolein coadministration caused peripancreatic fat stranding, higher cytokines, UFAs, multisystem organ failure (MSOF) and mortality in 97% animals, which were prevented by orlistat. Conclusions UFAs, IL-1β and IL-8 are elevated in NCs. However, UFAs generated via peripancreatic fat lipolysis causes worse inflammation and MSOF, converting mild AP to SAP. PMID:25500204

  1. Light intensity and N/P nutrient affect the accumulation of lipid and unsaturated fatty acids by Chlorella sp.

    PubMed

    Guo, Xiaoyi; Su, Gaomin; Li, Zheng; Chang, Jingyu; Zeng, Xianhai; Sun, Yong; Lu, Yinghua; Lin, Lu

    2015-09-01

    In this study, different light intensities (80, 160, 240 and 320 μmol/m(2) s) and various mediums including control medium (CM), N/P rich medium (NPM), N rich medium (NM), and P rich medium (PM) were applied for cultivation of Chlorella sp. It was revealed that cultivation of Chlorella sp. in CM under the light intensity of 320 μmol/m(2) s led to a lipid content up to 30% enhancement, which was higher than the results of other cases. A rather high unsaturated fatty acid (UFA) content of 7.5% and unsaturated fatty acid/total fatty acid (UFA/TFA) ratio of 0.73 were obtained under 320 μmol/m(2) s in CM, indicating that the CM-320 system was applicable for the generation of UFA. Moreover, Chlorella sp. cultivated in PM under 320 μmol/m(2) s provided higher TFA content (7.3%), which was appropriate for biofuel production. PMID:25899143

  2. Unsaturated Fatty Acid, cis-2-Decenoic Acid, in Combination with Disinfectants or Antibiotics Removes Pre-Established Biofilms Formed by Food-Related Bacteria

    PubMed Central

    Sepehr, Shayesteh; Rahmani-Badi, Azadeh; Babaie-Naiej, Hamta; Soudi, Mohammad Reza

    2014-01-01

    Biofilm formation by food-related bacteria and food-related pathogenesis are significant problems in the food industry. Even though much disinfection and mechanical procedure exist for removal of biofilms, they may fail to eliminate pre-established biofilms. cis-2 decenoic acid (CDA), an unsaturated fatty acid messenger produced by Pseudomonas aeruginosa, is reportedly capable of inducing the dispersion of established biofilms by multiple types of microorganisms. However, whether CDA has potential to boost the actions of certain antimicrobials is unknown. Here, the activity of CDA as an inducer of pre-established biofilms dispersal, formed by four main food pathogens; Staphylococcus aureus, Bacillus cereus, Salmonella enterica and E. coli, was measured using both semi-batch and continuous cultures bioassays. To assess the ability of CDA combined biocides treatments to remove pre-established biofilms formed on stainless steel discs, CFU counts were performed for both treated and untreated cultures. Eradication of the biofilms by CDA combined antibiotics was evaluated using crystal violet staining. The effect of CDA combined treatments (antibiotics and disinfectants) on biofilm surface area and bacteria viability was evaluated using fluorescence microscopy, digital image analysis and LIVE/DEAD staining. MICs were also determined to assess the probable inhibitory effects of CDA combined treatments on the growth of tested microorganisms' planktonic cells. Treatment of pre-established biofilms with only 310 nM CDA resulted in at least two-fold increase in the number of planktonic cells in all cultures. While antibiotics or disinfectants alone exerted a trivial effect on CFU counts and percentage of surface area covered by the biofilms, combinational treatments with both 310 nM CDA and antibiotics or disinfectants led to approximate 80% reduction in biofilm biomass. These data suggests that combined treatments with CDA would pave the way toward developing new strategies

  3. Oxidation of cis-5-unsaturated fatty acids in intact rat liver mitochondria: the operation of reduction pathways.

    PubMed Central

    Tserng, K Y; Jin, S J

    1995-01-01

    The metabolism of cis-5 unsaturated fatty acids was studied in intact rat liver mitochondria to assess the operation of a reduction pathway. By using direct quantification of metabolites with a capillary-column gas chromatography, 3-hydroxydodecanoate was identified among other metabolites when cis-5-dodecenoate was metabolized in intact rat liver mitochondria. The formation of 3-hydroxydodecanoate supports the existence of a reduction pathway in the metabolism of cis-5-unsaturated fatty acids. This metabolite cannot be produced from the conventional isomerase-mediated pathway. However, the data also indicated the possible operation of the conventional isomerase-mediated pathway in intact rat liver mitochondria. The reduction pathway appears to account for at least 61% of the pathway for cis-5-dodecenoate. This reduction pathway was likely to proceed from the dehydrogenation to trans-2,cis-5-dodecadienoyl-CoA, which was isomerized to delta 3, delta 5-dodecadienoyl-CoA, then to trans-2,trans-4-dodecadienoate. The reduction was mediated by 2,4-dienoyl-CoA reductase by the conversion of trans-2,trans-4-dodecadienoyl-CoA into trans-3-dodecenoyl-CoA. However, direct reduction of the cis-5 double bond was also shown to be operating, although to a lesser extent. PMID:7755586

  4. Long-chain unsaturated fatty acids reduce the transcriptional activity of the rat follicle-stimulating hormone β-subunit gene

    PubMed Central

    MORIYAMA, Ryutaro; YAMAZAKI, Tsubasa; KATO, Takako; KATO, Yukio

    2016-01-01

    Here, we assessed the effects of long-chain fatty acids (LCFAs) and the LCFA receptor agonist GW9508 on the transcription of the gonadotropin subunit genes Cga, Lhb and Fshb because LCFA receptor GPR120 was observed in mouse gonadotropes in our recent study. A transcription assay using LβT2 cells demonstrated that LCFAs, oleic acid, α-linolenic acid, docosahexaenoic acid and palmitate, repressed the expression of Cga, Lhb, and Fshb at concentrations between 50 and 100 µM. On the other hand, treatment with 10 µM unsaturated LCFAs, oleic acid, α-linolenic acid and docosahexaenoic acid, repressed only Fshb expression, while the same dose of a saturated LCFA, palmitate, had no effect on the expression of gonadotropin subunit genes. Furthermore, GW9508 did not affect promoter activity. Next, we examined deletion mutants of the upstream region of Fshb and found that the upstream regulatory region (-2824 to -2343 bp) of Fshb was responsible for the notable repression by 10 µM unsaturated LCFAs. Our results suggest that the upstream region of Fshb is susceptible to unsaturated LCFAs. In addition, unsaturated LCFAs play a role in repressing Fshb expression through the distal -2824 to -2343 bp region, which might be independent of the LCFA receptor GPR120 pathway. PMID:26853521

  5. Combined effects of endurance training and dietary unsaturated fatty acids on physical performance, fat oxidation and insulin sensitivity.

    PubMed

    Boss, Andreas; Lecoultre, Virgile; Ruffieux, Christiane; Tappy, Luc; Schneiter, Philippe

    2010-04-01

    Endurance training improves exercise performance and insulin sensitivity, and these effects may be in part mediated by an enhanced fat oxidation. Since n-3 and n-9 unsaturated fatty acids may also increase fat oxidation, we hypothesised that a diet enriched in these fatty acids may enhance the effects of endurance training on exercise performance, insulin sensitivity and fat oxidation. To assess this hypothesis, sixteen normal-weight sedentary male subjects were randomly assigned to an isoenergetic diet enriched with fish and olive oils (unsaturated fatty acid group (UFA): 52 % carbohydrates, 34 % fat (12 % SFA, 12 % MUFA, 5 % PUFA), 14 % protein), or a control diet (control group (CON): 62 % carbohydrates, 24 % fat (12 % SFA, 6 % MUFA, 2 % PUFA), 14 % protein) and underwent a 10 d gradual endurance training protocol. Exercise performance was evaluated by measuring VO2max and the time to exhaustion during a cycling exercise at 80 % VO2max; glucose homeostasis was assessed after ingestion of a test meal. Fat oxidation was assessed by indirect calorimetry at rest and during an exercise at 50 % VO2max. Training significantly increased time to exhaustion, but not VO2max, and lowered incremental insulin area under the curve after the test meal, indicating improved insulin sensitivity. Those effects were, however, of similar magnitude in UFA and CON. Fat oxidation tended to increase in UFA, but not in CON. This difference was, however, not significant. It is concluded that a diet enriched with fish- and olive oil does not substantially enhance the effects of a short-term endurance training protocol in healthy young subjects. PMID:19948079

  6. Grape seed and linseed, alone and in combination, enhance unsaturated fatty acids in the milk of Sarda dairy sheep.

    PubMed

    Correddu, F; Gaspa, G; Pulina, G; Nudda, A

    2016-03-01

    This study evaluated the effect of dietary inclusion of grape seed and linseed, alone or in combination, on sheep milk fatty acids (FA) profile using 24 Sarda dairy ewes allocated to 4 isoproductive groups. Groups were randomly assigned to 4 dietary treatments consisting of a control diet (CON), a diet including 300 g/d per animal of grape seed (GS), a diet including 220 g/d per animal of extruded linseed (LIN), and a diet including a mix of 300 g/d per animal of grape seed and 220 g/d per animal of extruded linseed (MIX). The study lasted 10 wk, with a 2-wk adaptation period and an 8-wk experimental period. Milk FA composition was analyzed in milk samples collected in the last 4 wk of the trial. The milk concentration of saturated fatty acids (SFA) decreased and that of unsaturated, monounsaturated, and polyunsaturated fatty acids (UFA, MUFA, and PUFA, respectively) increased in GS, LIN, and MIX groups compared with CON. The MIX group showed the lowest values of SFA and the highest of UFA, MUFA, and PUFA. Milk from ewes fed linseed (LIN and MIX) showed an enrichment of vaccenic acid (VA), oleic acid (OA), α-linolenic acid (LNA), and cis-9,trans-11 conjugated linoleic acid (CLA) compared with milk from the CON group. The GS group showed a greater content of milk oleic acid (OA) and linoleic acid (LA) and tended to show a greater content of VA and cis-9,trans-11 CLA than the CON group. The inclusion of grape seed and linseed, alone and in combination, decreased the milk concentration of de novo synthesized FA C10:0, C12:0, and C14:0, with the MIX group showing the lowest values. In conclusion, grape seed and linseed could be useful to increase the concentration of FA with potential health benefits, especially when these ingredients are included in combination in the diet. PMID:26774716

  7. Formation and Fragmentation of Unsaturated Fatty Acid [M - 2H + Na]- Ions: Stabilized Carbanions for Charge-Directed Fragmentation

    NASA Astrophysics Data System (ADS)

    Thomas, Michael C.; Kirk, Benjamin B.; Altvater, Jens; Blanksby, Stephen J.; Nette, Geoffrey W.

    2013-12-01

    Fatty acids are long-chain carboxylic acids that readily produce [M - H]- ions upon negative ion electrospray ionization (ESI) and cationic complexes with alkali, alkaline earth, and transition metals in positive ion ESI. In contrast, only one anionic monomeric fatty acid-metal ion complex has been reported in the literature, namely [M - 2H + FeIICl]-. In this manuscript, we present two methods to form anionic unsaturated fatty acid-sodium ion complexes (i.e., [M - 2H + Na]-). We find that these ions may be generated efficiently by two distinct methods: (1) negative ion ESI of a methanolic solution containing the fatty acid and sodium fluoride forming an [M - H + NaF]- ion. Subsequent collision-induced dissociation (CID) results in the desired [M - 2H + Na]- ion via the neutral loss of HF. (2) Direct formation of the [M - 2H + Na]- ion by negative ion ESI of a methanolic solution containing the fatty acid and sodium hydroxide or bicarbonate. In addition to deprotonation of the carboxylic acid moiety, formation of [M - 2H + Na]- ions requires the removal of a proton from the fatty acid acyl chain. We propose that this deprotonation occurs at the bis-allylic position(s) of polyunsaturated fatty acids resulting in the formation of a resonance-stabilized carbanion. This proposal is supported by ab initio calculations, which reveal that removal of a proton from the bis-allylic position, followed by neutral loss of HX (where X = F- and -OH), is the lowest energy dissociation pathway.

  8. Animal performance and milk fatty acid profile of dairy goats fed diets with different unsaturated plant oils.

    PubMed

    Martínez Marín, A L; Gómez-Cortés, P; Gómez Castro, A G; Juárez, M; Pérez Alba, L M; Pérez Hernández, M; de la Fuente, M A

    2011-11-01

    The effect of supplementing a basal diet with 1 of 3 plant oils on productive efficiency and milk fatty acid composition was studied in dairy goats. Sixteen Malagueña goats were used in a 4×4 Latin square experiment with 21-d periods and 4 goats per treatment. The basal diet comprised 30% alfalfa hay and 70% pelleted concentrate. Experimental treatments were control (basal diet without added oil) and the basal diet supplemented with 48g/d of high oleic sunflower oil (HOSFO), regular sunflower oil (RSFO), or linseed oil (LO). Dry matter intake and body weight were not affected by treatments. Milk production was higher in HOSFO treatment and milk fat content was higher in RSFO and LO treatments, although no differences in milk energy production or milk renneting properties were found. The RSFO and LO treatments increased the proportion of vaccenic acid in milk fat more so than the HOSFO diet, and rumenic acid followed the same pattern. The content of trans10-18:1 remained low in all experimental diets (<0.7% of total fatty acid methyl esters) although HOSFO and RSFO diets increased it. The variations in the fatty acid profiles observed with the 4 diets, mainly the unsaturated fatty acid isomer contents, are extensively discussed. Compared with that in the control diet, the n-6:n-3 fatty acid ratio in milk fat substantially decreased with the LO, increased with RSFO, and did not change with HOSFO. The addition of moderate amounts of LO to the diets of dairy goats has favorable effects on milk fatty acid composition from the point of view of the human consumer, without negative effects on animal performance. PMID:22032358

  9. Chiral Nanoparticles/Lewis Acids as Cooperative Catalysts for Asymmetric 1,4-Addition of Arylboronic Acids to α,β-Unsaturated Amides.

    PubMed

    Yasukawa, Tomohiro; Saito, Yuuki; Miyamura, Hiroyuki; Kobayashi, Shū

    2016-07-01

    Cooperative catalysts consisting of chiral Rh/Ag nanoparticles and Sc(OTf)3 have been developed that catalyze asymmetric 1,4-addition reactions of arylboronic acids with α,β-unsaturated amides efficiently. The reaction has been considered one of the most challenging reactions because of the low reactivity of the amide substrates. The new catalysts provide the desired products with outstanding enantioselectivities (>98 % ee) in the presence of low loadings (<0.5 mol %) of the catalyst. PMID:27193210

  10. Combined analysis of C-18 unsaturated fatty acids using natural abundance deuterium 2D NMR spectroscopy in chiral oriented solvents.

    PubMed

    Lesot, Philippe; Baillif, Vincent; Billault, Isabelle

    2008-04-15

    The quantitative determination of isotopic (2H/1H)i ratios at natural abundance using the SNIF-NMR protocol is a well-known method for understanding the enzymatic biosynthesis of metabolites. However, this approach is not always successful for analyzing large solutes and, specifically, is inadequate for prochiral molecules such as complete essential unsaturated fatty acids. To overcome these analytical limitations, we use the natural abundance deuterium 2D NMR (NAD 2D NMR) spectroscopy on solutes embedded in polypeptide chiral liquid crystals. This approach, recently explored for measuring (2H/1H)i ratios of small analytes (Lesot, P.; Aroulanda, C.; Billault, I. Anal. Chem. 2004, 76, 2827-2835), is a powerful way to separate the 2H signals of all nonequivalent enantioisotopomers on the basis both of the 2H quadrupolar interactions and of the 2H chemical shift. Two significant advances over our previous work are presented here and allow the complete isotopic analysis of four mono- and polyunsaturated fatty acid methyl esters: methyl oleate (1), methyl linoleate (2), methyl linolenate (3), and methyl vernoleate (4). The first consists of using NMR spectrometers operating at higher magnetic field strength (14.1 T) and equipped with a selective cryoprobe optimized for deuterium nuclei. The second is the development of Q-COSY Fz 2D NMR experiments able to produce phased 2H 2D maps after a double Fourier transformation. This combination of modern hardware and efficient NMR sequences provides a unique tool to analyze the (2H/1H)i ratios of large prochiral molecules (C-18) dissolved in organic solutions of poly(gamma-benzyl-L-glutamate) and requires smaller amounts of solute than previous study on fatty acids. For each compound (1-4), all 2H quadrupolar doublets visible in the 2D spectra have been assigned on the basis of 2H chemical shifts, isotopic data obtained from isotropic quantitative NAD NMR, and by an interspectral comparison of the anisotropic NAD spectra of four

  11. Highly enantioselective hydrogenation of α-oxy functionalized α,β-unsaturated acids catalyzed by a ChenPhos-Rh complex in CF3CH2OH.

    PubMed

    Yao, Lin; Wen, Jialin; Liu, Shaodong; Tan, Renchang; Wood, Noel Marie; Chen, Weiping; Zhang, Shengyong; Zhang, Xumu

    2016-02-01

    Rhodium complexes coordinated by Chenphos are very effective catalysts for the enantioselective hydrogenation of α-aryloxy- and α-alkoxy-substituted α,β-unsaturated carboxylic acids under mild conditions in CF3CH2OH. The catalytic system could be successfully employed in building the core structure of a new FDA approved drug LCZ 696. PMID:26730444

  12. Nanohybrids of Mg/Al layered double hydroxide and long-chain (C18) unsaturated fatty acid anions: Structure and sorptive properties

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Long-chain (C18) unsaturated fatty acid anions, elaidate (ELA), oleate (OLE), linoleate (LINO), and linolenate (LINOLEN), were intercalated into Mg/Al (3:1) layered double hydroxide (LDH) and the resultant organo-LDH nanohybrid materials were characterized and subsequently evaluated as sorbents of s...

  13. 40 CFR 721.3025 - Fatty acids C12-18, C18 unsaturated, C12-18 alkyl esters (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ..., C12-18 alkyl esters (generic). 721.3025 Section 721.3025 Protection of Environment ENVIRONMENTAL... alkyl esters (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as fatty acids C12-18, C18 unsaturated, C12-18 alkyl esters...

  14. Human platelets respond differentially to lysophosphatidic acids having a highly unsaturated fatty acyl group and alkyl ether-linked lysophosphatidic acids.

    PubMed Central

    Tokumura, Akira; Sinomiya, Junya; Kishimoto, Seishi; Tanaka, Tamotsu; Kogure, Kentaro; Sugiura, Takayuki; Satouchi, Kiyoshi; Waku, Keizo; Fukuzawa, Kenji

    2002-01-01

    Lysophosphatidic acid (LPA) is a physiological agonist that is produced by lysophospholipase D, phospholipase A(1) and phospholipase A(2) in the blood of animals. It exerts diverse biological actions on a broad range of animal cells. Specific receptors for this important agonist have been characterized. In this investigation, for the first time we prepared LPAs having a highly unsaturated fatty acyl group, such as the eicosapentaenoyl or docosahexaenoyl residue, and their acetylated derivatives. Human platelets aggregated more potently in response to the highly unsaturated acyl-LPAs than to LPAs with a C(18) fatty acyl group, such as an oleoyl group, while alkyl ether-linked LPAs (alkyl-LPA) had much stronger aggregating activity. Two positional isomers of LPAs with an arachidonoyl, eicosapentaenoyl or docosahexaenoyl group had equipotent aggregatory activity as well as the positional isomers of their acetylated analogues, indicating that putative LPA receptors could not distinguish the difference between the positional isomers. We found that platelet preparations from two individuals showed no aggregatory response to alkyl-LPAs, although they contained mRNAs for known LPA receptors in the following order of expression level: endothelial differentiation gene (Edg)-4>Edg-7>Edg-2. We also obtained evidence that 2-(p-amylcinnamoyl)amino-4-chlorobenzoic acid (ONO-RS-082), a phospholipase A(2) inhibitor, potentiated alkyl-LPA-induced platelet aggregation, but inhibited highly unsaturated acyl-LPA-induced platelet aggregation. These results indicated that human platelets express acyl-LPA-selective and alkyl-LPA-selective receptors on their plasma membrane. PMID:11982483

  15. Increase of Unsaturated Fatty Acids (Low Melting Point) of Broiler Fatty Waste Obtained Through Staphylococcus xylosus Fermentation.

    PubMed

    Marques, Roger V; Duval, Eduarda H; Corrêa, Luciara B; Corrêa, Érico K

    2015-11-01

    The increasing rise in the production of meat around the world causes a significant generation of agro-industrial waste--most of it with a low value added. Fatty wastes have the potential of being converted into biodiesel, given the overcome of technological and economical barriers, as well as its presentation in solid form. Therefore, the aim of this work was to investigate the capacity of Staphylococcus xylosus strains to modify the chemical structure of chicken fatty wastes intending to reduce the melting points of the wastes to mild temperatures, thereby breaking new ground in the production of biodiesel from these sources in an economically attractive and sustainable manner. The effects in time of fermentation and concentration of the fat in the medium were investigated, assessing the melting point and profile of fatty acids. The melting temperature showed a decrease of approximately 22 °C in the best operational conditions, due to reduction in the content of saturated fatty acids (high melting point) and increase of unsaturated fatty acids (low melting point). PMID:26289722

  16. Dietary supplementation with either saturated or unsaturated fatty acids does not affect the mechanoenergetics of the isolated rat heart

    PubMed Central

    Goo, Soyeon; Han, June‐Chiew; Nisbet, Linley A.; LeGrice, Ian J.; Taberner, Andrew J.; Loiselle, Denis S.

    2014-01-01

    Abstract It is generally recognized that increased consumption of polyunsaturated fatty acids, fish oil (FO) in particular, is beneficial to cardiac and cardiovascular health, whereas equivalent consumption of saturated fats is deleterious. In this study, we explore this divergence, adopting a limited purview: The effect of dietary fatty acids on the mechanoenergetics of the isolated heart per se. Mechanical indices of interest include left‐ventricular (LV) developed pressure, stroke work, cardiac output, coronary perfusion, and LV power. The principal energetic index is whole‐heart oxygen consumption, which we subdivide into its active and basal moieties. The primary mechanoenergetic index of interest is cardiac efficiency, the ratio of work performance to metabolic energy expenditure. Wistar rats were divided into three Diet groups and fed, ad libitum, reference (REF), fish oil‐supplemented (FO), or saturated fatty acid‐supplemented (SFA) food for 6 weeks. At the end of the dietary period, hearts were excised, mounted in a working‐heart rig, and their mechanoenergetic performance quantified over a range of preloads and afterloads. Analyses of Variance revealed no difference in any of the individual mechanoenergetic indices among the three Diet groups. In particular, we found no effect of prior dietary supplementation with either saturated or unsaturated fatty acids on the global efficiency of the heart. PMID:24760525

  17. Visible Light-Induced Lipid Peroxidation of Unsaturated Fatty Acids in the Retina and the Inhibitory Effects of Blueberry Polyphenols.

    PubMed

    Liu, Yixiang; Zhang, Di; Hu, Jimei; Liu, Guangming; Chen, Jun; Sun, Lechang; Jiang, Zedong; Zhang, Xichun; Chen, Qingchou; Ji, Baoping

    2015-10-28

    The lipid peroxidation of unsaturated fatty acids (UFAs) in the retina not only threatens visual cells but also affects the physiological health of the retina. In this work, the potential damages caused by daily visible light exposure on retinal UFAs were evaluated via a simulated in vitro model. At the same time, the benefits of dietary supplementation of blueberries to the eyes were also assessed. After prolonged light exposure, lipid peroxidation occurred for both docosahexaenoic and arachidonic acids (DHA and AA, respectively). The oxidized UFAs presented obvious cytotoxicity and significantly inhibited cell growth in retinal pigment epithelium cells. Among the different blueberry polyphenol fractions, the flavonoid-rich fraction, in which quercetin was discovered as the main component, was considerably better in preventing visible light-induced DHA lipid peroxidation than the anthocyanin- and phenolic acid-rich fractions. Then the retinal protective activity of blueberry polyphenols against light-induced retinal injury was confirmed in vivo. On the basis of the above results, inhibiting lipid peroxidation of UFAs in the retina is proposed to be another important function mechanism for antioxidants to nourish eyes. PMID:26456696

  18. Marine omega-3 highly unsaturated fatty acids: From mechanisms to clinical implications in heart failure and arrhythmias.

    PubMed

    Glück, Tobias; Alter, Peter

    2016-07-01

    Therapeutic implications of marine omega-3 highly unsaturated fatty acids (HUFA) in cardiovascular disease are still discussed controversially. Several clinical trials report divergent findings and thus leave ambiguity on the meaning of oral omega-3 therapy. Potential prognostic indications of HUFA treatment have been predominantly studied in coronary artery disease, sudden cardiac death, ventricular arrhythmias, atrial fibrillation and heart failure of various origin. It is suspected that increased ventricular wall stress is crucially involved in the prognosis of heart failure. Increased wall stress and an unfavorable myocardial remodeling is associated with an increased risk of arrhythmias by stretch-activated membrane ion channels. Integration of HUFA into the microenvironment of cardiomyocyte ion channels lead to allosteric changes and increase the electrical stability. Increased ventricular wall stress appears to be involved in the local myocardial as well as in the hepatic fatty acid metabolism, i.e. a cardio-hepatic syndrome. Influences of an altered endogenous HUFA metabolism and an inverse shift of the fatty acid profile was underrated in the past. A better understanding of these interacting endogenous mechanisms appears to be required for interpreting the findings of recent experimental and clinical studies. The present article critically reviews major studies on basic pathophysiological mechanisms and treatment effects in clinical trials. PMID:27080538

  19. Process for the synthesis of unsaturated alcohols

    DOEpatents

    Maughon, Bob R.; Burdett, Kenneth A.; Lysenko, Zenon

    2007-02-13

    A process of preparing an unsaturated alcohol (olefin alcohol), such as, a homo-allylic mono-alcohol or homo-allylic polyol, involving protecting a hydroxy-substituted unsaturated fatty acid or fatty acid ester, such as methyl ricinoleate, derived from a seed oil, to form a hydroxy-protected unsaturated fatty acid or fatty acid ester; homo-metathesizing or cross-metathesizing the hydroxy-protected unsaturated fatty acid or fatty acid ester to produce a product mixture containing a hydroxy-protected unsaturated metathesis product; and deprotecting the hydroxy-protected unsaturated metathesis product under conditions sufficient to prepare the unsaturated alcohol. Preferably, methyl ricinoleate is converted by cross-metathesis or homo-metathesis into the homo-allylic mono-alcohol 1-decene-4-ol or the homo-allylic polyol 9-octadecene-7,12-diol, respectively.

  20. Acquisition and biosynthesis of saturated and unsaturated fatty acids by trypanosomatids.

    PubMed

    Uttaro, Antonio D

    2014-08-01

    As components of phospholipids and glycosylphosphatidylinositol anchors, fatty acids are responsible for forming the core of biological membranes and the correct localization of proteins within membranes. They also contribute to anchoring proteins by direct acylation of specific amino acids. Fatty acids can be used as energy sources and serve as signaling molecules or precursors for their synthesis. All these processes highlight the important role of fatty acids in cell physiology, justifying the diverse strategies for their acquisition evolved by different organisms. This review describes several recent findings in the salvage and biosynthesis of fatty acids by parasitic protists belonging to the class Kinetoplastea. They include two biosynthetic routes, the mitochondrial one and a peculiar membrane-associated pathway, the synthesis of polyunsaturated fatty acids, and the scavenging of lysophospholipids and lipoproteins from host plasma. These different processes are also explored as putative targets for chemotherapy. PMID:24726787

  1. QTL analysis of unsaturated fatty acids in a recombinant inbred population of soybean

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Soybean [Glycine max (L.) Merr.] is an important oilseed crop which produces around 30% of the world’s edible vegetable oil. The quality of soybean oil is determined by its fatty acid composition. Vegetable oils high in oleic and low in linolenic fatty acids are desirable for human consumption and...

  2. Analysis of Long-Chain Unsaturated Fatty Acids by Ionic Liquid Gas Chromatography.

    PubMed

    Weatherly, Choyce A; Zhang, Ying; Smuts, Jonathan P; Fan, Hui; Xu, Chengdong; Schug, Kevin A; Lang, John C; Armstrong, Daniel W

    2016-02-17

    Four ionic liquid (IL) columns, SLB-IL59, SLB-IL60, SLB-IL65, and SLB-IL111, were evaluated for more rapid analysis or improved resolution of long-chain methyl and ethyl esters of omega-3, omega-6, and additional positional isomeric and stereoisomeric blends of fatty acids found in fish oil, flaxseed oil, and potentially more complicated compositions. The three structurally distinct IL columns provided shorter retention times and more symmetric peak shapes for the fatty acid methyl or ethyl esters than a conventional polyethylene glycol column (PEG), resolving cis- and trans-fatty acid isomers that coeluted on the PEG column. The potential for improved resolution of fatty acid esters is important for complex food and supplement applications, where different forms of fatty acid can be incorporated. Vacuum ultraviolet detection contributed to further resolution for intricate mixtures containing cis- and trans-isomers, as exemplified in a fatty acid blend of shorter chain C18:1 esters with longer chain polyunsaturated fatty acid (PUFA) esters. PMID:26852774

  3. Effect of unsaturations on the physical properties of a model membrane with the highly polyunsaturated docosahexaenoic fatty acid

    NASA Astrophysics Data System (ADS)

    Saiz, Leonor; Klein, Michael L.

    2001-03-01

    Polyunsaturated fatty acids are an essential component of biomembranes. The docosahexaenoic fatty acid (DHA), in particular, is found in high concentrations in retinal and neuronal tissue and in the olfactory bulb. Furthermore, it is well known the ability of DHA rich membranes to modulate membrane protein function, in some situations, by modifying the membrane physical properties. A particularly well studied situation is the DHA effect onthe activity of the visual receptor (protein) rhodopsin. Here, we study at a microscopic level this type of complex systems under physiological conditions. In this way, we can probe the molecular origin of the peculiarities that the system confers to membranes. To this purpose, the structure of a fully hydrated mixed (saturated/polyunsaturated) chain lipid bilayer in the biologically relevant liquid crystalline phase has been examined by performing molecular dynamics simulations. The model membrane, a 1-stearoyl- 2-docosahexaenoic- sn-glycero- 3-phosphatidylcholine (18:0/22:6 PC) lipid bilayer, was investigated at room temperature and ambient pressure and the results obtained in the nanosecond time scale were in good agreement with the available experimental data. Among the effects of the multiple unsaturations on the physical properties of these membranes, we focus on the enhanced permeability to water and small organic solvents, the decreased area compressibility modulus, and the domain formation and chain segregation.

  4. Unsaturated Long Chain Free Fatty Acids Are Input Signals of the Salmonella enterica PhoP/PhoQ Regulatory System*

    PubMed Central

    Viarengo, Gastón; Sciara, Mariela I.; Salazar, Mario O.; Kieffer, Pablo M.; Furlán, Ricardo L. E.; García Véscovi, Eleonora

    2013-01-01

    The Salmonella enterica serovar Typhimurium PhoP/PhoQ system has largely been studied as a paradigmatic two-component regulatory system not only to dissect structural and functional aspects of signal transduction in bacteria but also to gain knowledge about the versatile devices that have evolved allowing a pathogenic bacterium to adjust to or counteract environmental stressful conditions along its life cycle. Mg2+ limitation, acidic pH, and the presence of cationic antimicrobial peptides have been identified as cues that the sensor protein PhoQ can monitor to reprogram Salmonella gene expression to cope with extra- or intracellular challenging conditions. In this work, we show for the first time that long chain unsaturated free fatty acids (LCUFAs) present in Salmonella growth medium are signals specifically detected by PhoQ. We demonstrate that LCUFAs inhibit PhoQ autokinase activity, turning off the expression of the PhoP-dependent regulon. We also show that LCUFAs exert their action independently of their cellular uptake and metabolic utilization by means of the β-oxidative pathway. Our findings put forth the complexity of input signals that can converge to finely tune the activity of the PhoP/PhoQ system. In addition, they provide a new potential biochemical platform for the development of antibacterial strategies to fight against Salmonella infections. PMID:23782700

  5. A study of the autoxidation of some unsaturated fatty acid methyl esters using Fourier transform Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Agbenyega, J. K.; Claybourn, M.; Ellis, G.

    Near-infrared Fourier transform Raman and Fourier transform infrared spectroscopy have been used to investigate the chemical changes taking place during the curing reaction of several fatty acid methyl esters, which are used for modelling processes in the autoxidation of alkyd resin coatings. We have studied methyl oleate, methyl linoleate, and methyl linolenate in an attempt to monitor the degree of unsaturation within the fatty acid methyl esters (FAMES) during the complex autoxidation/polymerisation reaction that takes place once the paint system is coated onto a substrate and exposed to the atmosphere. The peaks around 1655 cm -1 have been assigned as follows: to the trans isomer at 1670 cm -1, the cis isomer at 1655 cm -1 and the conjugated structure at 1640 cm -1 [B. Schrader, Raman/Infrared Atlas of Organic Compounds (2nd Edn), VCH, Weinheim (1989); J. K. Abenyega, M. Claybourn and G. Ellis, in preparations]. Raman spectra for the cure of methyl linoleate after 24 h show several interesting features, suggesting the formation of a highly conjugated cyclic structure. Current theories about the mechanism for the autoxidation of methyl linoleate make no mention of this aromatic product.

  6. Unsaturated long chain free fatty acids are input signals of the Salmonella enterica PhoP/PhoQ regulatory system.

    PubMed

    Viarengo, Gastón; Sciara, Mariela I; Salazar, Mario O; Kieffer, Pablo M; Furlán, Ricardo L E; García Véscovi, Eleonora

    2013-08-01

    The Salmonella enterica serovar Typhimurium PhoP/PhoQ system has largely been studied as a paradigmatic two-component regulatory system not only to dissect structural and functional aspects of signal transduction in bacteria but also to gain knowledge about the versatile devices that have evolved allowing a pathogenic bacterium to adjust to or counteract environmental stressful conditions along its life cycle. Mg(2+) limitation, acidic pH, and the presence of cationic antimicrobial peptides have been identified as cues that the sensor protein PhoQ can monitor to reprogram Salmonella gene expression to cope with extra- or intracellular challenging conditions. In this work, we show for the first time that long chain unsaturated free fatty acids (LCUFAs) present in Salmonella growth medium are signals specifically detected by PhoQ. We demonstrate that LCUFAs inhibit PhoQ autokinase activity, turning off the expression of the PhoP-dependent regulon. We also show that LCUFAs exert their action independently of their cellular uptake and metabolic utilization by means of the β-oxidative pathway. Our findings put forth the complexity of input signals that can converge to finely tune the activity of the PhoP/PhoQ system. In addition, they provide a new potential biochemical platform for the development of antibacterial strategies to fight against Salmonella infections. PMID:23782700

  7. Unsaturated C3,5,7,9-Monocarboxylic Acids by Aqueous, One-Pot Carbon Fixation: Possible Relevance for the Origin of Life

    PubMed Central

    Scheidler, Christopher; Sobotta, Jessica; Eisenreich, Wolfgang; Wächtershäuser, Günter; Huber, Claudia

    2016-01-01

    All scientific approaches to the origin of life share a common problem: a chemical path to lipids as main constituents of extant cellular enclosures. Here we show by isotope-controlled experiments that unsaturated C3,5,7,9-monocarboxylic acids form by one-pot reaction of acetylene (C2H2) and carbon monoxide (CO) in contact with nickel sulfide (NiS) in hot aqueous medium. The primary products are toto-olefinic monocarboxylic acids with CO-derived COOH groups undergoing subsequent stepwise hydrogenation with CO as reductant. In the resulting unsaturated monocarboxylic acids the double bonds are mainly centrally located with mainly trans-configuration. The reaction conditions are compatible with an origin of life in volcanic-hydrothermal sub-seafloor flow ducts. PMID:27283227

  8. [Bounds of change in unsaturation index of fatty acid composition of phospholipids at adaptation of molluscs to biogenic and abiogenic factors of external medium].

    PubMed

    Chebotareva, M A; Zabelinskiĭ, S A; Shukoliukova, E P; Krivchenko, A I

    2011-01-01

    Comparative study of fatty acid composition of total phospholipids, as well as of phosphatidylcholine and phosphatidylethanolamine from hepatopancreas and leg muscle was performed on several representatives of gasteropods (Gastropoda) molluscs and bivalve (Bivalvia) mussel (Mytilus edulus). The objects of our study were marine litorins (Littorina saxsatilis) adapted to different temperature conditions of White Sea and Barents Sea, freshwater lymnaea (Lymnaea stagnalis) infested by Trematoda and mussels from White Sea and Black Sea. It was shown that depending on the existence conditions of studied tissue or lipid, the maximal change is observed in the percentage of saturated acids (4-83 %), the percentage of unsaturated acids was less expressed (1-14 %) and the changes in unsaturation index (UI) did not exceed 20 % on average. It was supposed that observed quantitative bounds of UI change under the action of different external factors is utmost for maintenance of membrane fluidity necessary for normal vital activity of cell, particularly in studied ectothermic molluscs. PMID:22145319

  9. Unsaturated C3,5,7,9-Monocarboxylic Acids by Aqueous, One-Pot Carbon Fixation: Possible Relevance for the Origin of Life.

    PubMed

    Scheidler, Christopher; Sobotta, Jessica; Eisenreich, Wolfgang; Wächtershäuser, Günter; Huber, Claudia

    2016-01-01

    All scientific approaches to the origin of life share a common problem: a chemical path to lipids as main constituents of extant cellular enclosures. Here we show by isotope-controlled experiments that unsaturated C3,5,7,9-monocarboxylic acids form by one-pot reaction of acetylene (C2H2) and carbon monoxide (CO) in contact with nickel sulfide (NiS) in hot aqueous medium. The primary products are toto-olefinic monocarboxylic acids with CO-derived COOH groups undergoing subsequent stepwise hydrogenation with CO as reductant. In the resulting unsaturated monocarboxylic acids the double bonds are mainly centrally located with mainly trans-configuration. The reaction conditions are compatible with an origin of life in volcanic-hydrothermal sub-seafloor flow ducts. PMID:27283227

  10. The influence of thermal processing on the fatty acid profile of pork and lamb meat fed diet with increased levels of unsaturated fatty acids.

    PubMed

    Janiszewski, Piotr; Grześkowiak, Eugenia; Lisiak, Dariusz; Borys, Bronisław; Borzuta, Karol; Pospiech, Edward; Poławska, Ewa

    2016-01-01

    The research was carried out on 32 crossbred pigs of Polish Large White × Danish Landrace with Duroc and 80 rams, crossbreds of the Prolific-Dairy Koludzka Sheep with the Ile de France, a meat sheep. The fodder for the animals was enriched with the unsaturated fatty acids originated mainly from linseed and rapeseed oils. The fatty acid profile was determined in cooked longissimus lumborum, roasted triceps brachii and raw ripened rump from pigs as well as in grilled lambs' legs and their corresponding raw materials. Roasting caused the most pronounced increase of the saturated fatty acids and decrease in the polyunsaturated fatty acids of heated pork muscles. The smallest changes were observed in grilled lamb legs. The heating processes applied in this study, in most cases, did not cause essential changes in the indices of pro-health properties of fatty acid, therefore meat in the majority fulfil the latest recommendations of EFSA and FAO/WHO according to human health. PMID:26422798

  11. Engineering Escherichia coli for the synthesis of short- and medium-chain α,β-unsaturated carboxylic acids.

    PubMed

    Kim, Seohyoung; Cheong, Seokjung; Gonzalez, Ramon

    2016-07-01

    Concerns over sustained availability of fossil resources along with environmental impact of their use have stimulated the development of alternative methods for fuel and chemical production from renewable resources. In this work, we present a new approach to produce α,β-unsaturated carboxylic acids (α,β-UCAs) using an engineered reversal of the β-oxidation (r-BOX) cycle. To increase the availability of both acyl-CoAs and enoyl-CoAs for α,β-UCA production, we use an engineered Escherichia coli strain devoid of mixed-acid fermentation pathways and known thioesterases. Core genes for r-BOX such as thiolase, hydroxyacyl-CoA dehydrogenase, enoyl-CoA hydratase, and enoyl-CoA reductase were chromosomally overexpressed under the control of a cumate inducible phage promoter. Native E. coli thioesterase YdiI was used as the cycle-terminating enzyme, as it was found to have not only the ability to convert trans-enoyl-CoAs to the corresponding α,β-UCAs, but also a very low catalytic efficiency on acetyl-CoA, the primer and extender unit for the r-BOX pathway. Coupling of r-BOX with YdiI led to crotonic acid production at titers reaching 1.5g/L in flask cultures and 3.2g/L in a controlled bioreactor. The engineered r-BOX pathway was also used to achieve for the first time the production of 2-hexenoic acid, 2-octenoic acid, and 2-decenoic acid at a final titer of 0.2g/L. The superior nature of the engineered pathway was further validated through the use of in silico metabolic flux analysis, which showed the ability of r-BOX to support growth-coupled production of α,β-UCAs with a higher ATP efficiency than the widely used fatty acid biosynthesis pathway. Taken together, our findings suggest that r-BOX could be an ideal platform to implement the biological production of α,β-UCAs. PMID:26996381

  12. The Effect of Unsaturated Fatty Acids on Molecular Markers of Cholesterol Homeostasis in THP-1 Macrophages

    PubMed Central

    Zavar Reza, Javad; Nahangi, Hossein; Mansouri, Reza; Dehghani, Ali; Mojarrad, Majid; Fathi, Mohammad; Nikzamir, Abdolrahim; Yekaninejad, Mir Saeed

    2013-01-01

    Background Macrophages derived foam cells are key factors in the maladaptive immune and inflammatory response. Objectives The study of the cholesterol homeostasis and the molecular factor involved in these cells is very important in understanding the process of atherosclerosis and the mechanisms that prevent its occurrence. Materials and Methods This experimental study investigated the effects of c9, t11-Conjugated Linoleic Acid (c9, t11-CLA). Alpha Linolenic Acid (LA), and Eicosapentaenoic Acid (EPA) on the PPARα and ACAT1 mRNA expression by Real time PCR and cholesterol homeostasis in THP-1 macrophages derived foam cells. Results Incubation of CLA, LA, EPA, and synthetic ligands did not prevent increasing the cellular total cholesterol (TC). Free cholesterol (FC) is increased by Sandoz58-035 (P = 0.024) and decreased by fatty acids and Wy14643 (Pirinixic acid) (P = 0.035). The pattern of distribution of %EC is similar to the EC pattern distribution. The ACAT1 mRNA expression was significantly increased by EPA (P = 0.009), but c9, t11- CLA, LA, Wy14643, and Sandoz58-035 had no significant effect on the mRNA level of ACAT1 expression compared to DMSO(Dimethyl sulfoxide). Discussions In comparison to the control of Wy14643, Sandoz58-035, c9 and t11-CLA, EPA increased the PPARα mRNA levels (P = 0.024, P = 0.041, P = 0.043, and P = 0.004, respectively), even though, LA had no significant effect on the PPARα mRNA expression (P = 0.489). Conclusions Variations in the chemical structure of fatty acids can affect their physiological function. PMID:24396573

  13. Use of vitamin E to protect highly unsaturated fatty acids in poultry feeds

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Vitamin E can protect sensitive compounds from oxidative degradation but at high concentrations it acts as a prooxidant to accelerate oxidative degradation process. The addition of polyunsaturated acids to poultry feeds provides a straightforward approach to improve the nutritional quality of poultr...

  14. Bioavailability of xenobiotics in unsaturated soils – implications for nucleic acid based stable isotope probing

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The use of stable isotopes to label phylogenetically informative biomolecules (phospholipid fatty acids, DNA, or RNA), typically referred to as stable isotope probing (SIP) has the potential of providing definitive evidence that a detected population is active in a specific process, if that process ...

  15. The intracellular parasite Toxoplasma gondii depends on the synthesis of long chain and very long-chain unsaturated fatty acids not supplied by the host cell

    PubMed Central

    Ramakrishnan, Srinivasan; Docampo, Melissa D.; MacRae, James I.; Ralton, Julie E.; Rupasinghe, Thusitha; McConville, Malcolm J.; Striepen, Boris

    2015-01-01

    SUMMARY Apicomplexa are parasitic protozoa that cause important human diseases including malaria, cryptosporidiosis and toxoplasmosis. The replication of these parasites within their target host cell is dependent on both salvage as well as de novo synthesis of fatty acids. In T. gondii, fatty acid synthesis via the apicoplast-localized FASII is essential for pathogenesis, while the role of two other fatty acid biosynthetic complexes remains unclear. Here we demonstrate that the ER-localized fatty acid elongation (ELO) is essential for parasite growth. Conditional knock-down of the non-redundant hydroxyacyl-CoA dehydratase and enoyl-CoA reductase enzymes in the ELO pathway severely repressed intracellular parasite growth. 13C-glucose and 13C-acetate labeling and comprehensive lipidomic analyses of these mutants showed a selective defect in synthesis of unsaturated long and very long chain fatty acids (LCFAs and VLCFAs) and depletion of phosphatidylinositol and phosphatidylethanolamine species containing unsaturated LCFAs and VLCFAs. This requirement for ELO pathway was by-passed by supplementing the media with specific fatty acids, indicating active, but inefficient import of host fatty acids. Our experiments highlight a gap between the fatty acid needs of the parasite and availability of specific fatty acids in the host cell that the parasite has to close using a dedicated synthesis and modification pathway. PMID:25825226

  16. Adipose tissue fatty acid chain length and mono-unsaturation increases with obesity and insulin resistance

    PubMed Central

    Yew Tan, Chong; Virtue, Samuel; Murfitt, Steven; Robert, Lee D.; Phua, Yi Hui; Dale, Martin; Griffin, Julian L.; Tinahones, Francisco; Scherer, Philipp E.; Vidal-Puig, Antonio

    2015-01-01

    The non-essential fatty acids, C18:1n9, C16:0, C16:1n7, C18:0 and C18:1n7 account for over 75% of fatty acids in white adipose (WAT) triacylglycerol (TAG). The relative composition of these fatty acids (FA) is influenced by the desaturases, SCD1-4 and the elongase, ELOVL6. In knock-out models, loss of SCD1 or ELOVL6 results in reduced Δ9 desaturated and reduced 18-carbon non-essential FA respectively. Both Elovl6 KO and SCD1 KO mice exhibit improved insulin sensitivity. Here we describe the relationship between WAT TAG composition in obese mouse models and obese humans stratified for insulin resistance. In mouse models with increasing obesity and insulin resistance, there was an increase in scWAT Δ9 desaturated FAs (SCD ratio) and FAs with 18-carbons (Elovl6 ratio) in mice. Data from mouse models discordant for obesity and insulin resistance (AKT2 KO, Adiponectin aP2-transgenic), suggested that scWAT TAG Elovl6 ratio was associated with insulin sensitivity, whereas SCD1 ratio was associated with fat mass. In humans, a greater SCD1 and Elovl6 ratio was found in metabolically more harmful visceral adipose tissue when compared to subcutaneous adipose tissue. PMID:26679101

  17. A bifunctional Delta12,Delta15-desaturase from Acanthamoeba castellanii directs the synthesis of highly unusual n-1 series unsaturated fatty acids.

    PubMed

    Sayanova, Olga; Haslam, Richard; Guschina, Irina; Lloyd, David; Christie, William W; Harwood, John L; Napier, Johnathan A

    2006-12-01

    The free-living soil protozoon Acanthamoeba castellanii synthesizes a range of polyunsaturated fatty acids, the balance of which can be altered by environmental changes. We have isolated and functionally characterized in yeast a microsomal desaturase from A. castellanii, which catalyzes the sequential conversion of C(16) and C(18) Delta9-monounsaturated fatty acids to di- and tri-unsaturated forms. In the case of C(16) substrates, this bifunctional A. castellanii Delta12,Delta15-desaturase generated a highly unusual fatty acid, hexadecatrienoic acid (16:3Delta(9,12,15)(n-1)). The identification of a desaturase, which can catalyze the insertion of a double bond between the terminal two carbons of a fatty acid represents a new addition to desaturase functionality and plasticity. We have also co-expressed in yeast the A. castellanii bifunctional Delta12,Delta15-desaturase with a microsomal Delta6-desaturase, resulting in the synthesis of the highly unsaturated C(16) fatty acid hexadecatetraenoic acid (16:4Delta(6,9,12,15)(n-1)), previously only reported in marine microorganisms. Our work therefore demonstrates the feasibility of the heterologous synthesis of polyunsaturated fatty acids of the n-1 series. The presence of a bifunctional Delta12,Delta15-desaturase in A. castellanii is also considered with reference to the evolution of desaturases and the lineage of this protist. PMID:16950768

  18. Effect of unsaturated fatty acids and triglycerides from soybeans on milk fat synthesis and biohydrogenation intermediates in dairy cattle.

    PubMed

    Boerman, J P; Lock, A L

    2014-11-01

    Increased rumen unsaturated fatty acid (FA) load is a risk factor for milk fat depression. This study evaluated if increasing the amount of unsaturated FA in the diet as triglycerides or free FA affected feed intake, yield of milk and milk components, and feed efficiency. Eighteen Holstein cows (132 ± 75 d in milk) were used in a replicated 3 × 3 Latin square design. Treatments were a control (CON) diet, or 1 of 2 unsaturated FA (UFA) treatments supplemented with either soybean oil (FA present as triglycerides; TAG treatment) or soybean FA distillate (FA present as free FA; FFA treatment). The soybean oil contained a higher concentration of cis-9 C18:1 (26.0 vs. 11.8 g/100g of FA) and lower concentrations of C16:0 (9.6 vs. 15.0 g/100g of FA) and cis-9,cis-12 C18:2 (50.5 vs. 59.1g/100g of FA) than the soybean FA distillate. The soybean oil and soybean FA distillate were included in the diet at 2% dry matter (DM) to replace soyhulls in the CON diet. Treatment periods were 21 d, with the final 4 d used for sample and data collection. The corn silage- and alfalfa silage-based diets contained 23% forage neutral detergent fiber and 17% crude protein. Total dietary FA were 2.6, 4.2, and 4.3% of diet DM for CON, FFA, and TAG treatments, respectively. Total FA intake was increased 57% for UFA treatments and was similar between FFA and TAG. The intakes of individual FA were similar, with the exception of a 24 g/d lower intake of C16:0 and a 64 g/d greater intake of cis-9 C18:1 for the TAG compared with the FFA treatment. Compared with CON, the UFA treatments decreased DM intake (1.0 kg/d) but increased milk yield (2.2 kg/d) and milk lactose concentration and yield. The UFA treatments reduced milk fat concentration, averaging 3.30, 3.18, and 3.11% for CON, FFA, and TAG treatments, respectively. Yield of milk fat, milk protein, and 3.5% fat-corrected milk remained unchanged when comparing CON with the UFA treatments. No differences existed in the yield of milk or milk

  19. Unsaturated fatty acids as high-affinity ligands of the C-terminal Per-ARNT-Sim domain from the Hypoxia-inducible factor 3α

    PubMed Central

    Fala, Angela M.; Oliveira, Juliana F.; Adamoski, Douglas; Aricetti, Juliana A.; Dias, Marilia M.; Dias, Marcio V. B.; Sforça, Maurício L.; Lopes-de-Oliveira, Paulo S.; Rocco, Silvana A.; Caldana, Camila; Dias, Sandra M. G.; Ambrosio, Andre L. B.

    2015-01-01

    Hypoxia-inducible transcription factors (HIF) form heterodimeric complexes that mediate cell responses to hypoxia. The oxygen-dependent stability and activity of the HIF-α subunits is traditionally associated to post-translational modifications such as hydroxylation, acetylation, ubiquitination, and phosphorylation. Here we report novel evidence showing that unsaturated fatty acids are naturally occurring, non-covalent structural ligands of HIF-3α, thus providing the initial framework for exploring its exceptional role as a lipid sensor under hypoxia. PMID:26237540

  20. Unsaturated fatty acids as high-affinity ligands of the C-terminal Per-ARNT-Sim domain from the Hypoxia-inducible factor 3α.

    PubMed

    Fala, Angela M; Oliveira, Juliana F; Adamoski, Douglas; Aricetti, Juliana A; Dias, Marilia M; Dias, Marcio V B; Sforça, Maurício L; Lopes-de-Oliveira, Paulo S; Rocco, Silvana A; Caldana, Camila; Dias, Sandra M G; Ambrosio, Andre L B

    2015-01-01

    Hypoxia-inducible transcription factors (HIF) form heterodimeric complexes that mediate cell responses to hypoxia. The oxygen-dependent stability and activity of the HIF-α subunits is traditionally associated to post-translational modifications such as hydroxylation, acetylation, ubiquitination, and phosphorylation. Here we report novel evidence showing that unsaturated fatty acids are naturally occurring, non-covalent structural ligands of HIF-3α, thus providing the initial framework for exploring its exceptional role as a lipid sensor under hypoxia. PMID:26237540

  1. Conjugate addition of indoles to alpha,beta-unsaturated ketones using a Brønsted acid ionic liquid as an efficient catalyst.

    PubMed

    Yu, Chuan-Ji; Liu, Chen-Jiang

    2009-01-01

    The Brønsted acid ionic liquid [PyN(CH(2))(4)SO(3)H][p-CH(3)PhSO(3)] has been reported as an efficient catalyst for the Michael addition reaction of indoles to alpha,beta-unsaturated ketones. Satisfactory results were obtained, with excellent yields and a simple experimental procedure. The catalyst could be recycled and reused up to three times without any noticeable decrease in the catalytic activity. PMID:19783920

  2. Cancer cell dependence on unsaturated fatty acids implicates stearoyl-CoA desaturase as a target for cancer therapy.

    PubMed

    Roongta, Urvashi V; Pabalan, Jonathan G; Wang, Xinyu; Ryseck, Rolf-Peter; Fargnoli, Joseph; Henley, Benjamin J; Yang, Wen-Pin; Zhu, Jun; Madireddi, Malavi T; Lawrence, R Michael; Wong, Tai W; Rupnow, Brent A

    2011-11-01

    Emerging literature suggests that metabolic pathways play an important role in the maintenance and progression of human cancers. In particular, recent studies have implicated lipid biosynthesis and desaturation as a requirement for tumor cell survival. In the studies reported here, we aimed to understand whether tumor cells require the activity of either human isoform of stearoyl-CoA-desaturase (SCD1 or SCD5) for survival. Inhibition of SCD1 by siRNA or a small molecule antagonist results in strong induction of apoptosis and growth inhibition, when tumor cells are cultured in reduced (2%) serum conditions, but has little impact on cells cultured in 10% serum. Depletion of SCD5 had minimal effects on cell growth or apoptosis. Consistent with the observed dependence on SCD1, but not SCD5, levels of SCD1 protein increased in response to decreasing serum levels. Both induction of SCD1 protein and sensitivity to growth inhibition by SCD1 inhibition could be reversed by supplementing growth media with unsaturated fatty acids, the product of the enzymatic reaction catalyzed by SCD1. Transcription profiling of cells treated with an SCD inhibitor revealed strong induction of markers of endoplasmic reticulum stress. Underscoring its importance in cancer, SCD1 protein was found to be highly expressed in a large percentage of human cancer specimens. SCD inhibition resulted in tumor growth delay in a human gastric cancer xenograft model. Altogether, these results suggest that desaturated fatty acids are required for tumor cell survival and that SCD may represent a viable target for the development of novel agents for cancer therapy. PMID:21954435

  3. Novel bioactive polyester scaffolds prepared from unsaturated resins based on isosorbide and succinic acid.

    PubMed

    Smiga-Matuszowicz, Monika; Janicki, Bartosz; Jaszcz, Katarzyna; Łukaszczyk, Jan; Kaczmarek, Marcin; Lesiak, Marta; Sieroń, Aleksander L; Simka, Wojciech; Mierzwiński, Maciej; Kusz, Damian

    2014-12-01

    In this study new biodegradable materials obtained by crosslinking poly(3-allyloxy-1,2-propylene succinate) (PSAGE) with oligo(isosorbide maleate) (OMIS) and small amount of methyl methacrylate were investigated. The porous scaffolds were obtained in the presence of a foaming system consisted of calcium carbonate/carboxylic acid mixture, creating in situ porous structure during crosslinking of liquid formulations. The maximum crosslinking temperature and setting time, the cured porous materials morphology as well as the effect of their porosity on mechanical properties and hydrolytic degradation process were evaluated. It was found that the kind of carboxylic acid used in the foaming system influenced compressive strength and compressive modulus of porous scaffolds. The MTS cytotoxicity assay was carried out for OMIS using hFOB1.19 cell line. OMIS resin was found to be non-toxic in wide range of concentrations. On the ground of scanning electron microscopy (SEM) observations and energy X-ray dispersive analysis (EDX) it was found that hydroxyapatite (HA) formation at the scaffolds surfaces within short period of soaking in phosphate buffer solution occurs. After 3h immersion a compact layer of HA was observed at the surface of the samples. The obtained results suggest potential applicability of resulted new porous crosslinked polymeric materials as temporary bone void fillers. PMID:25491802

  4. Availability of oxygen in radiation-induced peroxidation of unsaturated fatty acids

    NASA Astrophysics Data System (ADS)

    Katus̆in-Raz̆em, B.; Raz̆em, D.

    2003-06-01

    Radiation—induced peroxidation of polyunsaturated fatty acids (LH) was measured as function of surface-to-volume ratio. Linoleic (LiH), linolenic (LinH) and arachidonic (ArH) acid were irradiated by 60Co gamma rays in the form of small droplets without bubbling with oxygen, and in bulk, which was bubbled with oxygen during irradiation. As the surface-to-volume ratio of droplets increased, the G(LOOH) values also increased to approach the values in bulk. The largest volumes which could be adequately oxygenated only by diffusion at a relatively high rate of oxygen consumption (at the dose rate 5.5 Gy/s) were 7, 6, and 5 mg of LiH, LinH and ArH, respectively. Penetration depths of oxygen were calculated as 0.068, 0.062 and 0.050 cm, which correspond to 9, 7 and 5 mg of LiH, LinH and ArH, respectively, which is in reasonable agreement with the experiment.

  5. The trans/cis ratio of unsaturated fatty acids is not applicable as biomarker for environmental stress in case of long-term contaminated habitats.

    PubMed

    Fischer, Janett; Schauer, Frieder; Heipieper, Hermann J

    2010-06-01

    Cis-trans isomerization of unsaturated fatty acids is a crucial adaptive reaction of Pseudomonas and Vibrio species to toxic organic compounds or other environmental stress factors. In order to test the long-term performance of this adaptive mechanism as well as to assess its application as biomarker for environmental contamination studies were performed in batch cultures and in continuously running sand columns, simulating long-term contamination with bisphenol A (BPA). In short-term grown batch cultures a high correlation between trans/cis ratio and added BPA concentration and toxicity was observed. In contrary, this did not occur in the case of long-term sand columns. An increase in trans/cis ratio of unsaturated fatty acids only appeared in a limited period of time. Afterwards the trans/cis ratio reached the values measured for non-stressed cultures. Cis-trans isomerization is only an urgent response mechanism that is later substituted by other adaptive mechanisms. Therefore, it can be concluded that the trans/cis ratio of unsaturated fatty acids was shown not to be an appropriate biomarker for durable stress in the environment. PMID:20352421

  6. Roles of unsaturated fatty acids (especially omega-3 fatty acids) in the brain at various ages and during ageing.

    PubMed

    Bourre, J M

    2004-01-01

    Among various organs, in the brain, the fatty acids most extensively studied are omega-3 fatty acids. Alpha-linolenic acid (18:3omega3) deficiency alters the structure and function of membranes and induces minor cerebral dysfunctions, as demonstrated in animal models and subsequently in human infants. Even though the brain is materially an organ like any other, that is to say elaborated from substances present in the diet (sometimes exclusively), for long it was not accepted that food can have an influence on brain structure, and thus on its function. Lipids, and especially omega-3 fatty acids, provided the first coherent experimental demonstration of the effect of diet (nutrients) on the structure and function of the brain. In fact the brain, after adipose tissue, is the organ richest in lipids, whose only role is to participate in membrane structure. First it was shown that the differentiation and functioning of cultured brain cells requires not only alpha-linolenic acid (the major component of the omega-3, omega3 family), but also the very long omega-3 and omega-6 carbon chains (1). It was then demonstrated that alpha-linolenic acid deficiency alters the course of brain development, perturbs the composition and physicochemical properties of brain cell membranes, neurones, oligodendrocytes, and astrocytes (2). This leads to physicochemical modifications, induces biochemical and physiological perturbations, and results in neurosensory and behavioural upset (3). Consequently, the nature of polyunsaturated fatty acids (in particular omega-3) present in formula milks for infants (premature and term) conditions the visual and cerebral abilities, including intellectual. Moreover, dietary omega-3 fatty acids are certainly involved in the prevention of some aspects of cardiovascular disease (including at the level of cerebral vascularization), and in some neuropsychiatric disorders, particularly depression, as well as in dementia, notably Alzheimer's disease. Recent

  7. Cell membrane fatty acid changes and desaturase expression of Saccharomyces bayanus exposed to high pressure homogenization in relation to the supplementation of exogenous unsaturated fatty acids

    PubMed Central

    Serrazanetti, Diana I.; Patrignani, Francesca; Russo, Alessandra; Vannini, Lucia; Siroli, Lorenzo; Gardini, Fausto; Lanciotti, Rosalba

    2015-01-01

    Aims: The aim of this work was to study the responses of Saccharomyces bayanus cells exposed to sub-lethal high-pressure homogenization (HPH) and determine whether the plasmatic membrane can sense HPH in the presence, or absence, of exogenous unsaturated fatty acids (UFAs) in the growth medium. Methods and Results: High-pressure homogenization damaged and caused the collapse of cell walls and membranes of a portion of cells; however, HPH did not significantly affect S. bayanus cell viability (less than 0.3 Log CFU ml-1). HPH strongly affected the membrane fatty acid (FA) composition by increasing the percentage of total UFA when compared with saturated fatty acids. The gene expression showed that the transcription of OLE1, ERG3, and ERG11 increased after HPH. The presence of exogenous UFA abolished HPH-induced effects on the OLE1 and ERG3 genes, increased the percentage of membrane lipids and decreased the expression of OLE1 and ERG3 within 30 min of treatment. Conclusion: The results suggest a key role for UFA in the microbial cell response to sub-lethal stress. In addition, these data provide insight into the molecular basis of the response of S. bayanus to this innovative technology. Significance and Impact of the Study: Elucidation of the mechanism of action for sub-lethal HPH will enable the utilization of this technology to modulate the starter performance at the industrial scale. PMID:26528258

  8. Effect of diet fermentability and unsaturated fatty acid concentration on recovery from diet-induced milk fat depression.

    PubMed

    Rico, D E; Holloway, A W; Harvatine, K J

    2015-11-01

    Diet-induced milk fat depression is caused by highly fermentable and high-unsaturated fatty acid (FA) diets, and results in reduced milk fat concentration and yield, reduced de novo FA, and increased trans isomers of the alternate biohydrogenation pathways. The hypothesis of the current experiment was that a diet higher in fermentability and lower in unsaturated FA (UFA) would accelerate recovery compared with a high-UFA and lower-fermentability diet. Eight ruminally cannulated and 9 noncannulated multiparous Holstein cows were randomly assigned to treatment sequences in a replicated Latin square design. During each period milk fat depression was induced for 10 d by feeding a low-fiber, high-UFA diet [25.9% neutral detergent fiber (NDF) and 3.3% C18:2]. Following the induction phase, cows were switched to recovery treatments for 18 d designed to correct dietary fermentability, UFA, or both fermentability and UFA concentration. Treatments during recovery were (1) correction of fiber and UFA diet [control; 31.8% NDF and 1.65% C18:2], (2) a diet predominantly correcting fiber, but not UFA [high oil (HO); 31.3% NDF and 2.99% C18:2], and (3) a diet predominantly correcting UFA, but not fiber concentration [low fiber (LF); 28.4% NDF and 1.71% C18:2]. Milk and milk component yield, milk FA profile, ruminal pH, and 11 rumen microbial taxa were measured every third day during recovery. Milk yield decreased progressively in HO and control, whereas it was maintained in the LF diet. Milk fat concentration increased progressively during recovery in all treatments, but was on average 9% lower in LF than control from d 12 to 18. Milk fat yield increased progressively in all treatments and was not different between control and LF at any time point, but was lower in HO than control on d 15. Milk trans-10 C18:1 and trans-10,cis-12 conjugated linoleic acid decreased progressively in all treatments, but was higher in HO than control from d 3 to 18 [136 ± 50 and 188 ± 57% (mean ± SD

  9. Involvement of the CasK/R two-component system in optimal unsaturation of the Bacillus cereus fatty acids during low-temperature growth.

    PubMed

    Diomandé, Sara Esther; Nguyen-the, Christophe; Abee, Tjakko; Tempelaars, Marcel H; Broussolle, Véronique; Brillard, Julien

    2015-11-20

    Bacillus cereus sensu lato is composed of a set of ubiquitous strains including human pathogens that can survive a range of food processing conditions, grow in refrigerated food, and sometimes cause food poisoning. We previously identified the two-component system CasK/R that plays a key role in cold adaptation. To better understand the CasK/R-controlled mechanisms that support low-temperature adaptation, we performed a transcriptomic analysis on the ATCC 14579 strain and its isogenic ∆casK/R mutant grown at 12°C. Several genes involved in fatty acid (FA) metabolism were downregulated in the mutant, including desA and desB encoding FA acyl-lipid desaturases that catalyze the formation of a double-bond on the FA chain in positions ∆5 and ∆10, respectively. A lower proportion of FAs presumably unsaturated by DesA was observed in the ΔcasK/R strain compared to the parental strain while no difference was found for FAs presumably unsaturated by DesB. Addition of phospholipids from egg yolk lecithin rich in unsaturated FAs, to growth medium, abolished the cold-growth impairment of ΔcasK/R suggesting that exogenous unsaturated FAs can support membrane-level modifications and thus compensate for the decreased production of these FAs in the B. cereus ∆casK/R mutant during growth at low temperature. Our findings indicate that CasK/R is involved in the regulation of FA metabolism, and is necessary for cold adaptation of B. cereus unless an exogenous source of unsaturated FAs is available. PMID:25987542

  10. A novel unsaturated fatty acid hydratase toward C16 to C22 fatty acids from Lactobacillus acidophilus

    PubMed Central

    Hirata, Akiko; Kishino, Shigenobu; Park, Si-Bum; Takeuchi, Michiki; Kitamura, Nahoko; Ogawa, Jun

    2015-01-01

    Hydroxy FAs, one of the gut microbial metabolites of PUFAs, have attracted much attention because of their various bioactivities. The purpose of this study was to identify lactic acid bacteria with the ability to convert linoleic acid (LA) to hydroxy FAs. A screening process revealed that a gut bacterium, Lactobacillus acidophilus NTV001, converts LA mainly into 13-hydroxy-cis-9-octadecenoic acid and resulted in the identification of the hydratase responsible, fatty acid hydratase 1 (FA-HY1). Recombinant FA-HY1 was purified, and its enzymatic characteristics were investigated. FA-HY1 could convert not only C18 PUFAs but also C20 and C22 PUFAs. C18 PUFAs with a cis carbon-carbon double bond at the Δ12 position were converted into the corresponding 13-hydroxy FAs. Arachidonic acid and DHA were converted into the corresponding 15-hydroxy FA and 14-hydroxy FA, respectively. To the best of our knowledge, this is the first report of a bacterial FA hydratase that can convert C20 and C22 PUFAs into the corresponding hydroxy FAs. These novel hydroxy FAs produced by using FA-HY1 should contribute to elucidating the bioactivities of hydroxy FAs. PMID:25966711

  11. New cofactor supports α,β-unsaturated acid decarboxylation via 1,3-dipolar cycloaddition

    PubMed Central

    Payne, Karl A.P.; White, Mark D.; Fisher, Karl; Khara, Basile; Bailey, Samuel S.; Parker, David; Rattray, Nicholas J.W.; Trivedi, Drupad K.; Goodacre, Royston; Beveridge, Rebecca; Barran, Perdita; Rigby, Stephen E.J.; Scrutton, Nigel S.; Hay, Sam; Leys, David

    2016-01-01

    The ubiD/ubiX or the homologous fdc/pad genes have been implicated in the non-oxidative reversible decarboxylation of aromatic substrates, and play a pivotal role in bacterial ubiquinone biosynthesis1–3 or microbial biodegradation of aromatic compounds4–6 respectively. Despite biochemical studies on individual gene products, the composition and co-factor requirement of the enzyme responsible for in vivo decarboxylase activity remained unclear7–9. We show Fdc is solely responsible for (de)carboxylase activity, and that it requires a new type of cofactor: a prenylated flavin synthesised by the associated UbiX/Pad10. Atomic resolution crystal structures reveal two distinct isomers of the oxidized cofactor can be observed: an isoalloxazine N5-iminium adduct and a N5 secondary ketimine species with drastically altered ring structure, both having azomethine ylide character. Substrate binding positions the dipolarophile enoic acid group directly above the azomethine ylide group. The structure of a covalent inhibitor-cofactor adduct suggests 1,3-dipolar cycloaddition chemistry supports reversible decarboxylation in these enzymes. While 1,3-dipolar cycloaddition is commonly used in organic chemistry11–12, we propose this presents the first example of an enzymatic 1,3-dipolar cycloaddition reaction. Our model for Fdc/UbiD catalysis offers new routes in alkene hydrocarbon production or aryl (de)carboxylation. PMID:26083754

  12. Coordination compounds of hafnium(IV) with some N-substituted derivatives of unsaturated hydroxamic acids

    SciTech Connect

    Stratulat, A.A.; Batyr, D.G.

    1987-05-01

    Coordination compounds of hafnium(IV) with N-o(or m)-X-phenylacryl- and methacrylhydroxamic acids with the general formula (Hf/XC/sub 6/H/sub 4/-N(O)-C(O)-R//sub 4/), where X = 4-CH/sub 3/, H, 4-Cl, 4-Br, 4-CH/sub 3/C(O), 4-CH=CH/sub 2/, 4-CH/sub 3/OC(O), 3-CH/sub 3/, 3-Cl, and 3-Br, and R = CH=CH/sub 2/ and C(CH/sub 3/)=CH/sub 2/, have been synthesized and characterized. The type of coordination of the organic ligands and the structure of the complexes have been established on the basis of the data from IR, electronic, and PMR spectra. It has been shown that the complexation process involves the replacement of the proton of the hydroxyl group of the hydroxamic grouping by a metal ion and the coordination of the oxygen atom of the carbonyl group. The coordination compounds obtained have been assigned a square-antiprismatic structure. The introduction of a methyl radical into the vinyl grouping R results in a significant increase in the strength of the complex.

  13. Effects of dietary n-3 highly unsaturated fatty acids (HUFAs) on growth, fatty acid profiles, antioxidant capacity and immunity of sea cucumber Apostichopus japonicus (Selenka).

    PubMed

    Yu, Haibo; Gao, Qinfeng; Dong, Shuanglin; Zhou, Jishu; Ye, Zhi; Lan, Ying

    2016-07-01

    The present study was conducted to understand the effects of dietary n-3 highly unsaturated fatty acids (HUFAs) on growth, fatty acid profiles, antioxidant capacity and the immunity of sea cucumber Apostichopus japonicus (Selenka). Five experimental diets were prepared, containing graded levels of n-3 HUFAs (0.46%, 0.85%, 1.25%, 1.61% and 1.95%, respectively), and the 0.46% group was used as control group. The specific growth rates, fatty acid profiles, activities and gene expression of antioxidative enzymes and lysozyme of the sea cucumbers that were fed with the 5 experimental diets were determined. The results showed that the specific growth rate of sea cucumbers in all the treatment groups significantly increased compared to the control group (P < 0.05), indicating the positive effects of n-3 HUFAs on the growth of sea cucumbers. The contents of eicosapentaenoic acid (EPA; 20:5n-3) and docosahexaenoic acid (DHA; 22:6n-3) in the body wall of the sea cucumbers gradually increased with the increasing levels of n-3 HUFAs in the diets. The suitable supplement of n-3 HUFAs in diets improved the activities of superoxide dismutase (SOD) and catalase (CAT) of sea cucumbers by up-regulating the expression of SOD and CAT mRNA in sea cucumbers. However, excess n-3 HUFAs in diets caused lipid peroxidation, inhibited the expression of lysozyme (LSZ) mRNA and decreased the activities of LSZ in sea cucumbers. In summary, the suitable supplement levels of n-3 HUFAs in diets of sea cucumbers A. japonicus were estimated between 0.85% and 1.25% considering the growth performance, cost and the indicators of antioxidant capacity and immunity. PMID:27079426

  14. Magnetoliposomes Loaded with Poly-Unsaturated Fatty Acids as Novel Theranostic Anti-Inflammatory Formulations

    PubMed Central

    Calle, Daniel; Negri, Viviana; Ballesteros, Paloma; Cerdán, Sebastián

    2015-01-01

    We describe the preparation, physico-chemical characterization and anti-inflammatory properties of liposomes containing the superparamagnetic nanoparticle Nanotex, the fluorescent dye Rhodamine-100 and omega-3 polyunsaturated fatty acid ethyl ester (ω-3 PUFA-EE), as theranostic anti-inflammatory agents. Liposomes were prepared after drying chloroform suspensions of egg phosphatidylcholine, hydration of the lipid film with aqueous phases containing or not Nanotex, Rhodamine-100 dye or ω-3 PUFA-EE, and eleven extrusion steps through nanometric membrane filters. This resulted in uniform preparations of liposomes of approximately 200 nm diameter. Extraliposomal contents were removed from the preparation by gel filtration chromatography. High Resolution Magic Angle Spinning 1H NMR Spectroscopy of the liposomal preparations containing ω-3 PUFA-EE revealed well resolved 1H resonances from highly mobile ω-3 PUFA-EE, suggesting the formation of very small (ca. 10 nm) ω-3 PUFA-EE nanogoticules, tumbling fast in the NMR timescale. Chloroform extraction of the liposomal preparations revealed additionally the incorporation of ω-3 PUFA-EE within the membrane domain. Water diffusion weighted spectra, indicated that the goticules of ω-3 PUFA-EE or its insertion in the membrane did not affect the average translational diffusion coefficient of water, suggesting an intraliposomal localization, that was confirmed by ultrafiltration. The therapeutic efficacy of these preparations was tested in two different models of inflammatory disease as inflammatory colitis or the inflammatory component associated to glioma development. Results indicate that the magnetoliposomes loaded with ω-3 PUFA-EE allowed MRI visualization in vivo and improved the outcome of inflammatory disease in both animal models, decreasing significantly colonic inflammation and delaying, or even reversing, glioma development. Together, our results indicate that magnetoliposomes loaded with ω-3 PUFA-EE may become

  15. Magnetoliposomes loaded with poly-unsaturated fatty acids as novel theranostic anti-inflammatory formulations.

    PubMed

    Calle, Daniel; Negri, Viviana; Ballesteros, Paloma; Cerdán, Sebastián

    2015-01-01

    We describe the preparation, physico-chemical characterization and anti-inflammatory properties of liposomes containing the superparamagnetic nanoparticle Nanotex, the fluorescent dye Rhodamine-100 and omega-3 polyunsaturated fatty acid ethyl ester (ω-3 PUFA-EE), as theranostic anti-inflammatory agents. Liposomes were prepared after drying chloroform suspensions of egg phosphatidylcholine, hydration of the lipid film with aqueous phases containing or not Nanotex, Rhodamine-100 dye or ω-3 PUFA-EE, and eleven extrusion steps through nanometric membrane filters. This resulted in uniform preparations of liposomes of approximately 200 nm diameter. Extraliposomal contents were removed from the preparation by gel filtration chromatography. High Resolution Magic Angle Spinning (1)H NMR Spectroscopy of the liposomal preparations containing ω-3 PUFA-EE revealed well resolved (1)H resonances from highly mobile ω-3 PUFA-EE, suggesting the formation of very small (ca. 10 nm) ω-3 PUFA-EE nanogoticules, tumbling fast in the NMR timescale. Chloroform extraction of the liposomal preparations revealed additionally the incorporation of ω-3 PUFA-EE within the membrane domain. Water diffusion weighted spectra, indicated that the goticules of ω-3 PUFA-EE or its insertion in the membrane did not affect the average translational diffusion coefficient of water, suggesting an intraliposomal localization, that was confirmed by ultrafiltration. The therapeutic efficacy of these preparations was tested in two different models of inflammatory disease as inflammatory colitis or the inflammatory component associated to glioma development. Results indicate that the magnetoliposomes loaded with ω-3 PUFA-EE allowed MRI visualization in vivo and improved the outcome of inflammatory disease in both animal models, decreasing significantly colonic inflammation and delaying, or even reversing, glioma development. Together, our results indicate that magnetoliposomes loaded with ω-3 PUFA-EE may

  16. Conversion of cis unsaturated fatty acids to trans, a possible mechanism for the protection of phenol-degrading Pseudomonas putida P8 from substrate toxicity

    SciTech Connect

    Heipieper, H.J.; Diefenbach, R.; Keweloh, H. )

    1992-06-01

    A trans unsaturated fatty acid was found as a major constituent in the lipids of Pseudomonas putida P8. The fatty acid was identified as 9-trans-hexadecenoic acid by gas chromatography, argentation thin-layer chromatography, and infrared absorption spectrometry. Growing cells of P. putida P8 reacted to the presence of sublethal concentrations of phenol in the medium with changes in the fatty acid composition of the lipids, thereby increasing the degree of saturation. At phenol concentrations which completely inhibited the growth of P.putida, the cells were still able to increase the content of the trans unsaturated fatty acid and simultaneously induced by 4-chlorophenol in nongrowing cells in which the de novo synthesis of lipids has stopped, as shown by incorporation experiments with labeled acetate. The isomerization of the double bond in the presence of cholramphenicol indicates a constitutively operating enzyme system. The cis-to-trans modification of the fatty acids studied here apparently is a new way of adapting the membrane fluidity to the presence of phenols, thereby compensating for the elevation of membrane permeability induced by these toxic substances.

  17. Effects of dietary calcium soaps of unsaturated fatty acids on digestion, milk composition and physical properties of butter.

    PubMed

    Enjalbert, F; Nicot, M C; Bayourthe, C; Vernay, M; Moncoulon, R

    1997-05-01

    Dairy cows fitted with ruminal, duodenal and ileal cannulas were utilized to investigate the effects of feeding with Ca soaps (CaS) of palm fatty acids (FA) and rapeseed FA. Diets compared were control diet based on maize silage and concentrate, and two diets with 40 g CaS of palm oil FA or rapeseed oil FA/kg diet, replacing part of the concentrates of the control diet. Total digestibilities of dry matter, fibre and fat, and ruminal fermentation were not significantly altered by giving CaS; the extent of ruminal biohydrogenation of total unsaturated C18 FA was significantly reduced by both CaS diets. Apparent intestinal digestibility of FA was not different among diets, although the amount of FA absorbed with the CaS diets was twice that with the control diet. No difference among diets was observed for milk production, or fat and protein contents. Giving CaS diets decreased the proportions of 4:0 to 14:0 FA in milk fat, and increased cis-18:1n-9, compared with control diet. The rapeseed diet lowered the content of 16:0, and increased the contents of 18:0 and trans-18:1n-7. CaS diets did not result in a marked increase of polyunsaturated FA content in milk fat. Butter from cows fed on the CaS diets contained more liquid fat at 6 and 14 degrees C than butter from the cows fed on the control diet. Incorporating CaS, particularly those from rapeseed, in dairy cows' diets increased C18 FA in milk and improved butter spreadability. PMID:9161912

  18. Divergent reactivity in palladium-catalyzed annulation with diarylamines and α,β-unsaturated acids: direct access to substituted 2-quinolinones and indoles.

    PubMed

    Kancherla, Rajesh; Naveen, Togati; Maiti, Debabrata

    2015-06-01

    A palladium-catalyzed CH activation strategy has been successfully employed for exclusive synthesis of a variety of 3-substituted indoles. A [3+3] annulation for synthesizing substituted 2-quinolinones was recently developed by reaction of α,β-unsaturated carboxylic acids with diarylamines under acidic conditions. In the present work, an analogous [3+2] annulation is achieved from the same set of starting materials under basic conditions to generate 1,3-disubstituted indoles exclusively. Mechanistic studies revealed an ortho-palladation-π-coordination-β-migratory insertion-β-hydride elimination reaction sequence to be operative under the reaction conditions. PMID:25941155

  19. Pomegranate seed oil: Effect on 3-nitropropionic acid-induced neurotoxicity in PC12 cells and elucidation of unsaturated fatty acids composition.

    PubMed

    Al-Sabahi, Bushra N; Fatope, Majek O; Essa, Musthafa Mohamed; Subash, Selvaraju; Al-Busafi, Saleh N; Al-Kusaibi, Fatma S N; Manivasagam, Thamilarasan

    2014-09-19

    Background Seed oils are used as cosmetics or topical treatment for wounds, allergy, dandruff, and other purposes. Natural antioxidants from plants were recently reported to delay the onset or progress of various neurodegenerative conditions. Over one thousand cultivars of Punica granatum (Punicaceae) are known and some are traditionally used to treat various ailments. Aim The effect of pomegranate oil on 3-nitropropionic acid- (3-NP) induced cytotoxicity in rat pheochromocytoma (PC12) neuronal cells was analyzed in this study. Furthermore, the analysis of unsaturated fatty acid composition of the seed oil of pomegranate by gas chromatography-electron impact mass spectrometry (GC-MS) was done. Results GC-MS study showed the presence of 6,9-octadecadiynoic acid (C18:2(6,9)) as a major component (60%) as 4,4-dimethyloxazoline derivative. The total extractable oil with light petroleum ether by Soxhlet from the dry seed of P. granatum was 4-6%. The oil analyzed for 48.90 ± 1.50 mg gallic acid equivalents/g of oil, and demonstrated radical-scavenging-linked antioxidant activities in various in vitro assays like the DPPH (2,2-diphenyl-l-picrylhydrazyl, % IP = 35.2 ± 0.9%), ABTS (2,2'-azino-bis-3-ethylene benzothiozoline-6-sulfonic acid, % IP 2.2 ± 0.1%), and β-carotene bleaching assay (% IP = 26 ± 3%), respectively, which could be due the possible role of one methylene interrupted diynoic acid system for its radical-scavenging/antioxidant properties of oil. The oil also reduced lipid peroxidation, suppressed reactive oxygen species, extracellular nitric oxide, lactate/pyruvate ratio, and lactase dehydrogenase generated by 3-NP- (100 mM) induced neurotoxicity in PC12 cells, and enhanced the levels of enzymatic and non-enzymatic antioxidants at 40 μg of gallic acid equivalents. Conclusion The protective effect of pomegranate seed oil might be due to the ability of an oil to neutralize ROS or enhance the expression of antioxidant gene. PMID:25238165

  20. Fatty acid binding protein 7 and n-3 poly unsaturated fatty acid supply in early rat brain development.

    PubMed

    Maximin, Elise; Langelier, Bénédicte; Aïoun, Josiane; Al-Gubory, Kaïs H; Bordat, Christian; Lavialle, Monique; Heberden, Christine

    2016-03-01

    Fatty acid binding protein 7 (FABP7), abundant in the embryonic brain, binds with the highest affinity to docosahexaenoic acid (DHA) and is expressed in the early stages of embryogenesis. Here, we have examined the consequences of the exposure to different DHA levels and of the in utero depletion of FABP7 on early rat brain development. Neurodevelopment was evaluated through the contents of two proteins, connexin 43 (Cx43) and cyclin-dependent kinase 5 (CDK5), both involved in neuroblast proliferation, differentiation, and migration. The dams were fed with diets presenting different DHA contents, from deficiency to supplementation. DHA brain embryos contents already differed at embryonic day 11.5 and the differences kept increasing with time. Cx43 and CDK5 contents were positively associated with the brain DHA levels. When FABP7 was depleted in vivo by injections of siRNA in the telencephalon, the enhancement of the contents of both proteins was lost in supplemented animals, but FABP7 depletion did not modify phospholipid compositions regardless of the diets. Thus, FABP7 is a necessary mediator of the effect of DHA on these proteins synthesis, but its role in DHA uptake is not critical, although FABP7 is localized in phospholipid-rich areas. Our study shows that high contents of DHA associated with FABP7 are necessary to promote early brain development, which prompted us to recommend DHA supplementation early in pregnancy. PMID:26037116

  1. Inhibition of lysophospholipase D activity by unsaturated lysophosphatidic acids or seed extracts containing 1-linoleoyl and 1-oleoyl lysophosphatidic acid.

    PubMed

    Liu, Xi-Wen; Sok, Dai-Eun; Yook, Hong-Sun; Sohn, Cheon-Bae; Chung, Young-Jin; Kim, Mee Ree

    2007-10-17

    Lysophospholipase D (lysoPLD), generating lipid mediator lysophosphatidic acid (LPA) from lysophosphatidyclcholine (LPC), is known to be inhibited by lysophosphatidic acids. Meanwhile, some plant lipids are known to contain lysophospholipids as minor components. Therefore, it is interesting to test whether edible seed samples, rich in phospholipids, may contain lysophospholipids, which express a strong inhibition of lysoPLD activity. First, the structural importance of fatty acyl group in LPAs was examined by determining the inhibitory effect of various LPAs on bovine lysoPLD activity. The most potent in the inhibition of lysoPLD activity was linoleoyl-LPA ( K i, 0.21 microM), followed by arachidonoyl-LPA ( K i, 0.55 microM), oleoyl-LPA ( K i, 1.2 microM), and palmitoyl-LPA ( K i, 1.4 microM), based on the fluoresecent assay. The same order of inhibitory potency among LPA analogs with different acyl chains was also found in the spectrophotometric assay. Subsequently, the extracts of 12 edible seeds were screened for the inhibition of lysoPLD activity using both spectrophotometric and fluorescent assays. Among seed extracts tested, the extract from soybean seed, sesame seed, or sunflower seed (30 mg seed weight/mL) was found to exhibit a potent inhibition (>80%) of lysoPLD activity. In further study employing ESI-MS/MS analysis, major LPA components in seed extracts were identified to be 1-linoleoyl LPA, 1-oleoyl LPA, and 1-palmitoyl LPA with 1-linoleoyl LPA being more predominant. Thus, the potent inhibition of lysoPLD activity by seed extracts might be ascribed to the presence of LPA with linoleoyl group rather than other acyl chains. PMID:17887800

  2. Regulation of epidermal-growth-factor-receptor signal transduction by cis-unsaturated fatty acids. Evidence for a protein kinase C-independent mechanism.

    PubMed Central

    Casabiell, X; Pandiella, A; Casanueva, F F

    1991-01-01

    The effect of acute treatment with non-esterified fatty acids (NEFA) on transmembrane signalling has been investigated in three different cell lines. In EGFR T17 cells, pretreatment with cis-unsaturated (oleic and palmitoleic acids) NEFA, but not with saturated or trans-unsaturated NEFA, inhibited the epidermal-growth-factor (EGF)-induced increases in cytosolic [Ca2+], membrane potential and Ins(1,4,5)P3 generation. The blocking effect was found to be time- and dose-dependent and rapidly reversible after washout. However, oleic acid treatment did not block either binding of 125I-EGF to its receptor or EGF-induced autophosphorylation of the EGF receptor. The mechanism of action of NEFA could not be attributed to protein kinase C activation, since (i) down-regulation of the enzyme by long-term treatment with phorbol esters did not prevent blockade by oleic acid, and (ii) the effects of acutely administered phorbol ester and oleic acid were additive. In this cell line, signalling at bradykinin and bombesin receptors was also impaired by oleic acid. In A431 cells, oleic acid also blocked signal transduction at the EGF and B2 bradykinin receptors. Finally, in PC12 cells, oleic acid blocked the Ca2+ influx mediated by the activation of B2 bradykinin receptors. In conclusion: (1) NEFA block signal transduction by interfering with receptor-phospholipase C or phospholipase C-substrate interaction without preventing ligand binding; (2) NEFA do not act by a protein kinase C-mediated mechanism; (3) the effect of NEFA is dependent on their configuration rather than hydrophobicity or chain length; (4) this effect is evident in several different cell lines and receptor systems. Images Fig. 4. PMID:1898356

  3. Liver-specific mono-unsaturated fatty acid synthase-1 inhibitor for anti-hepatitis C treatment.

    PubMed

    Nio, Yasunori; Hasegawa, Hikari; Okamura, Hitomi; Miyayama, Yohei; Akahori, Yuichi; Hijikata, Makoto

    2016-08-01

    Recently, direct antiviral agents against hepatitis C virus (HCV) infection have been developed as highly effective anti-HCV drugs. However, the appearance of resistant viruses against direct anti-viral agents is an unsolved problem. One of the strategies considered to suppress the emergence of the drug-resistant viruses is to use drugs inhibiting the host factor, which contributes to HCV proliferation, in combination with direct anti-viral agents. The replication complex was reported to be present in the membranous compartment in the cells. Thus, lipid metabolism modulators are good candidates to regulate virus assembly and HCV replication. Recent studies have shown that stearoyl-CoA desaturase (SCD), an enzyme for long-chain mono-unsaturated fatty acid (LCMUFA) synthesis, is a key factor that defines HCV replication efficiency. Systemic exposure to SCD-1 inhibor induces some side effects in the eyes and skin. Thus, systemic SCD-1 inhibitors are considered inappropriate for HCV therapy. To avoid the side effects of systemic SCD-1 inhibitors, the liver-specific SCD-1 inhibitor, MK8245, was synthesized; it showed antidiabetic effects in diabetic model mice with no side effects. In the phase 1 clinical study on measurement of MK8245 tolerability, no significant side effects were reported (ClinicalTrials.gov Identifier: NCT00790556). Therefore, we thought liver-specific SCD-1 inhibitors would be suitable agents for HCV-infected patients. MK8245 was evaluated using recombinant HCV culture systems. Considering current HCV treatments, to avoid the emergence of direct anti-viral agents-resistant viruses, combination therapy with direct anti-viral agents and host-targeted agents would be optimal. With this viewpoint, we confirmed MK8245's additive or synergistic anti-HCV effects on current direct anti-viral agents and interferon-alpha therapy. The results suggest that MK8245 is an option for anti-HCV multi-drug therapy with a low risk of emergence of drug-resistant HCV

  4. [Deposition of exogenous and endogenously generated unsaturated fatty acids in lipid droplets triacylglycerol as a mechanism of its sequestration in epithelial cells].

    PubMed

    Fedorova, E V; Fok, E M; Bakhteeva, V T; Lavrova, E A; Parnova, R G

    2014-08-01

    Neutral lipids are deposited in intracellular compartments called lipid droplets, which are known to be critically implicated in regulation of cellular lipid metabolism. These organelles consist of a core of neutral lipids, mainly triacylglycerol (TAG) and cholesteryl esters, surrounded by phospholipid monolayer. Using Nile red lipid staining and [3H]-arachidonic and [3H]-oleic acids as precursors for lipid biosynthesis, we have evaluated the mechanisms of lipid body induction elicited by exogenous fatty acids within primary cultured epithelial cells from the frog urinary bladder. It was found that arachidonic and oleic acids at concentrations 10-50 tM stimulated lipid droplets formation accompanied by accumulation of TAG and by the significant increase of incorporation of fatty acids into TAG indicating an enhanced TAG biosynthesis. No changes of cholesteryl esters content were observed under these conditions. In cells, prelabelled with [3H]-oleic acids, etomoxir, an inhibitor of O-carnitine palmitroyltansferase 1, decreased oxidation of oleic acid and increased its incorporation into TAG leading to intracellular TAG accumulation. In cells, prelabelled with [3H]-arachidonic acid, diclofenac, an inhibitor of cyclooxygenase 1 and 2, led to significant decrease in cellular PGE2 production and to reesterification of free arachidonic acid to TAG but not to phospholipids. Taking together, these data evidence that in isolated frog urinary bladder epithelial cells, reacylation of unsaturated free fatty acids into TAG is a main route of their metabolic conversion under the conditions of the increased cytosolic level of free fatty acids. PMID:25682688

  5. Production of 10R-hydroxy unsaturated fatty acids from hempseed oil hydrolyzate by recombinant Escherichia coli cells expressing PpoC from Aspergillus nidulans.

    PubMed

    Han, Jeong-Eun; Seo, Min-Ju; Shin, Kyung-Chul; Oh, Deok-Kun

    2016-09-01

    The first and second preferred substrates of recombinant Escherichia coli cells expressing 10R-dioxygenase (PpoC) from Aspergillus nidulans and the purified enzyme were linoleic acid and α-linolenic acid, respectively. PpoC in cells showed higher thermal and reaction stabilities compared to purified PpoC. Thus, 10R-hydroxy unsaturated fatty acids were produced from linoleic acid, α-linolenic acid, and hempseed oil hydrolyzate containing linoleic acid and α-linolenic acid as substrates by whole recombinant cells expressing PpoC. The optimal reaction conditions for the production of 10R-hydroxy-8E,12Z-octadecadienoic acid (10R-HODE) were pH 8.0, 30 °C, 250 rpm, 5 % (v/v) dimethyl sulfoxide, 5 g l(-1) linoleic acid, and 60 g l(-1) cells in 100-ml baffled flask. Under these conditions, whole recombinant cells expressing PpoC produced 2.7 g l(-1) 10R-HODE from 5 g l(-1) linoleic acid for 40 min, with a conversion yield of 54 % (w/w) and a productivity of 4.0 g l(-1) h(-1); produced 2.2 g l(-1) 10R-hydroxy-8E,12Z,15Z-octadecatrienoic acid (10R-HOTrE) from 3 g l(-1) α-linolenic acid for 30 min, with a conversion yield of 72 % (w/w) and a productivity of 4.3 g l(-1) h(-1); and produced 1.8 g l(-1) 10R-HODE and 0.5 g l(-1) 10R-HOTrE from 5 g l(-1) hempseed oil hydrolyzate containing 2.5 g l(-1) linoleic acid and 1.0 g l(-1) α-linolenic acid for 30 min, with a conversion yield of 74 and 51 % (w/w), respectively, and a productivity of 3.6 and 1.0 g l(-1) h(-1), respectively. To the best of our knowledge, this is the first report on the biotechnological production of 10R-hydroxy unsaturated fatty acids. PMID:27129531

  6. Naquihexcin A, a S-Bridged Pyranonaphthoquinone Dimer Bearing an Unsaturated Hexuronic Acid Moiety from a Sponge-Derived Streptomyces sp. HDN-10-293.

    PubMed

    Che, Qian; Tan, Hongsheng; Han, Xiaoning; Zhang, Xiaomin; Gu, Qianqun; Zhu, Tianjiao; Li, Dehai

    2016-07-15

    S-Bridged pyranonaphthoquinone dimers, naquihexcins A and B (1 and 2), together with a related analogue (-)-BE-52440A (3) were obtained from the culture of a sponge-derived Streptomyces sp. HDN-10-293. Naquihexcin A (1) bears a rare unsaturated hexuronic acid moiety, and (-)-BE-52440A (3) has been discovered from natural resources. Compound 3 showed cytotoxicity against NB4 and HL-60 cells, while 1 could inhibit the proliferation of the adriamycin resistant human breast cancer cell line MCF-7 ADM. PMID:27341525

  7. Evaluation of biohydrogenation rate of canola vs. soya bean seeds as unsaturated fatty acids sources for ruminants in situ.

    PubMed

    Pashaei, S; Ghoorchi, T; Yamchi, A

    2016-04-01

    An experiment was conducted to study disappearance of C14 to C18 fatty acids, lag times and biohydrogenation (BH) rates of C18 fatty acids of ground soya bean and canola seeds in situ. Three ruminally fistulated Dallagh sheep were used to determine ruminal BH of unsaturated fatty acids (UFAs). Differences in the disappearance of fatty acids through the bags and lag times were observed between the oilseeds. We saw that the longer the incubation time of the oilseeds in the rumen, the lower the content of C18:2 and C18:3. Significantly higher lag times for both C18:2 and C18:3 were observed in ground canola compared to ground soya bean. BH rates of C18:2 and C18:3 fatty acids in soya bean were three times higher than those of canola. These results suggest that the fatty acid profile of fat source can affect the BH of UFAs by rumen micro-organisms. So that UFAs of canola had higher ability to escape from ruminal BH. It seems that fatty acid profile of ruminant products is more affected by canola seed compared to soya bean seed. PMID:26094995

  8. Perturbations in polar lipids, starvation survival and reproduction following exposure to unsaturated fatty acids or environmental toxicants in Daphnia magna.

    PubMed

    Sengupta, Namrata; Gerard, Patrick D; Baldwin, William S

    2016-02-01

    Acclimating to toxicant stress is energy expensive. In laboratory toxicology tests dietary conditions are ideal, but not in natural environments where nutrient resources vary in quality and quantity. We compared the effects of additional lipid resources, docosahexaenoic acid (n-3; DHA) or linoleic acid (n-6; LA), or the effects of the toxicants, atrazine or triclosan on post-treatment starvation survival, reproduction, and lipid profiles. Chemical exposure prior to starvation had chemical-specific effects as DHA showed moderately beneficial effects on starvation survival and all of the other chemicals showed adverse effects on either survival or reproduction. Surprisingly, pre-exposure to triclosan inhibits adult maturation and in turn completely blocks reproduction during the starvation phase. The two HR96 activators tested, atrazine and LA adversely reduce post-reproduction survival 70% during starvation and in turn show poor fecundity. DHA and LA show distinctly different lipid profiles as DHA primarily increases the percentage of large (>37 carbon) phosphatidylcholine (PC) species and LA primarily increases the percentage of smaller (<37 carbon) PC species. The toxicants atrazine and triclosan moderately perturb a large number of different phospholipids including several phosphatidylethanolamine species. Some of these polar lipid species may be biomarkers for diets rich in specific fatty acids or toxicant classes. Overall our data demonstrates that toxicants can perturb lipid utilization and storage in daphnids in a chemical specific manner, and different chemicals can produce distinct polar lipid profiles. In summary, biological effects caused by fatty acids and toxicants are associated with changes in the production and use of lipids. PMID:26606184

  9. Effects of dietary unsaturated fatty acids on oocyte quality and follicular development in lactating dairy cows in summer.

    PubMed

    Bilby, T R; Block, J; do Amaral, B C; Sa Filho, O; Silvestre, F T; Hansen, P J; Staples, C R; Thatcher, W W

    2006-10-01

    Dietary sources of fatty acids were evaluated for their influence on oocyte quality and follicular development using 54 lactating cows in summer. Fat supplements were 1) sunflower oil (80% cis 18:1), 2) Ca salt of transoctadecenoic acids (57% trans 18:1), 3) Ca salt of vegetable oils (30% 18:2), and 4) linseed oil (56% 18:3 and 16% 18:2). Fats were fed at 1.35% of dietary dry matter beginning at 5 wk prior to expected calving date and at 1.5% (oils) and 1.75% (Ca salts) of dietary dry matter for 15 wk after parturition. Four days following a programmed induced ovulation, 5 transvaginal oocyte aspirations were performed 3 or 4 d apart. Three days after the last aspiration, PGF2alpha was injected, followed 3 d later by a GnRH injection and a timed artificial insemination (d 0) 16 to 20 h later. For the first 4 aspirations, oocytes grading 1 or 2 were used for in vitro embryo production. Total cell number and the proportion of terminal deoxynucleotidyl transferase-mediated dUTP nick end labeling (TUNEL)-positive blastomeres were analyzed at d 8. At the fifth aspiration, the occurrence of metaphase II, group II caspase activity, and TUNEL labeling were determined after oocyte maturation. A total of 1,011 oocytes were collected. The proportion of oocytes with high caspase activity was greater for grade 3 compared with grades 1 and 2 (37.5 vs. 1.54 and 1.61%). Feeding polyunsaturated fatty acids, as compared with monosaturated fatty acids, failed to affect oocyte quality, as demonstrated by subsequent embryo development. Cows fed 18:2- or 18:3-enriched diets had a larger preovulatory follicle at insemination and subsequent volume of the corpus luteum compared with those fed cis 18:1 or trans 18:1 diets (16.8, 16.2 vs. 15.0, 14.9 +/- 0.7 mm; 7,323, 8,208 vs. 6,033, 5,495 +/- 644 mm3, respectively). The previously documented benefits of polyunsaturated fatty acids on reproductive performance appear to reflect actions at alternative biological windows in lactating dairy

  10. Metabolic Flux Between Unsaturated and Saturated Fatty Acids is Controlled by the FabA:FabB Ratio in the Fully Reconstituted Fatty Acid Biosynthetic Pathway of E. coli#

    PubMed Central

    Xiao, Xirui; Yu, Xingye; Khosla, Chaitan

    2013-01-01

    The entire fatty acid biosynthetic pathway from Escherichia coli, starting from the acetyl-CoA carboxylase, has been reconstituted in vitro from fourteen purified protein components. Radiotracer analysis verified stoichiometric conversion of acetyl-CoA and NAD(P)H into the free fatty acid product, allowing implementation of a facile spectrophotometric assay for kinetic analysis of this multi-enzyme system. At steady state, a maximum turnover rate of 0.5 s−1 was achieved. Under optimal turnover conditions, the predominant products were C16 and C18 saturated as well as monounsaturated fatty acids. The reconstituted system allowed us to quantitatively interrogate the factors that influence metabolic flux toward unsaturated versus saturated fatty acids. In particular, the concentrations of the dehydratase FabA and the β-ketoacyl synthase FabB were found to be crucial for controlling this property. By altering these variables, the percentage of unsaturated fatty acid produced could be adjusted between 10 and 50% without significantly affecting the maximum turnover rate of the pathway. Our reconstituted system provides a powerful tool to understand and engineer rate-limiting and regulatory steps in this complex and practically significant metabolic pathway. PMID:24147979

  11. Identification of the unsaturated heptadecyl fatty acids in the seed oils of Thespesia populnea and Gossypium hirsutum

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The fatty acid composition of the seed oils of Thespesia populnea and cotton variety SG-747 (Gossypium hirsutum) were studied to identity their 17-carbon fatty acids. With a combination of chemical derivatization, gas chromatography, and mass spectrometry, 8-heptadecenoic acid, 9-heptadecenoic acid...

  12. Seaweed extracts and unsaturated fatty acid constituents from the green alga Ulva lactuca as activators of the cytoprotective Nrf2–ARE pathway

    PubMed Central

    Wang, Rui; Paul, Valerie J.; Luesch, Hendrik

    2013-01-01

    Increased amounts of reactive oxygen species (ROS) have been implicated in many pathological conditions, including cancer. The major machinery that the cell employs to neutralize excess ROS is through the activation of the antioxidant-response element (ARE) that controls the activation of many phase II detoxification enzymes. The transcription factor that recognizes the ARE, Nrf2, can be activated by a variety of small molecules, most of which contain an α,β-unsaturated carbonyl system. In the pursuit of chemopreventive agents from marine organisms, we built, fractionated, and screened a library of 30 field-collected eukaryotic algae from Florida. An edible green alga, Ulva lactuca, yielded multiple active fractions by ARE–luciferase reporter assay. We isolated three monounsaturated fatty acid (MUFA) derivatives as active components, including a new keto-type C18 fatty acid (1), the corresponding shorter chain C16 acid (2), and an amide derivative (3) of the C18 acid. Their chemical structures were elucidated by NMR and mass spectrometry. All three contain the conjugated enone motif between C7 and C9, which is thought to be responsible for the ARE activity. Subsequent biological studies focused on 1, the most active and abundant ARE activator isolated. C18 acid 1 induced the expression of ARE-regulated cytoprotective genes, including NAD(P)H:quinone oxidoreductase 1, heme oxygenase 1, thioredoxin reductase 1, both subunits of the glutamate–cysteine ligase (catalytic subunit and modifier subunit), and the cystine/glutamate exchange transporter, in IMR-32 human neuroblastoma cells. Its cellular activity requires the presence of Nrf2 and PI3K function, based on RNA interference and pharmacological inhibitor studies, respectively. Treatment with 1 led only to Nrf2 activation, and not the increase in production of NRF2 mRNA. To test its ARE activity and cytoprotective potential in vivo, we treated mice with a single dose of a U. lactuca fraction that was enriched

  13. Seaweed extracts and unsaturated fatty acid constituents from the green alga Ulva lactuca as activators of the cytoprotective Nrf2-ARE pathway.

    PubMed

    Wang, Rui; Paul, Valerie J; Luesch, Hendrik

    2013-04-01

    Increased amounts of reactive oxygen species (ROS) have been implicated in many pathological conditions, including cancer. The major machinery that the cell employs to neutralize excess ROS is through the activation of the antioxidant-response element (ARE) that controls the activation of many phase II detoxification enzymes. The transcription factor that recognizes the ARE, Nrf2, can be activated by a variety of small molecules, most of which contain an α,β-unsaturated carbonyl system. In the pursuit of chemopreventive agents from marine organisms, we built, fractionated, and screened a library of 30 field-collected eukaryotic algae from Florida. An edible green alga, Ulva lactuca, yielded multiple active fractions by ARE-luciferase reporter assay. We isolated three monounsaturated fatty acid (MUFA) derivatives as active components, including a new keto-type C18 fatty acid (1), the corresponding shorter chain C16 acid (2), and an amide derivative (3) of the C18 acid. Their chemical structures were elucidated by NMR and mass spectrometry. All three contain the conjugated enone motif between C7 and C9, which is thought to be responsible for the ARE activity. Subsequent biological studies focused on 1, the most active and abundant ARE activator isolated. C18 acid 1 induced the expression of ARE-regulated cytoprotective genes, including NAD(P)H:quinone oxidoreductase 1, heme oxygenase 1, thioredoxin reductase 1, both subunits of the glutamate-cysteine ligase (catalytic subunit and modifier subunit), and the cystine/glutamate exchange transporter, in IMR-32 human neuroblastoma cells. Its cellular activity requires the presence of Nrf2 and PI3K function, based on RNA interference and pharmacological inhibitor studies, respectively. Treatment with 1 led only to Nrf2 activation, and not the increase in production of NRF2 mRNA. To test its ARE activity and cytoprotective potential in vivo, we treated mice with a single dose of a U. lactuca fraction that was enriched with

  14. Effects of two different dietary sources of long chain omega-3, highly unsaturated fatty acids on incorporation into the plasma, red blood cell, and skeletal muscle in horses.

    PubMed

    Hess, T M; Rexford, J K; Hansen, D K; Harris, M; Schauermann, N; Ross, T; Engle, T E; Allen, K G D; Mulligan, C M

    2012-09-01

    The objective of this study was to examine the effects of different sources of dietary omega-3 (n-3) fatty acid supplementation on plasma, red blood cell, and skeletal muscle fatty acid compositions in horses. Twenty-one mares were blocked by age, BW, and BCS and assigned to 1 of 3 dietary treatments with 7 mares per treatment. Dietary treatments were: 1) control or no fatty acid supplement (CON), 2) 38 g of n-3 long chain, highly unsaturated fatty acid (LCHUFA) supplement/d provided by algae and fish oil (MARINE) containing alpha-linolenic acid (ALA), eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), and docosapentaenoic acid (DPA), and 3) 38 g of n-3 LCHUFA supplement/d provided by a flaxseed meal (FLAX) containing ALA. Each supplement was added to a basal diet consisting of hay and barley and was fed for 90 d. Blood samples and muscle middle gluteal biopsies were taken at d 0, 30, 60 and 90 of supplementation. Plasma, red blood cell and skeletal muscle fatty acid profiles were determined via gas chromatography. Plasma linoleic acid (LA) and ALA were at least 10 and 60% less (P < 0.01), respectively, in the MARINE compared with the FLAX and CON groups. Plasma EPA and DHA were only detected in the MARINE group, and EPA increased 40% (P < 0.001) from d 30 to 60, and DHA 19% (P < 0.01) from d 30 to 90. Red blood cell LA and ALA were not different among treatments. Red blood cell EPA and DHA were only detected in the MARINE group, where EPA increased 38% (P < 0.01) from d 30 to 60, and DHA increased 56% (P < 0.001) between d 30 and 90. Skeletal muscle LA was at least 17% less (P < 0.001) in the MARINE group compared with the other treatments. Skeletal muscle ALA was 15% less (P = 0.03) in the MARINE group compared with FLAX and CON groups. Skeletal muscle EPA was at least 25% greater (P < 0.001) in MARINE group compared with other treatments and increased (P < 0.001) by 71% from d 30 to 60. Skeletal muscle DHA was at least 57% greater (P < 0.001) in the MARINE

  15. Unsaturated fatty acids show clear elicitation responses in a modified local lymph node assay with an elicitation phase, and test positive in the direct peptide reactivity assay.

    PubMed

    Yamashita, Kunihiko; Shinoda, Shinsuke; Hagiwara, Saori; Miyazaki, Hiroshi; Itagaki, Hiroshi

    2015-12-01

    The Organisation for Economic Co-operation and Development (OECD) Test Guidelines (TG) adopted the murine local lymph node assay (LLNA) and guinea pig maximization test (GPMT) as stand-alone skin sensitization test methods. However, unsaturated carbon-carbon double-bond and/or lipid acids afforded false-positive results more frequently in the LLNA compared to those in the GPMT and/or in human subjects. In the current study, oleic, linoleic, linolenic, undecylenic, fumaric, maleic, and succinic acid and squalene were tested in a modified LLNA with an elicitation phase (LLNA:DAE), and in a direct peptide reactivity assay (DPRA) to evaluate their skin-sensitizing potential. Oleic, linoleic, linolenic, undecylenic and maleic acid were positive in the LLNA:DAE, of which three, linoleic, linolenic, and maleic acid were positive in the DPRA. Furthermore, the results of the cross-sensitizing tests using four LLNA:DAE-positive chemicals were negative, indicating a chemical-specific elicitation response. In a previous report, the estimated concentration needed to produce a stimulation index of 3 (EC3) of linolenic acid, squalene, and maleic acid in the LLNA was < 10%. Therefore, these chemicals were classified as moderate skin sensitizers in the LLNA. However, the skin-sensitizing potential of all LLNA:DAE-positive chemicals was estimated as weak. These results suggested that oleic, linoleic, linolenic, undecylenic, and maleic acid had skin-sensitizing potential, and that the LLNA overestimated the skin-sensitizing potential compared to that estimated by the LLNA:DAE. PMID:26558466

  16. Effects of tung oilseed FAD2 and DGAT2 genes on unsaturated fatty acid accumulation in Rhodotorula glutinis and Arabidopsis thaliana.

    PubMed

    Chen, Yicun; Cui, Qinqin; Xu, Yongjie; Yang, Susu; Gao, Ming; Wang, Yangdong

    2015-08-01

    Genetic engineering to produce valuable lipids containing unsaturated fatty acids (UFAs) holds great promise for food and industrial applications. Efforts to genetically modify plants to produce desirable UFAs with single enzymes, however, have had modest success. The key enzymes fatty acid desaturase (FAD) and diacylglycerol acyltransferase (DGAT) are responsible for UFA biosynthesis (a push process) and assembling fatty acids into lipids (a pull process) in plants, respectively. To examine their roles in UFA accumulation, VfFAD2 and VfDGAT2 genes cloned from Vernicia fordii (tung tree) oilseeds were conjugated and transformed into Rhodotorula glutinis and Arabidopsis thaliana via Agrobacterium tumefaciens. Real-time quantitative PCR revealed variable gene expression levels in the transformants, with a much higher level of VfDGAT2 than VfFAD2. The relationship between VfFAD2 expression and linoleic acid (C18:2) increases in R. glutinis (R (2) = 0.98) and A. thaliana (R (2) = 0.857) transformants was statistically linear. The VfDGAT2 expression level was statistically correlated with increased total fatty acid content in R. glutinis (R (2) = 0.962) and A. thaliana (R (2) = 0.8157) transformants. With a similar expression level between single- and two-gene transformants, VfFAD2-VfDGAT2 co-transformants showed a higher linolenic acid (C18:3) yield in R. glutinis (174.36 % increase) and A. thaliana (14.61 % increase), and eicosatrienoic acid (C20:3) was enriched (17.10 % increase) in A. thaliana. Our data suggest that VfFAD2-VfDGAT2 had a synergistic effect on UFA metabolism in R. glutinis, and to a lesser extent, A. thaliana. These results show promise for further genetic engineering of plant lipids to produce desirable UFAs. PMID:25754996

  17. An organocatalytic Michael-cyclization cascade of 4-oxa-α,β-unsaturated carboxylic acids with aldehydes: facile synthesis of chiral γ-lactols and trisubstituted γ-lactones.

    PubMed

    Lin, Jun-Bing; Xu, Shi-Ming; Xie, Ji-Kang; Li, Hong-Yu; Xu, Peng-Fei

    2015-02-28

    An organocatalytic Michael-cyclization cascade of aldehydes with 4-oxa-α,β-unsaturated carboxylic acids has been developed, giving functionalized γ-lactols with high yields and enantioselectivities. The products could be easily transformed into complex trisubstituted γ-lactones and γ-lactams. PMID:25633800

  18. N-Heterocyclic carbene-catalyzed [4 + 2] cyclization of α,β-unsaturated carboxylic acids bearing γ-H with isatins: an enantioselective synthesis of spirocyclic oxindole-dihydropyranones.

    PubMed

    Zhu, Ling; Yu, Chenxia; Li, Tuanjie; Wang, Yuhong; Lu, Yinan; Wang, Wenjing; Yao, Changsheng

    2016-01-28

    An NHC-catalyzed asymmetric [4 + 2] annulation of isatins and α,β-unsaturated carboxylic acids bearing γ-H gave spirocyclic oxindole-dihydropyranones successfully via an in situ activation strategy. This protocol featured easy availability of raw materials, good yields and excellent enantioselectivities (up to 99% ee). PMID:26690686

  19. DIFFERENTIAL EFFECTS OF SATURATED AND UNSATURATED FATTY ACID DIETS ON CARDIOMYOCYTE APOPTOSIS, ADIPOSE DISTRIBUTION, AND SERUM LEPTIN

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Fatty acids are the primary fuel for the heart and are ligands for peroxisome proliferator-activated receptors (PPARs), which regulate the expression of genes encoding proteins involved in fatty acid metabolism. Saturated fatty acids, particularly palmitate, can be converted to the proapoptotic lipi...

  20. Dietary long-chain unsaturated fatty acids acutely and differently reduce the activities of lipogenic enzymes and of citrate carrier in rat liver.

    PubMed

    Gnoni, Antonio; Giudetti, Anna M

    2016-09-01

    The activities of lipogenic enzymes appear to fluctuate with changes in the level and type of dietary fats. Polyunsaturated fatty acids (PUFAs) are known to induce on hepatic de novo lipogenesis (DNL) the highest inhibitory effect, which occurs through a long-term adaptation. Data on the acute effects of dietary fatty acids on DNL are lacking. In this study with rats, the acute 1-day effect of high-fat (15 % w/w) diets (HFDs) enriched in saturated fatty acids (SFAs) or unsaturated fatty acids (UFAs), i.e., monounsaturated (MUFA) and PUFA, of the ω-6 and ω-3 series on DNL and plasma lipid level was investigated; a comparison with a longer time feeding (21 days) was routinely carried out. After 1-day HFD administration UFA, when compared to SFA, reduced plasma triacylglycerol (TAG) level and the activities of the lipogenic enzymes acetyl-CoA carboxylase (ACC) and fatty acid synthase (FAS), a decreased activity of the citrate carrier (CIC), a mitochondrial protein linked to lipogenesis, was also detected. In this respect, ω-3 PUFA was the most effective. On the other hand, PUFA maintained the effects at longer times, and the acute inhibition induced by MUFA feeding on DNL enzyme and CIC activities was almost nullified at 21 days. Mitochondrial fatty acid composition was slightly but significantly changed both at short- and long-term treatment, whereas the early changes in mitochondrial phospholipid composition vanished in long-term experiments. Our results suggest that in the early phase of administration, UFA coordinately reduced both the activities of de novo lipogenic enzymes and of CIC. ω-3 PUFA showed the greatest effect. PMID:27312217

  1. Identification of a conserved protein involved in anaerobic unsaturated fatty acid synthesis in Neiserria gonorrhoeae: implications for facultative and obligate anaerobes that lack FabA.

    PubMed

    Isabella, Vincent M; Clark, Virginia L

    2011-10-01

    Transcriptome analysis of the facultative anaerobe, Neisseria gonorrhoeae, revealed that many genes of unknown function were induced under anaerobic conditions. Mutation of one such gene, NGO1024, encoding a protein belonging to the 2-nitropropane dioxygenase-like superfamily of proteins, was found to result in an inability of gonococci to grow anaerobically. Anaerobic growth of an NG1024 mutant was restored upon supplementation with unsaturated fatty acids (UFA), but not with the saturated fatty acid palmitate. Gonococcal fatty acid profiles confirmed that NGO1024 was involved in UFA synthesis anaerobically, but not aerobically, demonstrating that gonococci contain two distinct pathways for the production of UFAs, with a yet unidentified aerobic mechanism, and an anaerobic mechanism involving NGO1024. Expression of genes involved in classical anaerobic UFA synthesis, fabA, fabM and fabB, was toxic in gonococci and unable to complement a NGO1024 mutation, suggesting that the chemistry involved in gonococcal anaerobic UFA synthesis is distinct from that of the classical pathway. NGO1024 homologues, which we suggest naming UfaA, form a distinct lineage within the 2-nitropropane dioxygenase-like superfamily, and are found in many facultative and obligate anaerobes that produce UFAs but lack fabA, suggesting that UfaA is part of a widespread pathway involved in UFA synthesis. PMID:21895795

  2. Simultaneous analysis of low plasma levels of deuterium-labeled saturated and unsaturated fatty acids as t-butyldimethylsilyl esters

    SciTech Connect

    Parsons, H.; Emken, E.M.; Marai, L.; Kuksis, A.

    1986-03-01

    A sensitive and accurate method for detection and quantitation of deuterated fatty acids in the presence of large amounts of unlabeled fatty acids is described using mass fragmentography in combination with the preparation of tertiarybutyldimethylsilyl esters (t-BDMS). The method has been applied to determination of deuterated stearic, oleic, elaidic and linoleic acids in human plasma lipoproteins following duodenal perfusion with a micellar mixture of acids. Over a concentration range of 10-1000 ng/ml, the average coefficient of variation for the linoleate was 3% and for the oleate (elaidate) ester was 2%.

  3. Mechanistic aspects of the rhodium-catalyzed enantioselective transfer hydrogenation of [alpha],[beta]-unsaturated carboxylic acids using formic acid/triethylamine (5:2) as the hydrogen source

    SciTech Connect

    Leitner, W. Universitaet Regensburg ); Brown, J.M. ); Brunner, H. )

    1993-01-13

    The mechanism of the rhodium-catalyzed enantioselective transfer hydrogenation of methylenebutanedioic acid (itaconic acid) (1) and related [alpha],[beta]-unsaturated carboxylic acids using formic acid/triethylamine (5:2) as the hydrogen source is investigated. Kinetic studies using [sup 1]H NMR spectroscopy are presented. Formic acid decomposition is shown to be the rate-limiting step with 1 as the substrate, while hydrogen transfer turns out to be rate determining in the case of (E)-(phenylmethylene)butanedioic acid ((E)-phenylitaconic acid) (3). Furthermore, extensive use is made of deuterium labeling and the analysis of part-deuterated products by [sup 1]H and [sup 13]C[l brace][sup 1]H,[sup 2]H[r brace] NMR spectroscopy. Taken together, these results indicate that the mechanism of rhodium-catalyzed transfer hydrogenation with formic acid/triethylamine as the hydrogen source most likely involves decarboxylation of a transient formate species to form hydridic complexes of rhodium, in which the Rh-H entity has a long lifetime relative to hydrogen transfer to the substrate. 40 refs., 5 figs., 1 tab.

  4. Influence of liposomes rich in unsaturated or saturated fatty acids on the growth of human xenotransplanted mammary carcinomas and on the levels of heart type fatty acid binding protein.

    PubMed

    Naundorf, H; Zschiesche, W; Reszka, R; Fichtner, I

    1995-01-01

    A panel of 4 human mammary carcinomas passaged in nude mice were subjected to intraperitoneal application of cholesterol-free liposomes enriched with linoleic (unsaturated fatty acid) or stearic acid (saturated fatty acid). The liposomes were examined with regard to their influence on the tumor growth and level of heart type fatty acid binding protein (FABP). Liposomes with different fatty acid composition influenced the growth of mammary carcinomas 3366, BO, 4000 and 4151 in distinct ways. Liposomes with a high content of stearic acid significantly inhibited the growth of mammary carcinomas 3366 and BO, whereas mammary carcinomas 4000 and 4151 were not affected. The growth of mammary carcinoma 3366 was moderately increased after supplementation of liposomes rich in linoleic acid, the tumor BO was significantly inhibited and the growth of MaCa 4000 and 4151 was unchanged. Liposome treatment led to a significant increase in heart type FABP in mammary carcinomas 3366 and BO regardless of whether the animals were treated with liposomes rich in stearic or linoleic acid. Such significant changes of FABP level could not be observed in mammary carcinomas 4000 or 4151. We suggest that the lipid-mediated growth modulation seems to be dependent on an increase of heart type FABPs in these tumor models. PMID:8562891

  5. Effects of dietary palmitoleic acid on plasma lipoprotein profile and aortic cholesterol accumulation are similar to those of other unsaturated fatty acids in the F1B golden Syrian hamster.

    PubMed

    Matthan, Nirupa R; Dillard, Alice; Lecker, Jaime L; Ip, Blanche; Lichtenstein, Alice H

    2009-02-01

    The lower susceptibility of palmitoleic acid (16:1) to oxidation compared to PUFA may confer functional advantages with respect to finding acceptable alternatives to partially hydrogenated fats, but limited data are available on its effect on cardiovascular risk factors. This study investigated the effect of diets (10% fat, 0.1% cholesterol, wt:wt) enriched with macadamia [monounsaturated fatty acid (MUFA)16:1], palm (SFA,16:0), canola (MUFA,18:1), or safflower (PUFA,18:2) oils on lipoprotein profiles and aortic cholesterol accumulation in F1B Golden Syrian hamsters (n = 16/group). After 12 wk, 8 hamsters in each group were killed (phase 1). The remaining hamsters fed palm oil were changed to a diet containing coconut oil, while hamsters in the other diet groups continued on their original diets for an additional 6 wk (phase 2). With minor exceptions, the time course and dietary SFA source did not alter the study outcomes. Macadamia oil-fed hamsters had lower non-HDL cholesterol and triglyceride concentrations compared with the palm and coconut oil-fed hamsters and higher HDL-cholesterol compared with the coconut, canola, and safflower oil-fed hamsters. The aortic cholesterol concentration was not affected by dietary fat type. The hepatic cholesterol concentration was higher in the unsaturated compared with the saturated oil-fed hamsters. RBC membrane and aortic cholesteryl ester, triglyceride, and phospholipid fatty acid profiles reflected that of the dietary oil. These data suggest that an oil relatively high in palmitoleic acid does not adversely affect plasma lipoprotein profiles or aortic cholesterol accumulation and was similar to other unsaturated fatty acid-rich oils. PMID:19106316

  6. The role of total fats, saturated/unsaturated fatty acids and cholesterol content in chicken meat as cardiovascular risk factors

    PubMed Central

    2014-01-01

    Background The objective of the study was to present information about the chemical composition, the fatty acids profile, and cholesterol content of chicken meat in order to investigate the impact of chicken meat consumption on cardiovascular risk in the general population. Methods A total of 48 6-wk-old broiler chickens broilers from two farms in June to November of 2012, and February of 2013, were used in this trial. Total lipid content was determined by extraction of fat by petrol ether (Soxhlet) after acid hydrolysis of samples. Fatty acids were determined by capillary gas chromatography. Cholesterol determination was performed by using HPLC/PDA system. Results The results indicate that the total free cholesterol content in raw breast and drumstick of chickens was in the range of 37,41–79,9 mg/100 g and 48,35-99,5 mg/100 g, respectively. The main fatty acids identified in all cuts were C18:1c9, C18:2n6, C16:0, C18:0, and C16:1. Decreasing the dietary n-6/n-3 clearly decreased the content in breast and drumstick muscle of C18:2n6, C18:3n3, and C20: 3n6, but increased that of C16:0, C18:0, and C20:2. Also, the major saturated fatty acid (SFA) (C16:0 and C18:0) was significantly differ among the four treatments. Conclusion Our study shows that dietary fat and fatty acid composition influence the concentrations of total cholesterol content, total fat content, and fatty acid composition in broiler muscle. This information will aid in determining the burden of chicken meat as a cardiovascular risk factors disease and act as a planning tool for public-health Programmes. PMID:24588940

  7. The effect of unsaturated fatty acid and triglyceride oil addition on the mechanical and antibacterial properties of acrylic bone cements.

    PubMed

    Persson, Cecilia; Robert, Elise; Carlsson, Elin; Robo, Céline; López, Alejandro; Godoy-Gallardo, Maria; Ginebra, Maria-Pau; Engqvist, Håkan

    2015-09-01

    Acrylic bone cements have an elastic modulus several times higher than the surrounding trabecular bone. This has been hypothesized to contribute to certain clinical complications. There are indications that the addition of specific fatty acids and triglyceride oils may reduce the elastic modulus of these types of cements. Some of these additives also appear to have inherent antibiotic properties, although this has never been evaluated in bone cements. In this study, several types of fatty acids and triglyceride oils were evaluated for use in acrylic bone cements. Their mechanical properties were evaluated under uniaxial compression testing and selected cements were then further characterized in terms of microstructure, handling and antibacterial properties using scanning electron microscopy, polymerization temperature measurements, agar diffusion tests and bactericidal activity assays of cement extracts. It was found that any of the evaluated fatty acids or triglyceride oils could be used to tailor the stiffness of acrylic bone cements, although at varying concentrations, which also depended on the type of commercial base cement used. In particular, the addition of very small amounts of linoleic acid (<2.0 wt%) resulted in Young's moduli and compressive strengths in the range of human trabecular bone, while maintaining a similar setting time. Further, the addition of 12.6 wt% ricinoleic acid to Osteopal V cement was found to have a significant antibacterial effect, inhibiting growth of Staphylococcus aureus in an agar diffusion test as well as demonstrating 100% bactericidal activity against the same strain. PMID:25876889

  8. Effect of the ratios of unsaturated fatty acids on the expressions of genes related to fat and protein in the bovine mammary epithelial cells.

    PubMed

    Sheng, R; Yan, S M; Qi, L Z; Zhao, Y L

    2015-04-01

    The objective of this study was to evaluate the effects of the different ratios of unsaturated fatty acids (UFAs) (oleic acid, linoleic acid, and linolenic acid) on the cell viability and triacylglycerol (TAG) content, as well as the mRNA expression of the genes related to lipid and protein synthesis in bovine mammary epithelial cells (BMECs). Primary cells were isolated from the mammary glands of Holstein dairy cows and were passaged twice. Afterward, the cells were randomly allocated to six treatments, five UFA-treated groups, and one control group. For all of the treatments, the the fetal bovine serum in the culture solution was replaced with fatty acid-free BSA (1 g/L), and the cells were treated with different ratios of oleic, linoleic, and linolenic acids (0.75:4:1, 1.5:10:1, 2:13.3:1, 3:20:1, and 4:26.7:1) for 48 h, which were group 1 to group 5. The control culture solution contained only fatty acid-free BSA without UFAs (0 μM). The results indicated that the cell viability was not affected by adding different ratios of UFAs, but the accumulation of TAG was significantly influenced by supplementing with different ratios of UFAs. Adding different ratios of UFAs suppressed the expression of ACACA and FASN but had the opposite effect on the abundances of FABP3 and CD36 mRNA. The expression levels of PPARG, SPEBF1, CSN1S1, and CSN3 mRNA in the BMECs were affected significantly after adding different ratios of UFAs. Our results suggested that groups 1, 2, and 3 (0.75:4:1, 1.5:10:1, and 2:13.3:1) had stronger auxo-action on fat synthesis in the BMECs, where group 3 (2:13.3:1) was the best, followed by group 4 (3:20:1). However, group 5 (4:26.7:1) was the worst. Genes related to protein synthesis in the BMECs were better promoted in groups 2 and 3, and group 3 had the strongest auxo-action, whereas the present study only partly examined the regulation of protein synthesis at the transcriptional level; more studies on translation level are needed in the future

  9. Temperature and pH responsiveness of poly-(DMAA-co-unsaturated carboxylic acid) hydrogels synthesized by UV-irradiation

    NASA Astrophysics Data System (ADS)

    Kakinoki, Sachiro; Kaetsu, Isao; Nakayama, Masashi; Sutani, Kouichi; Uchida, Kumao; Yukutake, Kouji

    2003-07-01

    Stimuli-responsive polyampholyte hydrogels were synthesized by the copolymerization of dimethylaminoethyl methacrylate (DMAA) and acrylic acid (AAc) or itaconic acid (IAc) by UV-irradiation. Temperature and pH responsiveness of these hydrogels were studied. The temperature responsiveness of poly-(DMAA-co-AAc, IAc) hydrogels shown in change of water content became dull compared to that of DMAA homo-polymer hydrogel. The water content of the poly-(DMAA-co-AAc, IAc) hydrogels showed a minimum at pH 8, and increased in more acidic and alkaline regions. This fact can be attributed to the coexistence of anions and cations in the poly-(DMAA-co-AAc, IAc) hydrogels. The poly-(DMAA-co-AAc, IAc) hydrogels were polyampholyte having both temperature responsiveness and pH responsiveness.

  10. Enhancing highly unsaturated omega-3 fatty acids in phase-fed rainbow trout (Oncorhynchus mykiss) using Alaskan fish oils

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The objective of this research was to investigate differences in the kinetics of fatty acids (FA) deposition in fillets of market-sized (approximately 450g) rainbow trout (Oncorhynchus mykiss) fed diets containing commercial Alaskan fish oils versus menhaden oil. Comparisons were made with FA leve...

  11. Chemical Evolution of Acid Precipitation in Unsaturated Zone of the Pennsylvanian Siltstones and Shales of Central Ohio

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The North Appalachian Experimental Watershed in Coshocton, Ohio has recorded over a 30-yr period average pH of precipitation of 4.7. The area lies within the Pennsylvanian siltstones and shale dominated by aluminosilicates and <5% calcite. A study was conducted to determine the evolution of acid dep...

  12. Physiological evidence for the presence of a cis-trans isomerase of unsaturated fatty acids in Methylococcus capsulatus Bath to adapt to the presence of toxic organic compounds.

    PubMed

    Löffler, Claudia; Eberlein, Christian; Mäusezahl, Ines; Kappelmeyer, Uwe; Heipieper, Hermann J

    2010-07-01

    The physiology of the response in the methanotrophic bacterium Methylococcus capsulatus Bath towards thermal and solvent stress was studied. A systematic investigation of the toxic effects of organic compounds (chlorinated phenols and alkanols) on the growth of this bacterium was carried out. The sensitivity to the tested alkanols correlated with their chain length and hydrophobicity; methanol was shown to be an exception to which the cells showed a very high tolerance. This can be explained by the adaptation of these bacteria to growth on C1 compounds. On the other hand, M. capsulatus Bath was very sensitive towards the tested chlorinated phenols. The high toxic effect of phenolic compounds on methanotrophic bacteria might be explained by the occurrence of toxic reactive oxygen species. In addition, a physiological proof of the presence of cis-trans isomerization as a membrane-adaptive response mechanism in M. capsulatus was provided. This is the first report on physiological evidence for the presence of the unique postsynthetic membrane-adaptive response mechanism of the cis-trans isomerization of unsaturated fatty acids in a bacterium that does not belong to the genera Pseudomonas and Vibrio where this mechanism was already reported and described extensively. PMID:20487020

  13. Ultrashort-TE stimulated echo acquisition mode (STEAM) improves the quantification of lipids and fatty acid chain unsaturation in the human liver at 7 T.

    PubMed

    Gajdošík, Martin; Chadzynski, Grzegorz L; Hangel, Gilbert; Mlynárik, Vladimír; Chmelík, Marek; Valkovič, Ladislav; Bogner, Wolfgang; Pohmann, Rolf; Scheffler, Klaus; Trattnig, Siegfried; Krššák, Martin

    2015-10-01

    Ultrahigh-field, whole-body MR systems increase the signal-to-noise ratio (SNR) and improve the spectral resolution. Sequences with a short TE allow fast signal acquisition with low signal loss as a result of spin-spin relaxation. This is of particular importance in the liver for the precise quantification of the hepatocellular content of lipids (HCL). In this study, we introduce a spoiler Gradient-switching Ultrashort STimulated Echo AcqUisition (GUSTEAU) sequence, which is a modified version of a stimulated echo acquisition mode (STEAM) sequence, with a minimum TE of 6 ms. With the high spectral resolution at 7 T, the efficient elimination of water sidebands and the post-processing suppression of the water signal, we estimated the composition of fatty acids (FAs) via the detection of the olefinic lipid resonance and calculated the unsaturation index (UI) of hepatic FAs. The performance of the GUSTEAU sequence for the assessment of UI was validated against oil samples and provided excellent results in agreement with the data reported in the literature. When measuring HCL with GUSTEAU in 10 healthy volunteers, there was a high correlation between the results obtained at 7 and 3 T (R(2) = 0.961). The test-retest measurements yielded low coefficients of variation for HCL (4 ± 3%) and UI (11 ± 8%) when measured with the GUSTEAU sequence at 7 T. A negative correlation was found between UI and HCL (n = 10; p < 0.033). The ultrashort TE MRS sequence (GUSTEAU; TE = 6 ms) provided high repeatability for the assessment of HCL. The improved spectral resolution at 7 T with the elimination of water sidebands and the offline water subtraction also enabled an assessment of the unsaturation of FAs. This all highlights the potential use of this MRS acquisition scheme for studies of hepatic lipid composition in vivo. PMID:26313737

  14. Cooperative Photo-/Lewis Acid Catalyzed Tandem Intramolecular [3 + 2] Cross-Cycloadditions of Cyclopropane 1,1-Diesters with α,β-Unsaturated Carbonyls for Medium-Sized Carbocycles.

    PubMed

    Wang, Zhenjun; Chen, Shuai; Ren, Jun; Wang, Zhongwen

    2015-09-01

    A tandem isomerization/intramolecular [3 + 2] cross-cycloaddition (IMCC) of cyclopropane 1,1-diesters with α,β-unsaturated ketones/aldehydes under a cooperative catalysis of photo and Lewis acids has been successfully developed. This supplied a general and efficient strategy for construction of medium-sized carbocyclic (8-, 9-, and 10-membered) skeletons as well as such carbocycle-based bridged oxa-bicyclo[n.2.1] (n = 4-6) skeletons. PMID:26313742

  15. Accumulation of Polyhydroxyalkanoic Acid Containing Large Amounts of Unsaturated Monomers in Pseudomonas fluorescens BM07 Utilizing Saccharides and Its Inhibition by 2-Bromooctanoic Acid

    PubMed Central

    Lee, Ho-Joo; Choi, Mun Hwan; Kim, Tae-Un; Yoon, Sung Chul

    2001-01-01

    A psychrotrophic bacterium, Pseudomonas fluorescens BM07, which is able to accumulate polyhydroxyalkanoic acid (PHA) containing large amounts of 3-hydroxy-cis-5-dodecenoate unit up to 35 mol% in the cell from unrelated substrates such as fructose, succinate, etc., was isolated from an activated sludge in a municipal wastewater treatment plant. When it was grown on heptanoic acid (C7) to hexadecanoic acid (C16) as the sole carbon source, the monomer compositional characteristics of the synthesized PHA were similar to those observed in other fluorescent pseudomonads belonging to rRNA homology group I. However, growth on stearic acid (C18) led to no PHA accumulation, but instead free stearic acid was stored in the cell. The existence of the linkage between fatty acid de novo synthesis and PHA synthesis was confirmed by using inhibitors such as acrylic acid and two other compounds, 2-bromooctanoic acid and 4-pentenoic acid, which are known to inhibit β-oxidation enzymes in animal cells. Acrylic acid completely inhibited PHA synthesis at a concentration of 4 mM in 40 mM octanoate-grown cells, but no inhibition of PHA synthesis occurred in 70 mM fructose-grown cells in the presence of 1 to 5 mM acrylic acid. 2-Bromooctanoic acid and 4-pentenoic acid were found to much inhibit PHA synthesis much more strongly in fructose-grown cells than in octanoate-grown cells over concentrations ranging from 1 to 5 mM. However, 2-bromooctanoic acid and 4-pentenoic acid did not inhibit cell growth at all in the fructose media. Especially, with the cells grown on fructose, 2-bromooctanoic acid exhibited a steep rise in the percent PHA synthesis inhibition over a small range of concentrations below 100 μM, a finding indicative of a very specific inhibition, whereas 4-pentenoic acid showed a broad, featureless concentration dependence, suggesting a rather nonspecific inhibition. The apparent inhibition constant Ki (the concentration for 50% inhibition of PHA synthesis) for 2

  16. Asymmetric synthesis of syn-propargylamines and unsaturated β-amino acids under Brønsted base catalysis

    PubMed Central

    Wang, Yingcheng; Mo, Mingjie; Zhu, Kongxi; Zheng, Chao; Zhang, Hongbin; Wang, Wei; Shao, Zhihui

    2015-01-01

    Propargylamines are important intermediates for the synthesis of polyfunctional amino derivatives and natural products and biologically active compounds. The classic method of synthesizing chiral propargylamines involves the asymmetric alkynylation of imines. Here, we report a significant advance in the catalytic asymmetric Mannich-type synthesis of propargylamines through catalytic asymmetric addition of carbon nucleophiles to C-alkynyl imines, culminating in a highly syn-selective catalytic asymmetric Mannich reaction of C-alkynyl imines that provide syn-configured propargylamines with two adjacent stereogenic centres and a transition metal-free organocatalytic asymmetric approach to β-alkynyl-β-amino acids with high efficiency and practicality, via a chiral Brønsted base-catalysed asymmetric Mannich-type reaction of in situ generated challenging N-Boc C-alkynyl imines from previously unreported C-alkynyl N-Boc-N,O-acetals, with α-substituted β-keto esters and less-acidic malonate (thio)esters as nucleophiles, respectively. A catalytic activation strategy is also disclosed, which may have broad implications for use in catalysis and synthesis. PMID:26423837

  17. Asymmetric synthesis of syn-propargylamines and unsaturated β-amino acids under Brønsted base catalysis.

    PubMed

    Wang, Yingcheng; Mo, Mingjie; Zhu, Kongxi; Zheng, Chao; Zhang, Hongbin; Wang, Wei; Shao, Zhihui

    2015-01-01

    Propargylamines are important intermediates for the synthesis of polyfunctional amino derivatives and natural products and biologically active compounds. The classic method of synthesizing chiral propargylamines involves the asymmetric alkynylation of imines. Here, we report a significant advance in the catalytic asymmetric Mannich-type synthesis of propargylamines through catalytic asymmetric addition of carbon nucleophiles to C-alkynyl imines, culminating in a highly syn-selective catalytic asymmetric Mannich reaction of C-alkynyl imines that provide syn-configured propargylamines with two adjacent stereogenic centres and a transition metal-free organocatalytic asymmetric approach to β-alkynyl-β-amino acids with high efficiency and practicality, via a chiral Brønsted base-catalysed asymmetric Mannich-type reaction of in situ generated challenging N-Boc C-alkynyl imines from previously unreported C-alkynyl N-Boc-N,O-acetals, with α-substituted β-keto esters and less-acidic malonate (thio)esters as nucleophiles, respectively. A catalytic activation strategy is also disclosed, which may have broad implications for use in catalysis and synthesis. PMID:26423837

  18. Membrane-lipid unsaturation and mitochondrial function in Saacharomyces cerevisiae.

    PubMed Central

    Watson, K; Houghton, R L; Bertoli, E; Griffiths, D E

    1975-01-01

    The lipid composition of yeast cells was manipulated by the use of an unsaturated fatty acid auxotroph of Saccharomyces cerevisiae. There was a 2-3-fold decrease in the concentration of cytochromes a+a3 when the unsaturated fatty acid content of the cells was decreased from 60-70% of the total fatty acid to 20-30%. The amounts of cytochromes b and c were also decreased under these conditions, but to a lesser extent. Further lipid depletion, to proportions of less than 20% unsaturated fatty acid, led to a dramatic decrease in the content of all cytochromes, particularly cytochromes a+a3. The ATPase (adenosine triphosphatase), succinate oxidase and NADH oxidase activities of the isolated mitochondria also varied with the degree of unsaturation of the membrane lipids. The lower the percentage of unsaturated fatty acid, the lower was the enzymic activity. Inhibition of mitochondrial ATPase by oligomycin, on the other hand, was not markedly influenced by the membrane-lipid unsaturation. Npn-linear Arrenius plots of mitochondrial membrane-bound enzymes showed transition temperatures that were dependent on the degree of membrane-lipid unsaturation. The greater the degree of lipid unsaturation, the lower was the transition temperature. It was concluded that the degree of unsaturation of the membrane lipids plays an important role in determining the properties of mitochondrial membrane-bound enzymes. PMID:125585

  19. A post-GWAS confirming the SCD gene associated with milk medium- and long-chain unsaturated fatty acids in Chinese Holstein population.

    PubMed

    Li, C; Sun, D; Zhang, S; Liu, L; Alim, M A; Zhang, Q

    2016-08-01

    The stearoyl-CoA desaturase (delta-9-desaturase) gene encodes a key enzyme in the cellular biosynthesis of monounsaturated fatty acids. In our initial genome-wide association study (GWAS) of Chinese Holstein cows, 19 SNPs fell in a 1.8-Mb region (20.3-22.1 Mb) on chromosome 26 underlying the SCD gene and were highly significantly associated with C14:1 or C14 index. The aims of this study were to verify whether the SCD gene has significant genetic effects on milk fatty acid composition in dairy cattle. By resequencing the entire coding region of the bovine SCD gene, a total of six variations were identified, including three coding variations (g.10153G>A, g.10213T>C and g.10329C>T) and three intronic variations (g.6926A>G, g.8646G>A and g.16158G>C). The SNP in exon 3, g.10329C>T, was predicted to result in an amino acid replacement from alanine (GCG) to valine (GTG) in the SCD protein. An association study for 16 milk fatty acids using 346 Chinese Holstein cows with accurate phenotypes and genotypes was performed using the mixed animal model with the proc mixed procedure in sas 9.2. All six detected SNPs were revealed to be associated with six medium- and long-chain unsaturated fatty acids (P = 0.0457 to P < 0.0001), specifically for C14:1 and C14 index (P = 0.0005 to P < 0.0001). Subsequently, strong linkage disequilibrium (D' = 0.88-1.00) was observed among all six SNPs in SCD and the five SNPs (rs41623887, rs109923480, rs42090224, rs42092174 and rs42091426) within the 1.8-Mb region identified in our previous GWAS, indicating that the significant association of the SCD gene with milk fatty acid content traits reduced the observed significant 1.8-Mb chromosome region in GWAS. Haplotype-based analysis revealed significant associations of the haplotypes encompassing the six SCD SNPs and one SNP (rs109923480) in a GWAS with C14:1, C14 index, C16:1 and C16 index (P = 0.0011 to P < 0.0001). In summary, our findings provide replicate evidence for our previous

  20. Unsaturated fatty acids promote proliferation via ERK1/2 and Akt pathway in bovine mammary epithelial cells

    SciTech Connect

    Yonezawa, Tomo Haga, Satoshi; Kobayashi, Yosuke; Katoh, Kazuo; Obara, Yoshiaki

    2008-03-21

    GPR40 has recently been identified as a G protein-coupled cell-surface receptor for long-chain fatty acids (LCFAs). The mRNA of the bovine ortholog of GPR40 (bGPR40) was detected by RT-PCR in cloned bovine mammary epithelial cells (bMEC) and in the bovine mammary gland at various stages of lactation. Oleate and linoleate caused an increase in intracellular Ca{sup 2+} concentrations in these cells, and significantly reduced forskolin-induced cAMP concentrations. Phosphorylation of extracellular signal-regulated kinase (ERK) 1/2 and Akt kinase, which regulates cell proliferation and survival, was rapidly increased by oleate. Incubation with oleate and linoleate for 24 h significantly promoted cell proliferation. Moreover, in serum-free medium, oleate significantly stimulated cell proliferation during a 7-day culture. These results suggest that bGPR40 mediates LCFA signaling in mammary epithelial cells and thereby plays an important role in cell proliferation and survival.

  1. Differential effects of saturated versus unsaturated dietary fatty acids on weight gain and myocellular lipid profiles in mice

    PubMed Central

    Timmers, S; de Vogel-van den Bosch, J; de Wit, N; Schaart, G; van Beurden, D; Hesselink, M; van der Meer, R; Schrauwen, P

    2011-01-01

    Objective: In conditions of continuous high-fat (HF) intake, the degree of saturation of the fatty acids (FAs) in the diet might have a crucial role in the onset of obesity and its metabolic complications. In particular, the FA composition of the diet might influence the storage form of lipids inside skeletal muscle. The aim of the present study was to examine whether the FA composition of HF diets differentially affects weight gain and accumulation of myocellular triacylglycerol (TAG) and diacylglycerol (DAG). Furthermore, we examined whether the FA composition of the diet was reflected in the composition of the myocellular lipid intermediates. Design: C57Bl6 mice were fed HF diets (45% energy) mainly containing palm oil (PO), cocoa butter (CB), olive oil (OO) or safflower oil (SO; n=6 per group) for 8 weeks. A low-fat diet (10% energy, PO) was used as control. Body weight was monitored weekly. At the end of the dietary intervention, myocellular TAG and DAG content and profiles were measured. Results: We here show that HF_CB prevented weight gain after 8 weeks of HF feeding. Furthermore, the HF diet rich in SO prevented the accumulation of both myocellular TAG and DAG. Interestingly, the FA composition of DAG and TAG in skeletal muscle was a reflection of the dietary FA composition. Conclusion: Already after a relatively short period, the dietary FA intake relates to the FA composition of the lipid metabolites in the muscle. A diet rich in polyunsaturated FAs seems to prevent myocellular lipid accumulation. PMID:23449423

  2. Effects of cis-unsaturated fatty acids on doxorubicin sensitivity in P388/DOX resistant and P388 parental cell lines.

    PubMed

    Liu, Q Y; Tan, B K

    2000-01-01

    It has been reported that several cis-unsaturated fatty acids (c-UFAs) could increase doxorubicin (DOX) accumulation in cancer cells and hence elevate its cytotoxicity. However, some researchers showed that c-UFA pretreatment did not affect its cytotoxicity in special cell lines. It is possible that the different results occurred due to different cellular characteristics. We hypothesized that c-UFA treatment might modulate the activities of some antioxidant enzymes to affect the resistance of cells to DOX. In the present study, we examined how c-UFA pretreatment affected DOX cytotoxicity on mouse leukemia cell line, P388, and its resistant subline, P388/DOX, which we found to have significantly higher glutathione peroxidase (GPx) activity as well as P-glycoprotein (p-gp) overexpression. We chose two c-UFAs, gamma-linolenic acid (GLA) (18:3n-6) and docosahexaenoic acid (DHA) (22:6n-3). Cytotoxicity was measured by MTT (3-(4.5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) and trypan blue exclusion assays. DOX accumulation and p-gp expression were measured by flow cytometry. The activities of catalase (CAT), superoxide dismutase (SOD), glutathione S-transferase (GST), and GPx were determined for both cell lines with and without treatment with GLA or DHA. Significant DOX accumulation occurred in both cell lines with GLA or DHA pretreatment, but without any change in p-gp expression in either cell line. Sensitivity to DOX cytotoxicity was improved by GLA or DHA pretreatment in P388/DOX in which only SOD activity was significantly increased, but not in the parental cell line P388 in which both SOD and CAT were significantly increased by the pretreatment. However, combined pretreatment of GLA or DHA with antioxidants, pyrrolidinedithiocarbamate (PDTC) or Vitamin C, could sensitize not only P388/DOX but also P388 cells to DOX. We conclude that the effects of c-UFA pretreatment on the sensitivity of cancer cells to DOX not only depend on the change in drug

  3. Increased fatty acid unsaturation and production of arachidonic acid by homologous over-expression of the mitochondrial malic enzyme in Mortierella alpina

    PubMed Central

    Hao, Guangfei; Du, Kai; Huang, Xiaoyun; Song, Yuanda; Gu, Zhennan; Wang, Lei; Zhang, Hao; Chen, Wei; Chen, Yong Q.

    2015-01-01

    Malic enzyme (ME) catalyses the oxidative decarboxylation of L-malate to pyruvate and provides NADPH for intracellular metabolism, such as fatty acid synthesis. Here, the mitochondrial ME (mME) gene from Mortierella alpina was homologously over-expressed. Compared with controls, fungal arachidonic acid (ARA; 20:4 n-6) content increased by 60 % without affecting the total fatty acid content. Our results suggest that enhancing mME activity may be an effective mean to increase industrial production of ARA in M. alpina. PMID:24863290

  4. Effects of even and odd number fatty acids cofeeding on PHA production and composition in Pseudomonas putida Bet001 isolated from palm oil mill effluent.

    PubMed

    Mohd Razaif-Mazinah, Mohd Rafais; Mohamad Annuar, Mohamad Suffian; Sharifuddin, Yusrizam

    2016-01-01

    The biosynthesis of medium-chain-length poly-3-hydroxyalkanoates by Pseudomonas putida Bet001 cultivated on mixed carbon sources was investigated. The mixed carbon sources consisted of heptanoic acid (HA) and oleic acid (OA). A relatively low PHA content at 1.2% (w/w) and 11.4% (w/w) was obtained when HA or OA was used as the sole carbon source. When these fatty acids were supplied as a mixture, PHA content increased threefold. Interestingly, the mixture-derived PHA composed of both odd and even monomer units, namely. 3-hydroxyheptanoate, 3-hydroxyoctanoate, 3-hydroxydecanoate, and 3-hydroxydodecanoate and no unsaturated monomer was detected. It is hypothesized that the even-numbered monomers were derived primarily from OA, whereas the odd-numbered monomer was derived from HA. This also points out to an efficient and yet distinct fatty acids metabolism that fed the PHA biosynthesis machinery of this particular microorganism. PHA obtained was elastomeric because melting temperature (Tm ) and crystallinity were absent. It showed good thermal stability with degradation temperature (Td ) ranging from 275.96 to 283.05 °C. PMID:25643814

  5. Carbon isotopic fractionation in the biosynthesis of bacterial fatty acids. Ozonolysis of unsaturated fatty acids as a means of determining the intramolecular distribution of carbon isotopes

    NASA Astrophysics Data System (ADS)

    Monson, K. David; Hayes, J. M.

    1982-02-01

    Methods for the determination of 13C abundances at individual olefinic carbon positions have been developed, tested, and shown to perform accurately. (1) The double bond is oxidized with ozone; (2) silver oxide is used to cleave the resulting ozonide quantitatively to carboxylic-acid fragments; (3) a modified Schmidt decarboxylation is used to produce CO 2 quantitatively from the carboxyl groups of the separated cleavage products; (4) the CO 2 is utilized for mass spectrometric analysis. The results of intramolecular isotopic analyses are combined with molecular-average isotopic compositions determined by total combustion in order to show that fatty acids biosynthesized by Escherichia coli grown aerobically with glucose as the sole carbon source and harvested at late log phase are depleted by approximately 3%. in 13C relative to the glucose. This fractionation arises in the formation of acetylcoenzyme A by pyruvate dehydrogenase and is localized at the carboxyl position in the acetyl-CoA product. The isotopic order in that two-carbon subunit is carried through the biosynthesis of fatty acids so that alternate positions in the fatty-acid chains are depleted in 13C by an amount equal to twice the molecular-average depletion. The kinetic isotope effect at C-2 for pyruvate dehydrogenase in vivo is shown to be approximately 2.3%. While it appears that no other fractionation mechanism has controlled the overall depletion of 13C in these fatty acids, a separate process responsible for control of isotopic abundances in the carboxyl groups has been identified and described elsewhere [Monson K.D. and Hayes J.M. (1980) J. Biol. Chem. 255, 11435-11441]. It is concluded that kinetic, rather than thermodynamic, factors have controlled isotopic distributions in these cells and that kinetic factors will be dominant in most biological reactions.

  6. Antidepressant-like activity of 10-hydroxy-trans-2-decenoic Acid, a unique unsaturated Fatty Acid of royal jelly, in stress-inducible depression-like mouse model.

    PubMed

    Ito, Satoru; Nitta, Yuji; Fukumitsu, Hidefumi; Soumiya, Hitomi; Ikeno, Kumiko; Nakamura, Tadashi; Furukawa, Shoei

    2012-01-01

    Symptoms of depression and anxiety appeared in mice after they had been subjected to a combination of forced swimming for 15 min followed by being kept in cages that were sequentially subjected to leaning, drenching, and rotation within 1-2 days for a total of 3 weeks. The animals were then evaluated by the tail-suspension test, elevated plus-maze test, and open-field test at 1 day after the end of stress exposure. Using these experimental systems, we found that 10-hydroxy-trans-2-decenoic acid (HDEA), an unsaturated fatty acid unique to royal jelly (RJ), protected against the depression and anxiety when intraperitoneally administered once a day for 3 weeks simultaneously with the stress loading. Intraperitoneally administered RJ, a rich source of HDEA, was also protective against the depression, but RJ given by the oral route was less effective. Our present results demonstrate that HDEA and RJ, a natural source of it, were effective in ameliorating the stress-inducible symptoms of depression and anxiety. PMID:21799699

  7. Oligomerization of Cu,Zn-Superoxide Dismutase (SOD1) by Docosahexaenoic Acid and Its Hydroperoxides In Vitro: Aggregation Dependence on Fatty Acid Unsaturation and Thiols

    PubMed Central

    Appolinário, Patricia Postilione; Medinas, Danilo Bilches; Chaves-Filho, Adriano B.; Genaro-Mattos, Thiago C.; Cussiol, José Renato Rosa; Netto, Luis Eduardo Soares; Augusto, Ohara; Miyamoto, Sayuri

    2015-01-01

    Docosahexaenoic acid (C22:6, n-3, DHA) is a polyunsaturated fatty acid highly enriched in the brain. This fatty acid can be easily oxidized yielding hydroperoxides as primary products. Cu, Zn-Superoxide dismutase (SOD1) aggregation is a common hallmark of Amyotrophic Lateral Sclerosis (ALS) and the molecular mechanisms behind their formation are not completely understood. Here we investigated the effect of DHA and its hydroperoxides (DHAOOH) on human SOD1 oligomerization in vitro. DHA induced the formation of high-molecular-weight (HMW) SOD1 species (>700 kDa). Aggregation was dependent on free thiols and occurred primarily with the protein in its apo-form. SOD1 incubation with DHA was accompanied by changes in protein structure leading to exposure of protein hydrophobic patches and formation of non-amyloid aggregates. Site-directed mutagenesis studies demonstrated that Cys 6 and Cys 111 in wild-type and Cys 6 in ALS-linked G93A mutant are required for aggregation. In contrast, DHAOOH did not induce HMW species formation but promoted abnormal covalent dimerization of apo-SOD1 that was resistant to SDS and thiol reductants. Overall, our data demonstrate that DHA and DHAOOH induce distinct types of apo-SOD1 oligomerization leading to the formation of HMW and low-molecular-weight species, respectively. PMID:25928076

  8. [Unsaturated fatty acid of Actinidia chinesis Planch seed oil enhances the antioxidative stress ability of rats with pulmonary fibrosis through activating Keap 1/Nrf 2 signaling pathway].

    PubMed

    Liu, Lijing; Qian, Hong; Yin, Huiming; He, Jianbin; Zhang, Ping; Wang, Zaiyan

    2016-04-01

    Objective To observe the effects of unsaturated fatty acid of Actinidia chinesis Planch(USFA-ACP) seed oil on bleomycin-induced pulmonary fibrosis in rats, and to explore whether the effect is mediated by Kelch-like ECH-associated protein 1 (Keap 1)/nuclear factor-erythroid 2-related factor 2 (Nrf 2)signaling pathway. Methods Sixty SD rats were randomly divided into control group, model group, (60, 120, 180) mg/kg USFA-ACP seed oil treatment group and 5 mg/kg prednisone group. Each group included 10 animals. Rats in the control group were intratracheally administered with normal saline, and the rest of five groups were intratracheally administered with bleomycin A5 to establish pulmonary fibrosis models. From the second day, rats in the three USFA-ACP seed oil treatment groups were intragastrically treated with 60, 120 and 180 mg/kg USFA-ACP seed oil correspondingly. The prednisone group were intragastrically administrated with 5 mg/kg prednisone acetate. Control and model groups were treated with normal saline. All rats were sacrificed on day 28. Pulmonary tissues were then removed, and HE and Masson staining were performed. The contents of hydroxyproline (HYP), reactive oxygen species(ROS), malondialdehyde (MDA), superoxide dismutase (SOD), catalase (CAT) and glutathione-peroxidase (GSH-Px) in pulmonary tissue homogenates were measured through the commercial kits. The protein expressions of Keap 1 and Nrf2 in pulmonary tissues were analyzed using Western blotting. Results Compared with the model group, the alveolitis and pulmonary fibrosis extent in 60, 120, 180 mg/kg USFA-ACP seed oil treatment groups as well as the prednisone group were significantly alleviated, HYP, ROS and MDA contents in pulmonary tissues, Keap 1 protein expression in the cytoplasm decreased remarkably, while SOD, CAT and GSH-Px contents in pulmonary tissues, Nrf2 protein expression in the nucleus increased. Moreover, compared with 60 mg/kg USFA-ACP seed oil treatment group, the above

  9. Precursor directed biosynthesis of odd-numbered fatty acids by different yeasts.

    PubMed

    Řezanka, Tomáš; Kolouchová, Irena; Sigler, Karel

    2015-09-01

    Precursor-directed biosynthesis was used for directed preparation of positional isomers of heptadecanoic acid (17:1), which have convenient pharmacological properties. Cultivation of Candida sp., Kluyveromyces polysporus, Rhodotorula glutinis, Saccharomyces cerevisiae, Torulaspora delbrueckii, Trichosporon cutaneum, and Yarrowia lipolytica on 20 g/L glucose, 4 g/L acetic, or 4 g/L propionic acids yielded different proportions of 17:1. Cultivation on carbon sources with even numbers of carbon atoms (glucose and acetic acid) produced preferentially 8Z- and 10Z-heptadecenoic acids in about equal amounts, in agreement with the proposed biosynthesis of fatty acids, whereas cultivation on propionic acid as the only carbon source produced over 90 % of total fatty acids of 9-17:1 out of all possible positional isomers. The structures of positional isomers of 17:1 acid were determined using dimethyl disulfides of fatty acid methyl esters. In cultivation of Candida sp. on propionic acid, the yield of heptadecenoic acid reached 111 mg/L cultivation medium. Principal component analysis was used for identifying the effect of cultivation conditions on the production of the 17:1 acid by individual yeast strains. PMID:25813199

  10. Lipid unsaturation and organelle dynamics.

    PubMed

    Barelli, Hélène; Antonny, Bruno

    2016-08-01

    The number of double bonds (=unsaturation) in the acyl chains of phospholipids (PL) influences the physical properties of cellular membranes. Here, we discuss disparate molecular processes, including vesicle budding, ion channel opening, and lipoprotein formation, which are greatly facilitated by PL polyunsaturation in membranes. Experimental and computer-based approaches for the structure and dynamics of PL suggest a common cause for these effects: the ability of the polyunsaturated acyl chain of PL to extend or bent along the membrane normal according to various constraints, thereby enabling a third dimension of motion in a structure that is essentially a 2D fluid. PMID:27062546

  11. Aqueous phase oligomerization of α,β-unsaturated carbonyls and acids investigated using ion mobility spectrometry coupled to mass spectrometry (IMS-MS)

    NASA Astrophysics Data System (ADS)

    Renard, Pascal; Tlili, Sabrine; Ravier, Sylvain; Quivet, Etienne; Monod, Anne

    2016-04-01

    One of the current essential issues to unravel our ability to forecast future climate change and air quality, implies a better understanding of natural processes leading to secondary organic aerosol (SOA) formation, and in particular the formation and fate of oligomers. The difficulty in characterizing macromolecules is to discern between large oxygenated molecules from series of oligomers containing repeated small monomers of diverse structures. In the present study, taking advantage from previously established radical vinyl oligomerization of methyl vinylketone (MVK) in the aqueous phase, where relatively simple oligomers containing up to 14 monomers were observed, we have investigated the same reactivity on several other unsaturated water soluble organic compounds (UWSOCs) and on a few mixtures of these precursor compounds. The technique used to characterize the formed oligomers was a traveling wave ion mobility spectrometry coupled to a hybrid quadrupole - time of flight mass spectrometer (IMS-MS) fitted with an electrospray source and ultra-high performance liquid chromatography (UPLC). The technique allows for an additional separation, especially for large ions, containing long carbon chains. We have shown the efficiency of the IMS-mass spectrometry technique to detect oligomers derived from MVK photooxidation in the aqueous phase. The results were then compared to other oligomers, derived from ten other individual biogenic UWSOCs. The technique allowed distinguishing between different oligomers arising from different precursors. It also clearly showed that compounds bearing a non-conjugated unsaturation did not provide oligomerization. Finally, it was shown that the IMS-mass spectrometry technique, applied to mixtures of unsaturated conjugated precursors, exhibited the ability of these precursors to co-oligomerize, i.e. forming only one complex oligomer system bearing monomers of different structures. The results are discussed in terms of atmospheric

  12. Using Acid Number as a Leading Indicator of Refrigeration and Air Conditioning System Performance

    SciTech Connect

    Dennis Cartlidge; Hans Schellhase

    2003-07-31

    This report summarizes a literature review to assess the acidity characteristics of the older mineral oil and newer polyolester (POE) refrigeration systems as well as to evaluate acid measuring techniques used in other non-aqueous systems which may be applicable for refrigeration systems. Failure in the older chlorofluorocarbon/hydrochlorofluorocarbon (CFC/HCFC) / mineral oil systems was primarily due to thermal degradation of the refrigerant which resulted in the formation of hydrochloric and hydrofluoric acids. These are strong mineral acids, which can, over time, severely corrode the system metals and lead to the formation of copper plating on iron surfaces. The oil lubricants used in the older systems were relatively stable and were not prone to hydrolytic degradation due to the low solubility of water in oil. The refrigerants in the newer hydrofluorocarbon (HFC)/POE systems are much more thermally stable than the older CFC/HCFC refrigerants and mineral acid formation is negligible. However, acidity is produced in the new systems by hydrolytic decomposition of the POE lubricants with water to produce the parent organic acids and alcohols used to prepare the POE. The individual acids can therefore vary but they are generally C5 to C9 carboxylic acids. Organic acids are much weaker and far less corrosive to metals than the mineral acids from the older systems but they can, over long time periods, react with metals to form carboxylic metal salts. The salts tend to accumulate in narrow areas such as capillary tubes, particularly if residual hydrocarbon processing chemicals are present in the system, which can lead to plugging. The rate of acid production from POEs varies on a number of factors including chemical structure, moisture levels, temperature, acid concentration and metals. The hydrolysis rate of reaction can be reduced by using driers to reduce the free water concentration and by using scavenging chemicals which react with the system acids. Total acid

  13. Standard test method for total base number of petroleum products by potentiometric perchloric acid titration

    SciTech Connect

    Not Available

    1980-01-01

    This method covers the determination of basic constituents in petroleum products by titration with perchloric acid. For many materials the results obtained by this method will be similar to those obtained by Method D 664-IP 177. With certain compounds such as strongly overbased oil additives and nitrogenous polymeric compounds, higher results may be obtained. Summary of method: the sample is dissolved in an essentially anhydrous mixture of chlorobenzene and glacial acetic acid and titrated with a solution of perchloric acid in glacial acetic acid with a potentiometric titrimeter. A glass indicating electrode and a calomel reference electrode are used, the latter being connected with the sample solution by means of a salt bridge. The meter readings are plotted against the respective volumes of titrating solution, and the end point is taken at the inflection in the resulting curve. Occasionally certain used oils give no inflection in the standard titration, in which case a back titration modification with sodium acetate titrant is employed. Total base number is the quantity of perchloric acid expressed in terms of the equivalent number of milligrams of potassium hydroxide that is required to neutralize all basic constituents present in 1 g of sample.

  14. Change in the plasmid copy number in acetic acid bacteria in response to growth phase and acetic acid concentration.

    PubMed

    Akasaka, Naoki; Astuti, Wiwik; Ishii, Yuri; Hidese, Ryota; Sakoda, Hisao; Fujiwara, Shinsuke

    2015-06-01

    Plasmids pGE1 (2.5 kb), pGE2 (7.2 kb), and pGE3 (5.5 kb) were isolated from Gluconacetobacter europaeus KGMA0119, and sequence analyses revealed they harbored 3, 8, and 4 genes, respectively. Plasmid copy numbers (PCNs) were determined by real-time quantitative PCR at different stages of bacterial growth. When KGMA0119 was cultured in medium containing 0.4% ethanol and 0.5% acetic acid, PCN of pGE1 increased from 7 copies/genome in the logarithmic phase to a maximum of 12 copies/genome at the beginning of the stationary phase, before decreasing to 4 copies/genome in the late stationary phase. PCNs for pGE2 and pGE3 were maintained at 1-3 copies/genome during all phases of growth. Under a higher concentration of ethanol (3.2%) the PCN for pGE1 was slightly lower in all the growth stages, and those of pGE2 and pGE3 were unchanged. In the presence of 1.0% acetic acid, PCNs were higher for pGE1 (10 copies/genome) and pGE3 (6 copies/genome) during the logarithmic phase. Numbers for pGE2 did not change, indicating that pGE1 and pGE3 increase their PCNs in response to acetic acid. Plasmids pBE2 and pBE3 were constructed by ligating linearized pGE2 and pGE3 into pBR322. Both plasmids were replicable in Escherichia coli, Acetobacter pasteurianus and G. europaeus, highlighting their suitability as vectors for acetic acid bacteria. PMID:25575969

  15. Measurements of mass attenuation coefficient, effective atomic number and electron density of some amino acids

    NASA Astrophysics Data System (ADS)

    Kore, Prashant S.; Pawar, Pravina P.

    2014-05-01

    The mass attenuation coefficients of some amino acids, such as DL-aspartic acid-LR(C4H7NO4), L-glutamine (C4H10N2O3), creatine monohydrate LR(C4H9N3O2H2O), creatinine hydrochloride (C4H7N3O·HCl) L-asparagine monohydrate(C4H9N3O2H2O), L-methionine LR(C5H11NO2S), were measured at 122, 356, 511, 662, 1170, 1275 and 1330 keV photon energies using a well-collimated narrow beam good geometry set-up. The gamma-rays were detected using NaI (Tl) scintillation detection system with a resolution of 0.101785 at 662 keV. The attenuation coefficient data were then used to obtain the effective atomic numbers (Zeff), and effective electron densities (Neff) of amino acids. It was observed that the effective atomic number (Zeff) and effective electron densities (Neff) initially decrease and tend to be almost constant as a function of gamma-ray energy. Zeff and Neff experimental values showed good agreement with the theoretical values with less than 1% error for amino acids.

  16. Identification of the phytosphingosine metabolic pathway leading to odd-numbered fatty acids.

    PubMed

    Kondo, Natsuki; Ohno, Yusuke; Yamagata, Maki; Obara, Takashi; Seki, Naoya; Kitamura, Takuya; Naganuma, Tatsuro; Kihara, Akio

    2014-01-01

    The long-chain base phytosphingosine is a component of sphingolipids and exists in yeast, plants and some mammalian tissues. Phytosphingosine is unique in that it possesses an additional hydroxyl group compared with other long-chain bases. However, its metabolism is unknown. Here we show that phytosphingosine is metabolized to odd-numbered fatty acids and is incorporated into glycerophospholipids both in yeast and mammalian cells. Disruption of the yeast gene encoding long-chain base 1-phosphate lyase, which catalyzes the committed step in the metabolism of phytosphingosine to glycerophospholipids, causes an ~40% reduction in the level of phosphatidylcholines that contain a C15 fatty acid. We also find that 2-hydroxypalmitic acid is an intermediate of the phytosphingosine metabolic pathway. Furthermore, we show that the yeast MPO1 gene, whose product belongs to a large, conserved protein family of unknown function, is involved in phytosphingosine metabolism. Our findings provide insights into fatty acid diversity and identify a pathway by which hydroxyl group-containing lipids are metabolized. PMID:25345524

  17. Synthesis, structure, antitumor activity of novel pharmaceutical co-crystals based on bispyridyl-substituted α, β-unsaturated ketones with gallic acid

    NASA Astrophysics Data System (ADS)

    Liu, Lian-Dong; Liu, Shu-Lian; Liu, Zhi-Xian; Hou, Gui-Ge

    2016-05-01

    Three novel pharmaceutical co-crystals, (A)·(gallic acid) (1), (B)·(gallic acid) (2), and (C)·(gallic acid) (3) were generated based on 2,6-bis((pyridin-4-yl)methylene)cyclohexanone (A), N-methyl-3,5-bis((pyridin-3-yl)methylene)-4-piperidone (B), N-methyl-3,5-bis((pyridin-4-yl)methylene)-4-piperidone (C) with gallic acid, respectively. They are characterized by elemental analysis, FTIR spectroscopy, 1H NMR and single-crystal X-ray diffraction. Structural analysis reveals that two pharmaceutical ingredients link each other into H-bonding-driven 3D network in 1, 2, or 2D plane in 3. In addition, their antitumor activities against human neoplastic cell lines A549, SGC-7901, MCF-7, OVCA-433, HePG2 and cytotoxicity for HUVEC cell lines by CCK-8 method were evaluated primarily. Compared with gallic acid and free A, B and C, their antitumor activities have improved distinctly, while cytotoxicities have reduced markedly, especially for co-crystal 1. This is mainly because of the synergistic effect between pharmaceutical ingredients A, B, and C and gallic acid.

  18. Nucleomorphin. A novel, acidic, nuclear calmodulin-binding protein from dictyostelium that regulates nuclear number.

    PubMed

    Myre, Michael A; O'Day, Danton H

    2002-05-31

    Probing of Dictyostelium discoideum cell extracts after SDS-PAGE using (35)S-recombinant calmodulin (CaM) as a probe has revealed approximately three-dozen Ca(2+)-dependent calmodulin binding proteins. Here, we report the molecular cloning, expression, and subcellular localization of a gene encoding a novel calmodulin-binding protein (CaMBP); we have called nucleomorphin, from D. discoideum. A lambdaZAP cDNA expression library of cells from multicellular development was screened using a recombinant calmodulin probe ((35)S-VU1-CaM). The open reading frame of 1119 nucleotides encodes a polypeptide of 340 amino acids with a calculated molecular mass of 38.7 kDa and is constitutively expressed throughout the Dictyostelium life cycle. Nucleomorphin contains a highly acidic glutamic/aspartic acid inverted repeat (DEED) with significant similarity to the conserved nucleoplasmin domain and a putative transmembrane domain in the carboxyl-terminal region. Southern blotting reveals that nucleomorphin exists as a single copy gene. Using gel overlay assays and CaM-agarose we show that bacterially expressed nucleomorphin binds to bovine CaM in a Ca(2+)-dependent manner. Amino-terminal fusion to the green fluorescence protein (GFP) showed that GFP-NumA localized to the nucleus as distinct arc-like patterns similar to heterochromatin regions. GFP-NumA lacking the acidic DEED repeat still showed arc-like accumulations at the nuclear periphery, but the number of nuclei in these cells was increased markedly compared with control cells. Cells expressing GFP-NumA lacking the transmembrane domain localized to the nuclear periphery but did not affect nuclear number or gross morphology. Nucleomorphin is the first nuclear CaMBP to be identified in Dictyostelium. Furthermore, these data present the first identification of a member of the nucleoplasmin family as a calmodulin-binding protein and suggest nucleomorphin has a role in nuclear structure in Dictyostelium. PMID:11919178

  19. BUOYANT ADVECTION OF GASES IN UNSATURATED SOIL

    PubMed Central

    Seely, Gregory E.; Falta, Ronald W.; Hunt, James R.

    2010-01-01

    In unsaturated soil, methane and volatile organic compounds can significantly alter the density of soil gas and induce buoyant gas flow. A series of laboratory experiments was conducted in a two-dimensional, homogeneous sand pack with gas permeabilities ranging from 110 to 3,000 darcy. Pure methane gas was injected horizontally into the sand and steady-state methane profiles were measured. Experimental results are in close agreement with a numerical model that represents the advective and diffusive components of methane transport. Comparison of simulations with and without gravitational acceleration permits identification of conditions where buoyancy dominates methane transport. Significant buoyant flow requires a Rayleigh number greater than 10 and an injected gas velocity sufficient to overcome dilution by molecular diffusion near the source. These criteria allow the extension of laboratory results to idealized field conditions for methane as well as denser-than-air vapors produced by volatilizing nonaqueous phase liquids trapped in unsaturated soil. PMID:20396624

  20. Adsorption of Carbon Dioxide on Unsaturated Metal Sites in M2 (dobpdc) Frameworks with Exceptional Structural Stability and Relation between Lewis Acidity and Adsorption Enthalpy.

    PubMed

    Yoo, Ga Young; Lee, Woo Ram; Jo, Hyuna; Park, Joonho; Song, Jeong Hwa; Lim, Kwang Soo; Moon, Dohyun; Jung, Hyun; Lim, Juhyung; Han, Sang Soo; Jung, Yousung; Hong, Chang Seop

    2016-05-23

    A series of metal-organic frameworks (MOFs) M2 (dobpdc) (M=Mn, Co, Ni, Zn; H4 dobpdc=4,4'-dihydroxy-1,1'-biphenyl-3,3'-dicarboxylic acid), with a highly dense arrangement of open metal sites along hexagonal channels were prepared by microwave-assisted or simple solvothermal reactions. The activated materials were structurally expanded when guest molecules including CO2 were introduced into the pores. The Lewis acidity of the open metal sites varied in the order MnZn, as confirmed by C=O stretching bands in the IR spectra, which are related to the CO2 adsorption enthalpy. DFT calculations revealed that the high CO2 binding affinity of transition-metal-based M2 (dobpdc) is primarily attributable to the favorable charge transfer from CO2 (oxygen lone pair acting as a Lewis base) to the open metal sites (Lewis acid), while electrostatic effects, the underlying factor responsible for the particular order of binding strength observed across different transition metals, also play a role. The framework stability against water coincides with the order of Lewis acidity. In this series of MOFs, the structural stability of Ni2 (dobpdc) is exceptional; it endured in water vapor, liquid water, and in refluxing water for one month, and the solid remained intact on exposure to solutions of pH 2-13. The DFT calculations also support the experimental finding that Ni2 (dobpdc) has higher chemical stability than the other frameworks. PMID:27105924

  1. Electrophilic Activation of α,β-Unsaturated Amides: Catalytic Asymmetric Vinylogous Conjugate Addition of Unsaturated γ-Butyrolactones.

    PubMed

    Zhang, Ming; Kumagai, Naoya; Shibasaki, Masakatsu

    2016-04-11

    Although catalytic asymmetric conjugate addition reactions have remarkably advanced over the last two decades, the application of less electrophilic α,β-unsaturated carboxylic acid derivatives in this useful reaction manifold remains challenging. Herein, we report that α,β-unsaturated 7-azaindoline amides act as reactive electrophiles to participate in catalytic diastereo- and enantioselective vinylogous conjugate addition of γ-butyrolactones in the presence of a cooperative catalyst comprising of a soft Lewis acid and a Brønsted base. Reactions mostly reached completion with as little as 1 mol % of catalyst loading to give the desired conjugate adducts in a highly stereoselective manner. PMID:26970428

  2. Studies of Human 2,4-Dienoyl CoA Reductase Shed New Light on Peroxisomal β-Oxidation of Unsaturated Fatty Acids

    SciTech Connect

    Hua, Tian; Wu, Dong; Ding, Wei; Wang, Jiangyun; Shaw, Neil; Liu, Zhi-Jie

    2012-10-15

    Peroxisomes play an essential role in maintaining fatty acid homeostasis. Although mitochondria are also known to participate in the catabolism of fatty acids via β-oxidation, differences exist between the peroxisomal and mitochondrial β-oxidation. Only peroxisomes, but not mitochondrion, can shorten very long chain fatty acids. Here, we describe the crystal structure of a ternary complex of peroxisomal 2,4-dienoyl CoA reductases (pDCR) with hexadienoyl CoA and NADP, as a prototype for comparison with the mitochondrial 2,4-dienoyl CoA reductase (mDCR) to shed light on the differences between the enzymes from the two organelles at the molecular level. Unexpectedly, the structure of pDCR refined to 1.84 Å resolution reveals the absence of the tyrosine-serine pair seen in the active site of mDCR, which together with a lysine and an asparagine have been deemed a hallmark of the SDR family of enzymes. Instead, aspartate hydrogen-bonded to the Cα hydroxyl via a water molecule seems to perturb the water molecule for protonation of the substrate. Our studies provide the first structural evidence for participation of water in the DCR-catalyzed reactions. Biochemical studies and structural analysis suggest that pDCRs can catalyze the shortening of six-carbon-long substrates in vitro. However, the Km values of pDCR for short chain acyl CoAs are at least 6-fold higher than those for substrates with 10 or more aliphatic carbons. Unlike mDCR, hinge movements permit pDCR to process very long chain polyunsaturated fatty acids.

  3. Medium-chain, even-numbered dicarboxylic acids as novel energy substrates: an update.

    PubMed

    Mingrone, Geltrude; Castagneto, Marco

    2006-10-01

    Medium-chain dicarboxylic acids are produced by higher plants and animals via fatty acid omega-oxidation or by beta-oxidation of longer-chain dicarboxylic acids. In plants, dicarboxylic acids are components of the natural protective polymers cutin and suberin; in animals, dicarboxylic acids are mainly oxidized in mitochondria, where they are transported through four different pathways. Their energy density is intermediate between glucose and fatty acids. Dicarboxylic acid administration does not require insulin or stimulate insulin secretion, and the beta-oxidation of dicarboxylic acids produces succinic acid, a gluconeogenic substrate. Therefore, dicarboxylic acids might be a suitable fuel substrate, particularly in clinical conditions in which marked insulin resistance and/or impairment of aerobic glycolysis occur. PMID:17063926

  4. The induction of CP43' by iron-stress in Synechococcus sp. PCC 7942 is associated with carotenoid accumulation and enhanced fatty acid unsaturation.

    PubMed

    Ivanov, Alexander G; Krol, Marianna; Selstam, Eva; Sane, Prafullachandra Vishnu; Sveshnikov, Dmitry; Park, Youn-Il; Oquist, Gunnar; Huner, Norman P A

    2007-06-01

    Comparative lipid analysis demonstrated reduced amount of PG (50%) and lower ratio of MGDG/DGDG in iron-stressed Synechococcus sp. PCC 7942 cells compared to cells grown under iron sufficient conditions. In parallel, the monoenoic (C:1) fatty acids in MGDG, DGDG and PG increased from 46.8%, 43.7% and 45.6%, respectively in control cells to 51.6%, 48.8% and 48.7%, respectively in iron-stressed cells. This suggests increased membrane dynamics, which may facilitate the diffusion of PQ and keep the PQ pool in relatively more oxidized state in iron-stressed compared to control cells. This was confirmed by chlorophyll fluorescence and thermoluminescence measurements. Analysis of carotenoid composition demonstrated that the induction of isiA (CP43') protein in response to iron stress is accompanied by significant increase of the relative abundance of all carotenoids. The quantity of carotenoids calculated on a Chl basis increased differentially with nostoxanthin, cryptoxanthin, zeaxanthin and beta-carotene showing 2.6-, 3.1-, 1.9- and 1.9-fold increases, respectively, while the relative amount of caloxanthin was increased only by 30%. HPLC analyses of the pigment composition of Chl-protein complexes separated by non-denaturating SDS-PAGE demonstrated even higher relative carotenoids content, especially of cryptoxanthin, in trimer and monomer PSI Chl-protein complexes co-migrating with CP43' from iron-stressed cells than in PSI complexes from control cells where CP43' is not present. This implies a carotenoid-binding role for the CP43' protein which supports our previous suggestion for effective energy quenching and photoprotective role of CP43' protein in cyanobacteria under iron stress. PMID:17362874

  5. Attenuation of Landfill Leachate In Unsaturated Sandstone

    NASA Astrophysics Data System (ADS)

    Butler, A. P.; Brook, C.; Godley, A.; Lewin, K.; Young, C. P.

    Landfill leachate emanating from old "dilute and disperse" sites represents a potential (and in many cases actual) threat to the integrity of groundwater. Indeed, this concern has been included in EU legislation (80/86/EEC), where key contaminants (e.g. ammonia, various toxic organic compounds and heavy metals) are explicitly highlighted in terms of their impact on groundwater. In the UK, whilst there are a substantial number of unlined landfills sited on major aquifers, many of these are in locations where there is a substantial unsaturated zone. Thus, there exists the opportunity for the modification and attenuation of contaminants prior to it encountering the water table. An understanding of likely changes in leachate content and concentrations at such sites will enable a more comprehensive assessment of the potential risks and liabilities posed by such sites to be evaluated. The Burntstump landfill, situated 8 km north of Nottingham (UK), is sited on an outcrop of Sherwood sandstone. The fine friable sand has been quarried since the 1960s and the excavated volume used to store municipal waste. Filling at the site commenced in the mid 1970s and originally was unlined. In 1978 the first of what was to become a series of boreholes was installed within an area of roughly 5 m radius over one of the original waste cells. Cores of the waste and underlying sandstone were extracted and analysed for a range of physical and chemical parameters. The most recent set of analyses were obtained in 2000. The series of investigations therefore provide an important record of leachate migration and modification through the unsaturated zone for over twenty years. The progression of the leachate front is clearly delineated by the chloride concentration profile with an average velocity of around 1.6 m.yr-1. Combining this value with an average (and reasonably uniform) measured moisture content of about 7% gives a mean inter-granular specific discharge of 110 mm.yr-1. An interesting

  6. Structure of unsaturated rhamnogalacturonyl hydrolase complexed with substrate

    SciTech Connect

    Itoh, Takafumi; Ochiai, Akihito; Mikami, Bunzo; Hashimoto, Wataru; Murata, Kousaku . E-mail: kmurata@kais.kyoto-u.ac.jp

    2006-09-08

    Bacillus subtilis strain 168 YteR has been identified as a novel enzyme 'unsaturated rhamnogalacturonyl hydrolase' classified in glycoside hydrolase family 105. This enzyme acts specifically on unsaturated rhamnogalacturonan (RG) produced from plant cell wall RG type-I treated with RG lyases, releasing unsaturated galacturonic acid ({delta}GalA) from the substrate. The most likely candidate catalytic residue is Asp-143. Here, we show the structure of D143N in complex with unsaturated RG disaccharide (substrate) determined at 1.9 A resolution by X-ray crystallography. This structural feature directly contributes to the postulation of the enzyme reaction mechanism. YteR triggers the hydration of vinyl ether group in {delta}GalA, but not of glycoside bond, by using Asp-143 as a general acid and base catalyst. Asp-143 donates proton to the double bond of {delta}GalA as an acid catalyst and also deprotonates a water molecule as a base catalyst. Deprotonated water molecule attacks the C5 atom of {delta}GalA.

  7. Intake of saturated and trans unsaturated fatty acids and risk of all cause mortality, cardiovascular disease, and type 2 diabetes: systematic review and meta-analysis of observational studies

    PubMed Central

    de Souza, Russell J; Mente, Andrew; Maroleanu, Adriana; Cozma, Adrian I; Kishibe, Teruko; Uleryk, Elizabeth; Budylowski, Patrick; Schünemann, Holger; Beyene, Joseph

    2015-01-01

    Objective To systematically review associations between intake of saturated fat and trans unsaturated fat and all cause mortality, cardiovascular disease (CVD) and associated mortality, coronary heart disease (CHD) and associated mortality, ischemic stroke, and type 2 diabetes. Design Systematic review and meta-analysis. Data sources Medline, Embase, Cochrane Central Registry of Controlled Trials, Evidence-Based Medicine Reviews, and CINAHL from inception to 1 May 2015, supplemented by bibliographies of retrieved articles and previous reviews. Eligibility criteria for selecting studies Observational studies reporting associations of saturated fat and/or trans unsaturated fat (total, industrially manufactured, or from ruminant animals) with all cause mortality, CHD/CVD mortality, total CHD, ischemic stroke, or type 2 diabetes. Data extraction and synthesis Two reviewers independently extracted data and assessed study risks of bias. Multivariable relative risks were pooled. Heterogeneity was assessed and quantified. Potential publication bias was assessed and subgroup analyses were undertaken. The GRADE approach was used to evaluate quality of evidence and certainty of conclusions. Results For saturated fat, three to 12 prospective cohort studies for each association were pooled (five to 17 comparisons with 90 501-339 090 participants). Saturated fat intake was not associated with all cause mortality (relative risk 0.99, 95% confidence interval 0.91 to 1.09), CVD mortality (0.97, 0.84 to 1.12), total CHD (1.06, 0.95 to 1.17), ischemic stroke (1.02, 0.90 to 1.15), or type 2 diabetes (0.95, 0.88 to 1.03). There was no convincing lack of association between saturated fat and CHD mortality (1.15, 0.97 to 1.36; P=0.10). For trans fats, one to six prospective cohort studies for each association were pooled (two to seven comparisons with 12 942-230 135 participants). Total trans fat intake was associated with all cause mortality (1.34, 1.16 to 1.56), CHD mortality

  8. Effects of dietary palmitoleic acid on plasma lipoprotein profile and aortic cholesterol accumulation are similar to those of other unsaturated fatty acids in the F1B golden syrian-hamster

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The lower susceptibility of palmitoleic acid (16:1) to oxidation compared to polyunsaturated fatty acids may confer functional advantages with respect to finding acceptable alternatives to hydrogenated fats but limited data are available on its effect on cardiovascular risk factors. This study inves...

  9. Hydraulic Properties of Unsaturated Soils

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Many agrophysical applications require knowledge of the hydraulic properties of unsaturated soils. These properties reflect the ability of a soil to retain or transmit water and its dissolved constituents. The objective of this work was to develop an entry for the Encyclopedia of Agrophysics that w...

  10. Repository site data report for unsaturated tuff, Yucca Mountain, Nevada

    SciTech Connect

    Tien, P.L.; Updegraff, C.D.; Siegel, M.D.; Wahi, K.K.; Guzowski, R.V.

    1985-11-01

    The US Department of Energy is currently considering the thick sequences of unsaturated, fractured tuff at Yucca Mountain, on the southwestern boundary of the Nevada Test Site, as a possible candidate host rock for a nuclear-waste repository. Yucca Mountain is in one of the most arid areas in the United States. The site is within the south-central part of the Great Basin section of the Basin and Range physiographic province and is located near a number of silicic calderas of Tertiary age. Although localized zones of seismic activity are common throughout the province, and faults are present at Yucca Mountain, the site itself is basically aseismic. No data are available on the composition of ground water in the unsaturated zone at Yucca Mountain. It has been suggested that the composition is bounded by the compositions of water from wells USW-H3, UE25p-1, J-13, and snow or rain. There are relatively few data available from Yucca Mountain on the moisture content and saturation, hydraulic conductivity, and characteristic curves of the unsaturated zone. The available literature on thermomechanical properties of tuff does not always distinguish between data from the saturated zone and data from the unsaturated zone. Geochemical, hydrologic, and thermomechanical data available on the unsaturated tuffs of Yucca Mountain are tabulated in this report. Where the data are very sparse, they have been supplemented by data from the saturated zone or from areas other than Yucca Mountain. 316 refs., 58 figs., 37 tabs.

  11. Number of free hydroxyl groups on bile acid phospholipids determines the fluidity and hydration of model membranes.

    PubMed

    Sreekanth, Vedagopuram; Bajaj, Avinash

    2013-10-10

    Interactions of synthetic phospholipids with model membranes determines the drug release capabilities of phospholipid vesicles at diseased sites. We performed 1,6-diphenyl-1,3,5-hexatriene (DPH)-based fluorescence anisotropy, Laurdan-based membrane hydration, and differential scanning calorimetry (DSC) studies to cognize the interactions of three bile acid phospholipids, lithocholic acid-phosphocholine (LCA-PC), deoxycholic acid-phosphocholine (DCA-PC), and cholic acid-phosphocholine (CA-PC) with model membranes. These studies revealed that bile acid phospholipids increases membrane fluidity in DCA-PC > CA-PC > LCA-PC order, indicating that induction of membrane fluidity is contingent on the number and positioning of free hydroxyl groups on bile acids. Similarly, DCA-PC causes maximum membrane perturbations due to the presence of a free hydroxyl group, whereas LCA-PC induces gel phase in membranes due to hydrophobic bile acid acyl chain interactions. These DCA-PC-induced membrane perturbations induce a drastic decrease in phase transition temperature (Tm) as determined by calorimetric studies, whereas doping of LCA-PC causes phase transition broadening without change in Tm. Doping of CA-PC induces membrane perturbations and membrane hydration like DCA-PC but sharpening of phase transition at higher doping suggests self-association of CA-PC molecules. Therefore these differential mode of interactions between bile acid phospholipids and model membranes would help in the future for their use in drug delivery. PMID:24079709

  12. Synergistic transcriptional enhancement does not depend on the number of acidic activation domains bound to the promoter.

    PubMed Central

    Oliviero, S; Struhl, K

    1991-01-01

    Many eukaryotic transcriptional activator proteins contain a DNA-binding domain that interacts with specific promoter sequences and an acidic activation region that is required to stimulate transcription. Transcriptional enhancement by such activator proteins is often synergistic and promiscuous; promoters containing multiple binding sites for an individual protein or even for unrelated proteins can be 10-100 times more active than promoters with single sites. It has been suggested that such synergy reflects a nonlinear response of the basic transcription machinery to the number and/or quality of acidic activation regions. Here, we determine the transcriptional activity of Jun-Fos heterodimers containing one or two GCN4 acidic activation regions on promoters containing one or two Ap-1 target sites. Surprisingly, heterodimers with one or two acidic regions activate transcription with similar efficiency and are equally synergistic (10- to 15-fold) on promoters containing two target sites. Thus, transcriptional synergy does not depend on the number of acidic activation regions but rather on the number of proteins bound to the promoter. This suggests that synergy is mediated either by cooperative DNA binding or by alternative mechanisms in which the DNA-binding domain plays a more direct role in transcription (e.g., changes in DNA structure, nucleosome displacement, or direct interactions with the transcriptional machinery). Images PMID:1898773

  13. Synthesis of unsaturated phosphatidylinositol 4-phosphates and the effects of substrate unsaturation on SopB phosphatase activity.

    PubMed

    Furse, Samuel; Mak, LokHang; Tate, Edward W; Templer, Richard H; Ces, Oscar; Woscholski, Rüdiger; Gaffney, Piers R J

    2015-02-21

    In this paper evidence is presented that the fatty acid component of an inositide substrate affects the kinetic parameters of the lipid phosphatase Salmonella Outer Protein B (SopB). A succinct route was used to prepare the naturally occurring enantiomer of phosphatidylinositol 4-phosphate (PI-4-P) with saturated, as well as singly, triply and quadruply unsaturated, fatty acid esters, in four stages: (1) The enantiomers of 2,3:5,6-O-dicyclohexylidene-myo-inositol were resolved by crystallisation of their di(acetylmandelate) diastereoisomers. (2) The resulting diol was phosphorylated regio-selectively exclusively on the 1-O using the new reagent tri(2-cyanoethyl)phosphite. (3) With the 4-OH still unprotected, the glyceride was coupled using phosphate tri-ester methodology. (4) A final phosphorylation of the 4-O, followed by global deprotection under basic then acidic conditions, provided PI-4-P bearing a range of sn-1-stearoyl, sn-2-stearoyl, -oleoyl, -γ-linolenoyl and arachidonoyl, glycerides. Enzymological studies showed that the introduction of cis-unsaturated bonds has a measurable influence on the activity (relative Vmax) of SopB. Mono-unsaturated PI-4-P exhibited a five-fold higher activity, with a two-fold higher KM, over the saturated substrate, when presented in DOPC vesicles. Poly-unsaturated PI-4-P showed little further change with respect to the singly unsaturated species. This result, coupled with our previous report that saturated PI-4-P has much higher stored curvature elastic stress than PI, supports the hypothesis that the activity of inositide phosphatase SopB has a physical role in vivo. PMID:25515724

  14. Unsaturated Shear Strength and Numerical Analysis Methods for Unsaturated Soils

    NASA Astrophysics Data System (ADS)

    Kim, D.; Kim, G.; Kim, D.; Baek, H.; Kang, S.

    2011-12-01

    The angles of shearing resistance(φb) and internal friction(φ') appear to be identical in low suction range, but the angle of shearing resistance shows non-linearity as suction increases. In most numerical analysis however, a fixed value for the angle of shearing resistance is applied even in low suction range for practical reasons, often leading to a false conclusion. In this study, a numerical analysis has been undertaken employing the estimated shear strength curve of unsaturated soils from the residual water content of SWCC proposed by Vanapalli et al.(1996). The result was also compared with that from a fixed value of φb. It is suggested that, in case it is difficult to measure the unsaturated shear strength curve through the triaxial soil tests, the estimated shear strength curve using the residual water content can be a useful alternative. This result was applied for analyzing the slope stablity of unsaturated soils. The effects of a continuous rainfall on slope stability were analyzed using a commercial program "SLOPE/W", with the coupled infiltration analysis program "SEEP/W" from the GEO-SLOPE International Ltd. The results show that, prior to the infiltration by the intensive rainfall, the safety factors using the estimated shear strength curve were substantially higher than that from the fixed value of φb at all time points. After the intensive infiltration, both methods showed a similar behavior.

  15. Photosensitized oxidation of unsaturated polymers

    NASA Technical Reports Server (NTRS)

    Golub, M. A.

    1979-01-01

    The photosensitized oxidation or singlet oxygenation of unsaturated hydrocarbon polymers and of their model compounds was reviewed. Emphasis was on cis and trans forms of 1,4-polyisoprene, 1,4-polybutadiene and 1,2-poly(1,4-hexadiene), and on 1,4-poly(2,3-dimethyl-1,3-butadiene). The microstructural changes which occur in these polymers on reaction with O2-1 in solution were investigated by infrared H-1 and C-13 NMR spectroscopy. The polymers were shown to yield allylic hydroperoxides with shifted double bonds according to the ene mechanism established for simple olefins. The photosensitized oxidation of the above unsaturated polymer exhibited zero order kinetics, the relative rates paralleling the reactivities of the corresponding simple olefins towards O2-1.

  16. Photosensitized oxidation of unsaturated polymers

    NASA Technical Reports Server (NTRS)

    Golub, M. A.

    1980-01-01

    A review of the photosensitized oxidation of singlet oxygenation of unsaturated hydrocarbon polymers and of their model compounds is presented. The cis and trans forms of 1,4-polyisoprene, 1,4-polybutadiene and 1,2-poly(1,4-hexadiene) are studied, and their microstructural changes which occur on reaction with (IO2) in solution were investigated by infrared, (H-1) and (C-13) NMR spectroscopy. The polymers yielded allylic hydroperoxides with shifted double bonds according to the 'ene' mechanism of simple olefins. It was shown that single oxygenation of unsaturated polymers is similar to their low molecular weight analogs, and that the differences are due to secondary processes affecting the (IO2)-reacted polymers.

  17. Unsaturated lipids protect the integral membrane peptide gramicidin A from singlet oxygen.

    PubMed

    Rokitskaya, Tatyana I; Kotova, Elena A; Agapov, Igor I; Moisenovich, Mikhail M; Antonenko, Yuri N

    2014-05-01

    In contrast to expectations that unsaturated fatty acids contribute to oxidative stress by providing a source of lipid peroxides, we demonstrated the protective effect of double bonds in lipids on oxidative damage to membrane proteins. Photodynamic inactivation of gramicidin channels was decreased in unsaturated lipid compared to saturated lipid bilayers. By estimating photosensitizer (boronated chlorine e6 amide) binding to the membrane with the current relaxation technique, the decrease in gramicidin photoinactivation was attributed to singlet oxygen scavenging by double bonds in lipids rather than to the reduction in photosensitizer binding. Gramicidin protection by unsaturated lipids was also observed upon induction of oxidative stress with tert-butyl hydroperoxide. PMID:24613917

  18. Numbers of bacteria recovered from broiler carcasses and chiller water treated with hypochlorous and carbonic acids

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A study was conducted to determine the effects of treating poultry chiller water with a mixture of hypochlorous and carbonic acids. Broiler carcasses and chiller water were obtained from a commercial processing facility which had recently installed a TOMCO Pathogen Management SystemJ to recycle wat...

  19. Adipocyte amino acid sensing controls adult germline stem cell number via the amino acid response pathway and independently of Target of Rapamycin signaling in Drosophila.

    PubMed

    Armstrong, Alissa R; Laws, Kaitlin M; Drummond-Barbosa, Daniela

    2014-12-01

    How adipocytes contribute to the physiological control of stem cells is a critical question towards understanding the link between obesity and multiple diseases, including cancers. Previous studies have revealed that adult stem cells are influenced by whole-body physiology through multiple diet-dependent factors. For example, nutrient-dependent pathways acting within the Drosophila ovary control the number and proliferation of germline stem cells (GSCs). The potential role of nutrient sensing by adipocytes in modulating stem cells in other organs, however, remains largely unexplored. Here, we report that amino acid sensing by adult adipocytes specifically modulates the maintenance of GSCs through a Target of Rapamycin-independent mechanism. Instead, reduced amino acid levels and the consequent increase in uncoupled tRNAs trigger activation of the GCN2-dependent amino acid response pathway within adipocytes, causing increased rates of GSC loss. These studies reveal a new step in adipocyte-stem cell crosstalk. PMID:25359724

  20. Adipocyte amino acid sensing controls adult germline stem cell number via the amino acid response pathway and independently of Target of Rapamycin signaling in Drosophila

    PubMed Central

    Armstrong, Alissa R.; Laws, Kaitlin M.; Drummond-Barbosa, Daniela

    2014-01-01

    How adipocytes contribute to the physiological control of stem cells is a critical question towards understanding the link between obesity and multiple diseases, including cancers. Previous studies have revealed that adult stem cells are influenced by whole-body physiology through multiple diet-dependent factors. For example, nutrient-dependent pathways acting within the Drosophila ovary control the number and proliferation of germline stem cells (GSCs). The potential role of nutrient sensing by adipocytes in modulating stem cells in other organs, however, remains largely unexplored. Here, we report that amino acid sensing by adult adipocytes specifically modulates the maintenance of GSCs through a Target of Rapamycin-independent mechanism. Instead, reduced amino acid levels and the consequent increase in uncoupled tRNAs trigger activation of the GCN2-dependent amino acid response pathway within adipocytes, causing increased rates of GSC loss. These studies reveal a new step in adipocyte-stem cell crosstalk. PMID:25359724

  1. A comprehensive evaluation of the cetane numbers of fatty acid methyl esters

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The cetane number (CN) is a prime indicator of the quality of diesel fuels, including those derived from renewable resources such as biodiesel. While many effects of compound structure are known or have been postulated, experimental data have not always been available for the various ester component...

  2. Liquefaction Potential of Unsaturated Nevada Sand at Different Initial Conditions

    NASA Astrophysics Data System (ADS)

    Xu, Jiting

    the specimen liquefy increased with the relative density. For the same other initial conditions, the number of cycles required to make the saturated specimen liquefy increased with an increase in the effective confining pressure. For unsaturated Nevada sand, the liquefaction potential generally decreased with an increase in effective confining pressure and an increase in relative density. When the initial degree of saturation was 95%, about 180% and 70% more cycles were needed to reach liquefaction for the loose Nevada sand (Dr=30%) and the dense Nevada sand (Dr=70%), respectively, if the effective confining pressure increased from 50kPa to 200kPa. When the initial degree of saturation was 95% and the effective confining pressure was 50kPa, about 45% more cycles were needed to make the specimen liquefy if the relative density changed from 30% to 50%. When the confining pressure was 200kPa and the degree of saturation was 95%, the relative density did not play a significant role in effecting liquefaction of Nevada sand. For the loose Nevada sand, the liquefaction potential decreased with a decrease in degree of saturation. When the confining pressure was 50kPa and the degree of saturation was 90%, the number of cycles required to liquefy doubled compared to the saturated case. When the effective confining pressure was 200kPa, twice of the number of cycles were needed for the sand to liquefy when the degree of saturation was decreased by 5%. For the dense Nevada sand, the degree of saturation did not play an important role on the number of cycles required to reach liquefaction under lower effective confining pressure (50kPa). However, when the effective confining pressure was increased to 200kPa, the number of cycles for liquefaction was significantly increased with the decreasing degree of saturation. When the degree of saturation was 90%, the 70% relative density specimen experienced 2.0% axial strain without liquefying.

  3. In situ bioremediation of contaminated unsaturated subsurface soils

    SciTech Connect

    Sims, J.L.; Sims, R.C.; Dupont, R.R.; Matthews, J.E.; Russell, H.H.

    1993-05-01

    An emerging technology for the remediation of unsaturated subsurface soils involves the use of microorganisms to degrade contaminants which are present in such soils. Understanding the processes which drive in situ bioremediation, as well as the effectiveness and efficiency of the utilization of these systems, are issues which have been identified by the Regional Superfund Engineering Forum as concerns of Superfund decision makers. Although in situ bioremediation has been used for a number of years in the restoration of ground water contaminated by petroleum hydrocarbons, it has only been in recent years that in situ systems have been directed toward contaminants in unsaturated subsurface soils. Research has contributed greatly to understanding the biotic, chemical, and hydrologic parameters which contribute to or restrict the application of in-situ bioremediation and has been successful at a number of locations in demonstrating its effectiveness at field scale.

  4. The Unsaturation of Membrane Lipids Stabilizes Photosynthesis against Heat Stress.

    PubMed Central

    Gombos, Z.; Wada, H.; Hideg, E.; Murata, N.

    1994-01-01

    The effect of the unsaturation of glycerolipids of thylakoid membranes on the heat tolerance of the photosynthetic evolution of oxygen was studied in vivo by mutation and transformation of fatty-acid desaturases in the cyanobacterium Synechocystis PCC6803. The experimental results indicate that elimination of dienoic lipid molecules decreases, to a small but distinct extent, the heat tolerance of photosynthetic oxygen evolution, but that elimination of trienoic lipid molecules has no effect on the heat tolerance. This conclusion contrasts with the previous hypothesis that the heat tolerance of photosynthesis is enhanced upon an increase in the level of saturation of membrane lipids. It is also shown that light does not affect the nature of the effect of lipid unsaturation on the heat tolerance of photosynthesis. PMID:12232106

  5. Enzyme-catalysed conjugations of glutathione with unsaturated compounds

    PubMed Central

    Boyland, E.; Chasseaud, L. F.

    1967-01-01

    1. Rat-liver supernatant catalyses the reaction of diethyl maleate with glutathione. 2. Evidence is presented that the enzyme involved is different from the known glutathione-conjugating enzymes, glutathione S-alkyltransferase, S-aryltransferase and S-epoxidetransferase. 3. Rat-liver supernatant catalyses the reaction of a number of other αβ-unsaturated compounds, including aldehydes, ketones, lactones, nitriles and nitro compounds, with glutathione: separate enzymes may be responsible for these reactions. PMID:6035529

  6. Analyzing unsaturated flow patterns in fractured rock using an integrated modeling approach

    NASA Astrophysics Data System (ADS)

    Wu, Yu-Shu; Lu, Guoping; Zhang, Keni; Pan, Lehua; Bodvarsson, Gudmundur S.

    2007-05-01

    Characterizing percolation patterns in unsaturated fractured rock has posed a greater challenge to modeling investigations than comparable saturated zone studies due to the heterogeneous nature of unsaturated media and the great number of variables impacting unsaturated flow. An integrated modeling methodology has been developed for quantitatively characterizing percolation patterns in the unsaturated zone of Yucca Mountain, Nevada (USA), a proposed underground repository site for storing high-level radioactive waste. The approach integrates moisture, pneumatic, thermal, and isotopic geochemical field data into a comprehensive three-dimensional numerical model for analyses. It takes into account the coupled processes of fluid and heat flow and chemical isotopic transport in Yucca Mountain’s highly heterogeneous, unsaturated fractured tuffs. Modeling results are examined against different types of field-measured data and then used to evaluate different hydrogeological conceptualizations through analyzing flow patterns in the unsaturated zone. In particular, this model provides clearer understanding of percolation patterns and flow behavior through the unsaturated zone, both crucial issues in assessing repository performance. The integrated approach for quantifying Yucca Mountain’s flow system is demonstrated to provide a practical modeling tool for characterizing flow and transport processes in complex subsurface systems.

  7. Modeling transient streaming potentials in coupled saturated-unsaturated zone flow to a pumping well

    NASA Astrophysics Data System (ADS)

    Malama, B.

    2012-12-01

    A semi-analytical model for transient response of streaming potentials (SP) to pumping in an unconfined aquifer, taking into account unsaturated zone flow, is presented. Flow in the unsaturated zone is modeled with a linearized Richards' equation with the moisture retention curve and unsaturated hydraulic conduc- tivity assumed to be exponential functions of matric potential. For the case presented here, the same sorption number is assumed for moisture retention and unsaturated hydraulic conductivity. The ratio of the unsaturated to satu- rated electrokinetic coupling coefficient is described by Cℓ,r = kr Sw-(d+1), where kr is relative hydraulic conductivity, Sw is saturation, and d is Archie's second exponent. Hence, based on the assumption of an exponential moisture retention curve, Cℓ,r is also an exponential function of matric potential. Model predicted responses in the saturated and unsaturated zones are compared with measured SP responses to pumping in a bench-scale experimental setup that simulates a radially bounded unconfined aquifer. Potential for using SP responses to esti- mate saturated and unsaturated hydraulic parameters is evaluated. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04- 94AL85000. This research is funded by WIPP programs administered by the Office of Environmental Management (EM) of the U.S Department of Energy.

  8. Acoustic behaviors of unsaturated soils

    NASA Astrophysics Data System (ADS)

    Lu, Z.

    2011-12-01

    Soils are unconsolidated granular materials, consisting of solid particles, water and air. Their mechanical and dynamic behaviors are determined by the discrete nature of the media as well as external and inter-particle forces. For unsaturated soils, two factors significantly affect soils acoustic/seismic responses: external pressure and internal water potential/matric suction. In triaxial cell tests, unsaturated soils were subjected to predefined stress paths to undergo stages of normal consolidation, unload-reload cycles, and failure. The stress deformation curve and stress-P-wave velocity were measured and compared. The study revealed that soil's dynamic response to external pressure are similar to those of the load-deformation behaviors and demonstrated that acoustic velocity can be used to monitor the state of stress of soils. In a long term field soil survey, the P-wave velocities were found to be correlated with water potential as expressed as a power-law relationship. The above phenomena can be understood by using the Terzaghi' s the principle of effective stress. The measured results were in good agreement with Brutsaert theory. The effective stress concept can also be applied to explain the observations in a soil pipe flow study in which soil internal erosion processes were monitored and interpreted by the temporal evolution of the P-wave velocity. In addition to above linear acoustic behaviors, soils, like other earth materials, exhibit astonishing non-classical nonlinear behaviors such as end-point memory, hysteresis, strain -dependent shear modulus, resonant frequency shift, and phase shift, harmonics generation, etc. A nonlinear acoustic study of a soil as a function of water content showed that the nonlinear acoustic parameter are much sensitive to the variations of soil water content than that of the acoustic velocity.

  9. Modeling Unsaturated Flow and Transport using Zones: Aliasing Errors

    NASA Astrophysics Data System (ADS)

    Schafer, A. L.; Holt, R. M.

    2001-12-01

    It is difficult and costly to accurately determine the spatial statistics of unsaturated hydraulic properties, whereas it is often easier to define hydraulic property zones. When heterogeneous hydraulic property fields are subdivided into zones, however, flow and transport predictions show aliasing errors that alter predicted concentrations and breakthrough curves. The amount of error varies with the number of zones, the character of the heterogeneity, and boundary and initial conditions. The objective of this work is to determine the number of zones required to preserve critical transport behavior during numerical simulation of flow and transport. For this exercise, we consider unsaturated flow and non-reactive transport only. We assume that Richard?s Equation is valid and that the Gardner-Russo parametric model exactly describes unsaturated constitutive relationships. Correlated random parameter fields are generated and unsaturated flow and transport through these fields is simulated. The fields are then zoned using quantiles (0.25, 0.1, 0.05, and 0.025), appropriate zonal averages are determined, and flow and transport is simulated through the zoned fields. Aliasing errors are assessed by comparing the first, second and third moments of concentration for the full and zoned fields. The number of zones is varied to elucidate the character of aliasing error. The style of heterogeneity is varied to reflect geologically relevant end members (statistically isotropic vs. perfectly layered fields). Simulations are repeated under unit gradient conditions at mean tensions of 10, 100, and 1000 cm. Aliasing errors will tend to be smallest in layered systems with flow perpendicular to layering, because zonal averaging does not obscure fast paths. In statistically isotropic systems, fast paths are reduced as the coarseness of the zones increases. At higher tensions, finer zones are required to preserve transport behavior.

  10. Storage and mobilization of natural and septic nitrate in thick unsaturated zones, California

    NASA Astrophysics Data System (ADS)

    Izbicki, John A.; Flint, Alan L.; O'Leary, David R.; Nishikawa, Tracy; Martin, Peter; Johnson, Russell D.; Clark, Dennis A.

    2015-05-01

    Mobilization of natural and septic nitrate from the unsaturated zone as a result of managed aquifer recharge has degraded water quality from public-supply wells near Yucca Valley in the western Mojave Desert, California. The effect of nitrate storage and potential for denitrification in the unsaturated zone to mitigate increasing nitrate concentrations were investigated. Storage of water extractable nitrate in unsaturated alluvium up to 160 meters (m) thick, ranged from 420 to 6600 kilograms per hectare (kg/ha) as nitrogen (N) beneath undeveloped sites, from 6100 to 9200 kg/ha as N beneath unsewered sites. Nitrate reducing and denitrifying bacteria were less abundant under undeveloped sites and more abundant under unsewered sites; however, δ15N-NO3, and δ18O-NO3 data show only about 5-10% denitrification of septic nitrate in most samples-although as much as 40% denitrification occurred in some parts the unsaturated zone and near the top of the water table. Storage of nitrate in thick unsaturated zones and dilution with low-nitrate groundwater are the primary attenuation mechanisms for nitrate from septic discharges in the study area. Numerical simulations of unsaturated flow, using the computer program TOUGH2, showed septic effluent movement through the unsaturated zone increased as the number and density of the septic tanks increased, and decreased with increased layering, and increased slope of layers, within the unsaturated zone. Managing housing density can delay arrival of septic discharges at the water table, especially in layered unsaturated alluvium, allowing time for development of strategies to address future water-quality issues.

  11. Storage and mobilization of natural and septic nitrate in thick unsaturated zones, California

    USGS Publications Warehouse

    Izbicki, John A.; Flint, Alan L.; O'Leary, David R.; Nishikawa, Tracy; Martin, Peter; Johnson, Russell D.; Clark, Dennis A.

    2015-01-01

    Mobilization of natural and septic nitrate from the unsaturated zone as a result of managed aquifer recharge has degraded water quality from public-supply wells near Yucca Valley in the western Mojave Desert, California. The effect of nitrate storage and potential for denitrification in the unsaturated zone to mitigate increasing nitrate concentrations were investigated. Storage of water extractable nitrate in unsaturated alluvium up to 160 meters (m) thick, ranged from 420 to 6600 kilograms per hectare (kg/ha) as nitrogen (N) beneath undeveloped sites, from 6100 to 9200 kg/ha as N beneath unsewered sites. Nitrate reducing and denitrifying bacteria were less abundant under undeveloped sites and more abundant under unsewered sites; however, δ15N–NO3, and δ18O–NO3 data show only about 5–10% denitrification of septic nitrate in most samples—although as much as 40% denitrification occurred in some parts the unsaturated zone and near the top of the water table. Storage of nitrate in thick unsaturated zones and dilution with low-nitrate groundwater are the primary attenuation mechanisms for nitrate from septic discharges in the study area. Numerical simulations of unsaturated flow, using the computer program TOUGH2, showed septic effluent movement through the unsaturated zone increased as the number and density of the septic tanks increased, and decreased with increased layering, and increased slope of layers, within the unsaturated zone. Managing housing density can delay arrival of septic discharges at the water table, especially in layered unsaturated alluvium, allowing time for development of strategies to address future water-quality issues.

  12. Polyfluorinated. cap alpha. ,. beta. -unsaturated ketons

    SciTech Connect

    Latypov, R.R.; Belogai, V.D.; Pashkevich, K.I.

    1986-07-10

    The ..cap alpha..,..beta..-unsaturated ketones (..cap alpha..,..beta..-UK), particularly those groups containing fluoroalkyl groups, are of interest as highly reactive compounds having two nonequivalent electrophilic centers. In the present investigation, by boiling polyfluorinated aldehydes with methylketones in glacial acetic acid, they have obtained for the first time the polyfluorinated ..beta..-hydroxy-ketones, the dehydration of which has been used to synthesize the corresponding polyfluorinated ..cap alpha..,..beta..-UK, and their structure and reactions with the nucleophiles NH/sub 3/, PhNH/sub 2/, MeOH have been studied. In the PMR spectra of the ..cap alpha..,..beta..-UK (X)-(XVI) two doublets of triplets are observed at 6.9 and 7.9 ppm, caused by the spin-spin coupling of the olefin protons with the CF/sub 2/ group of the substituent. For ..cap alpha..,..beta..-UK, apart from the cis-trans isomerism relative to the C=C bond, a rotational isomerism is possible, caused by rotation around the C-C single bond. The presence in the IR spectra of absorption bands from nonplanar torsion-deformation vibrations of C-H for a double bond (nu = 975-980 cm/sup -1/) and the high value of the spin-spin coupling constant of the olefin protons (J/sub HH/ = 15 Hz) indicate unambiguously the transconfiguration of the olefin protons.

  13. On Unsaturated Soil Mechanics - Personal Views on Current Research

    NASA Astrophysics Data System (ADS)

    Pande, G. N.; Pietruszczak, S.

    2015-09-01

    This paper presents the authors' personal views on current research being conducted by various research groups around the world in the broad area of mechanics of unsaturated geomaterials in general and soils in particular. The topic is of interest to a wide spectrum of scientists and engineers working in diverse areas such as geology and geophysics, powder technology, agricultural, petroleum, chemical, geotechnical, civil, environmental and nuclear engineering. Even if we restrict ourselves to civil, geotechnical and environmental engineering, it is noted that a plethora of hypotheses as well as a number of empirical and semi-empirical relations have been introduced for describing the mechanics of unsaturated porous media. However, many of these proposed advances as well as methods of testing may lack sound theoretical basis.

  14. Additive effects on the toughening of unsaturated polyester resins

    SciTech Connect

    Suspene, L.; Yang, Y.S.; Pascault, J.P.

    1993-12-31

    An elastomer additive, carboxy-terminated acrylonitrile-butadiene copolymer, was used for toughening in the free radical cross-linking copolymerization of unsaturated polyester (UP) resins. For molded parts, Charpy impact behavior was generally enhanced and the number of catastrophic failures was reduced. The miscibility and interfacial properties of additive and resin blends play important roles in the toughening process. Phase-diagram studies showed that the elastomer additive is immiscible with the UP resin and is phase-separated from the resin matrix during curing. This phase-separation phenomenon is similar to that in the low-profile mechanism of UP resins. Additive-resin system miscibility greatly influences curing morphology. Microvoids occurred in the additive phase of cured resin because of shrinkage stress. The intrinsic inhomogeneity of the polyester network and the existence of microvoids in the final product limit the toughening effect of additives on unsaturated polyester resins. 49 refs., 13 figs., 3 tabs.

  15. Effect of dietary soybean oil addition on the odd-numbered and branched-chain fatty acids in rabbit meat.

    PubMed

    Papadomichelakis, George; Karagiannidou, Areti; Anastasopoulos, Vasilios; Fegeros, Konstantinos

    2010-10-01

    The effect of dietary soybean oil (SO) inclusion (20g/kg) on the odd-numbered (ONFA) and branched-chain (BCFA) fatty acids (FA) of two muscles, differing in fatness (Longissimus lumborum and Biceps femoris), was studied in 24 New ZealandxCalifornian rabbits. The increased muscle fatness in Biceps femoris (P<0.001) was related to higher saturated (P<0.01) and monounsaturated (P<0.01) fatty acids. Intramuscular ONFA and BCFA contents were not affected, but their proportions were reduced (P<0.01 and P<0.001) by SO addition, suggesting a dilution effect of the dietary polyunsaturates accumulated in both muscles, except for 17:0i which decreased only in Longissimus lumborum due to significant (P<0.05) soybean oilxmuscle interaction. The higher (P<0.05) BCFA contents and the FA profile in Biceps femoris were not affected by fatness, indicating an association with other muscle properties. The present study supplies new information on ONFA and BCFA in rabbit meat. PMID:20493641

  16. Modifications of proteins by polyunsaturated fatty acid peroxidation products

    NASA Astrophysics Data System (ADS)

    Refsgaard, Hanne H. F.; Tsai, Lin; Stadtman, Earl R.

    2000-01-01

    The ability of unsaturated fatty acid methyl esters to modify amino acid residues in bovine serum albumin (BSA), glutamine synthetase, and insulin in the presence of a metal-catalyzed oxidation system [ascorbate/Fe(III)/O2] depends on the degree of unsaturation of the fatty acid. The fatty acid-dependent generation of carbonyl groups and loss of lysine residues increased in the order methyl linoleate < methyl linolenate < methyl arachidonate. The amounts of alkyl hydroperoxides, malondialdehyde, and a number of other aldehydes that accumulated when polyunsaturated fatty acids were oxidized in the presence of BSA were significantly lower than that observed in the absence of BSA. Direct treatment of proteins with various lipid hydroperoxides led to a slight increase in the formation of protein carbonyl derivatives, whereas treatment with the hydroperoxides together with Fe(II) led to a substantial increase in the formation of protein carbonyls. These results are consistent with the proposition that metal-catalyzed oxidation of polyunsaturated fatty acids can contribute to the generation of protein carbonyls by direct interaction of lipid oxidation products (α,β-unsaturated aldehydes) with lysine residues (Michael addition reactions) and also by interactions with alkoxyl radicals obtained by Fe(II) cleavage of lipid hydroperoxides that are formed. In addition, saturated aldehydes derived from the polyunsaturated fatty acids likely react with lysine residues to form Schiff base adducts.

  17. Modifications of proteins by polyunsaturated fatty acid peroxidation products

    PubMed Central

    Refsgaard, Hanne H. F.; Tsai, Lin; Stadtman, Earl R.

    2000-01-01

    The ability of unsaturated fatty acid methyl esters to modify amino acid residues in bovine serum albumin (BSA), glutamine synthetase, and insulin in the presence of a metal-catalyzed oxidation system [ascorbate/Fe(III)/O2] depends on the degree of unsaturation of the fatty acid. The fatty acid-dependent generation of carbonyl groups and loss of lysine residues increased in the order methyl linoleate < methyl linolenate < methyl arachidonate. The amounts of alkyl hydroperoxides, malondialdehyde, and a number of other aldehydes that accumulated when polyunsaturated fatty acids were oxidized in the presence of BSA were significantly lower than that observed in the absence of BSA. Direct treatment of proteins with various lipid hydroperoxides led to a slight increase in the formation of protein carbonyl derivatives, whereas treatment with the hydroperoxides together with Fe(II) led to a substantial increase in the formation of protein carbonyls. These results are consistent with the proposition that metal-catalyzed oxidation of polyunsaturated fatty acids can contribute to the generation of protein carbonyls by direct interaction of lipid oxidation products (α,β-unsaturated aldehydes) with lysine residues (Michael addition reactions) and also by interactions with alkoxyl radicals obtained by Fe(II) cleavage of lipid hydroperoxides that are formed. In addition, saturated aldehydes derived from the polyunsaturated fatty acids likely react with lysine residues to form Schiff base adducts. PMID:10639127

  18. Technological Aspects of Chemoenzymatic Epoxidation of Fatty Acids, Fatty Acid Esters and Vegetable Oils: A Review.

    PubMed

    Milchert, Eugeniusz; Malarczyk, Kornelia; Kłos, Marlena

    2015-01-01

    The general subject of the review is analysis of the effect of technological parameters on the chemoenzymatic epoxidation processes of vegetable oils, fatty acids and alkyl esters of fatty acids. The technological parameters considered include temperature, concentration, amount of hydrogen peroxide relative to the number of unsaturated bonds, the amounts of enzyme catalysts, presence of solvent and amount of free fatty acids. Also chemical reactions accompanying the technological processes are discussed together with different technological options and significance of the products obtained. PMID:26633342

  19. Enantioselective Palladium-Catalyzed Oxidative β,β-Fluoroarylation of α,β-Unsaturated Carbonyl Derivatives.

    PubMed

    Miró, Javier; Del Pozo, Carlos; Toste, F Dean; Fustero, Santos

    2016-07-25

    The site-selective palladium-catalyzed three-component coupling of deactivated alkenes, arylboronic acids, and N-fluorobenzenesulfonimide is disclosed herein. The developed methodology establishes a general, modular, and step-economical approach to the stereoselective β-fluorination of α,β-unsaturated systems. PMID:27272390

  20. Unsaturation ratios of novel tri-unsaturated alkenones from Northeastern Alaska: insights from water column calibration and sediments

    NASA Astrophysics Data System (ADS)

    Longo, W. M.; Dillon, J.; Giblin, A.; Huang, Y.

    2013-12-01

    Long chain alkenones (LCAs) are a class of C35 - C40 unsaturated ketones that have been established as important biomarkers for reconstructing sea surface temperature (SST), surface ocean primary productivity, salinity and pCO2. LCAs have also been investigated in lacustrine settings and a considerable number of studies have demonstrated that LCAs are widespread in lakes with varied properties. Furthermore, unsaturation ratios of LCAs in several lakes are well correlated with in situ and overlying temperature and have been used to reconstruct water and air temperature from sedimentary records. The paleoclimate community has been slow to adopt lacustrine alkenone paleothermometry, however, because variable and complex LCA distributions resulting from diverse haptophyte precursors often complicate our interpretation of LCA records. Here, we demonstrate that the improved separation of LCAs and alkenoates using an unconventional gas chromatographic (GC) stationary phase resolves complex LCAs from a variety of samples and we apply this new technique to lakes from Northeastern Alaska (NE AK). Analyses of LCAs using the stationary phase [poly(trifluoropropylmethylsiloxane)] revealed that NE AK lakes host a novel distribution of 16 LCAs, including the C37Me, C38Et, C38Me, C39Et homologs. Within each homologous group of LCAs, we identified a previously unresolved tri-unsaturated isomeric LCA, featuring different double bond positioning than the tri-unsaturated LCAs commonly observed in marine sediments. In addition to providing characterizations of these compounds, our investigation takes advantage of the improved GC separation to evaluate unsaturation ratios with the normal and isomeric C37, C38Et and C38Me LCAs. We find that several unsaturation ratios are well correlated with in situ lake water temperature and, furthermore, that the slopes of these correlations are not affected by the GC stationary phase used. The application of various unsaturation ratios to lacustrine

  1. Fatty acid specificity of hormone-sensitive lipase. Implication in the selective hydrolysis of triacylglycerols.

    PubMed

    Raclot, T; Holm, C; Langin, D

    2001-12-01

    The selective mobilization of fatty acids from white fat cells depends on their molecular structure, in particular the degree of unsaturation. The present study was designed to examine if the release of fatty acids by hormone-sensitive lipase (HSL) in vitro i) is influenced by the amount of unsaturation, ii) depends on the temperature, and iii) could explain the selective pattern of fatty acid mobilization and notably the preferential mobilization of certain highly unsaturated fatty acids. Recombinant rat and human HSL were incubated with a lipid emulsion. The hydrolysis of 35 individual fatty acids, ranging in chain length from 12 to 24 carbon atoms and in unsaturation from 0 to 6 double bonds was measured. Fatty acid composition of in vitro released NEFA was compared with that of fat cell triacylglycerols (TAG), the ratio % NEFA/% TAG being defined as the relative hydrolysis. The relative hydrolysis of individual fatty acids differed widely, ranging from 0.44 (24:1n-9) to 1.49 (18:1n-7) with rat HSL, and from 0.38 (24:1n-9) to 1.67 (18:1n-7) with human HSL. No major difference was observed between rat and human HSL. The relative release was dependent on the number of double bonds according to chain length. The amount of fatty acid released by recombinant rat HSL was decreased but remained robust at 4 degrees C compared with 37 degrees C, and the relative hydrolysis of some individual fatty acids was affected. The relative hydrolysis of fatty acids moderately, weakly, and highly mobilized by adipose tissue in vivo was similar and close to unity in vitro. We conclude that i) the release of fatty acids by HSL is only slightly affected by their degree of unsaturation, ii) the ability of HSL to efficiently and selectively release fatty acids at low temperature could reflect a cold adaptability for poikilotherms or hibernators when endogenous lipids are needed, and iii) the selectivity of fatty acid hydrolysis by HSL does not fully account for the selective pattern of

  2. Solid-state NMR and DFT predictions of differences in COOH hydrogen bonding in odd and even numbered n-alkyl fatty acids.

    PubMed

    Powell, Jacob; Kalakewich, Keyton; Uribe-Romo, Fernando J; Harper, James K

    2016-05-14

    For nearly 140 years n-alkyl monocarboxylic acids have been known to exhibit unusual non-monotonic melting between odd and even numbered acids. This behavior has been rationalized in terms of packing density at the hydrocarbon tails, with COOH hydrogen bonding considered to be invariant among different acids. A recent ambiguity involving the COOH conformation between two crystal structures of lauric acid suggests that COOH structure and hydrogen bonding may play a role in these differences. Here, the two conflicting lauric acid crystal structures are further refined using lattice-including DFT refinement methods. Solid-state NMR (SSNMR) (13)C chemical shift tensor data are employed to monitor refinement quality by comparing experimental and computed tensors. This comparison provides a more sensitive measure of structure than X-ray data due to SSNMR's ability to accurately locate hydrogens. Neither diffraction structure agrees with SSNMR data and an alternative is proposed involving a hydrogen disordered COOH moiety. The disordered hydrogen dynamically samples two most probable positions on the NMR timescale with O-H bond lengths of 1.16 and 1.46 Å. This disordered structure is consistent with SSNMR, IR and X-ray C-O and C[double bond, length as m-dash]O bond lengths. The hydrogen disorder appears to be restricted to even numbered acids based on undecanoic acid's (13)COOH tensor data and C-O and C[double bond, length as m-dash]O bond lengths for other n-alkyl acids. This disorder in even numbered acids results in stronger hydrogen bonds than are found in odd acids and invites a reevaluation of the melting behavior of n-alkyl acids that includes these differences in hydrogen bonding. PMID:27087051

  3. Selection of a numerical unsaturated flow code for tilted capillary barrier performance evaluation

    SciTech Connect

    Webb, S.W.

    1996-09-01

    Capillary barriers consisting of tilted fine-over-coarse layers have been suggested as landfill covers as a means to divert water infiltration away from sensitive underground regions under unsaturated flow conditions, especially for arid and semi-arid regions. Typically, the HELP code is used to evaluate landfill cover performance and design. Unfortunately, due to its simplified treatment of unsaturated flow and its essentially one-dimensional nature, HELP is not adequate to treat the complex multidimensional unsaturated flow processes occurring in a tilted capillary barrier. In order to develop the necessary mechanistic code for the performance evaluation of tilted capillary barriers, an efficient and comprehensive unsaturated flow code needs to be selected for further use and modification. The present study evaluates a number of candidate mechanistic unsaturated flow codes for application to tilted capillary barriers. Factors considered included unsaturated flow modeling, inclusion of evapotranspiration, nodalization flexibility, ease of modification, and numerical efficiency. A number of unsaturated flow codes are available for use with different features and assumptions. The codes chosen for this evaluation are TOUGH2, FEHM, and SWMS{_}2D. All three codes chosen for this evaluation successfully simulated the capillary barrier problem chosen for the code comparison, although FEHM used a reduced grid. The numerical results are a strong function of the numerical weighting scheme. For the same weighting scheme, similar results were obtained from the various codes. Based on the CPU time of the various codes and the code capabilities, the TOUGH2 code has been selected as the appropriate code for tilted capillary barrier performance evaluation, possibly in conjunction with the infiltration, runoff, and evapotranspiration models of HELP. 44 refs.

  4. Effect of Selection for High Activity-Related Metabolism on Membrane Phospholipid Fatty Acid Composition in Bank Voles.

    PubMed

    Stawski, Clare; Valencak, Teresa G; Ruf, Thomas; Sadowska, Edyta T; Dheyongera, Geoffrey; Rudolf, Agata; Maiti, Uttaran; Koteja, Paweł

    2015-01-01

    Endothermy, high basal metabolic rates (BMRs), and high locomotor-related metabolism were important steps in the evolution of mammals. It has been proposed that the composition of membrane phospholipid fatty acids plays an important role in energy metabolism and exercise muscle physiology. In particular, the membrane pacemaker theory of metabolism suggests that an increase in cell membrane fatty acid unsaturation would result in an increase in BMR. We aimed to determine whether membrane phospholipid fatty acid composition of heart, liver, and gastrocnemius muscles differed between lines of bank voles selected for high swim-induced aerobic metabolism-which also evolved an increased BMR-and unselected control lines. Proportions of fatty acids significantly differed among the organs: liver was the least unsaturated, whereas the gastrocnemius muscles were most unsaturated. However, fatty acid proportions of the heart and liver did not differ significantly between selected and control lines. In gastrocnemius muscles, significant differences between selection directions were found: compared to control lines, membranes of selected voles were richer in saturated C18:0 and unsaturated C18:2n-6 and C18:3n-3, whereas the pattern was reversed for saturated C16:0 and unsaturated C20:4n-6. Neither unsaturation index nor other combined indexes of fatty acid proportions differed between lines. Thus, our results do not support the membrane pacemaker hypothesis. However, the differences between selected and control lines in gastrocnemius muscles reflect chain lengths rather than number of double bonds and are probably related to differences in locomotor activity per se rather than to differences in the basal or routine metabolic rate. PMID:26658414

  5. Fourier Transform Infrared Imaging Showing Reduced Unsaturated Lipid Content in the Hippocampus of a mouse Model of Alzheimer's Disease

    SciTech Connect

    Leskovjan, A.C.; Kretlow, A.; Miller, L.M.

    2010-04-01

    Polyunsaturated fatty acids are essential to brain functions such as membrane fluidity, signal transduction, and cell survival. It is also thought that low levels of unsaturated lipid in the brain may contribute to Alzheimer's disease (AD) risk or severity. However, it is not known how accumulation of unsaturated lipids is affected in different regions of the hippocampus, which is a central target of AD plaque pathology, during aging. In this study, we used Fourier transform infrared imaging (FTIRI) to visualize the unsaturated lipid content in specific regions of the hippocampus in the PSAPP mouse model of AD as a function of plaque formation. Specifically, the unsaturated lipid content was imaged using the olefinic {double_bond}CH stretching mode at 3012 cm{sup -1}. The axonal, dendritic, and somatic layers of the hippocampus were examined in the mice at 13, 24, 40, and 56 weeks old. Results showed that lipid unsaturation in the axonal layer was significantly increased with normal aging in control (CNT) mice (p < 0.01) but remained low and relatively constant in PSAPP mice. Thus, these findings indicate that unsaturated lipid content is reduced in hippocampal white matter during amyloid pathogenesis and that maintaining unsaturated lipid content early in the disease may be critical in avoiding progression of the disease.

  6. Improved zeolite regeneration processes for preparing saturated branched-chain fatty acids

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Ferrierite zeolite solid is an excellent catalyst for the skeletal isomerization of unsaturated linear-chain fatty acids (i.e., oleic acid) to unsaturated branched-chain fatty acids (i.e., iso-oleic acid) follow by hydrogenation to give saturated branched-chain fatty acids (i.e., isostearic acid). ...

  7. Formulation of thermo-hydro-mechanical coupling behavior of unsaturated soils based on hybrid mixture theory

    NASA Astrophysics Data System (ADS)

    Cai, Guo-Qing; Zhao, Cheng-Gang; Sheng, Dai-Chao; Zhou, An-Nan

    2014-08-01

    Thermo-Hydro-Mechanical (THM) coupling processes in unsaturated soils are very important in both theoretical researches and engineering applications. A coupled formulation based on hybrid mixture theory is derived to model the THM coupling behavior of unsaturated soils. The free-energy and dissipative functions for different phases are derived from Taylor's series expansions. Constitutive relations for THM coupled behaviors of unsaturated soils, which include deformation, entropy change, fluid flow, heat conduction, and dynamic compatibility conditions on the interfaces, are then established. The number of field equations is shown to be equal to the number of unknown variables; thus, a closure of this coupling problem is established. In addition to modifications of the physical conservation equations with coupling effect terms, the constitutive equations, which consider the coupling between elastoplastic deformation of the soil skeleton, fluid flow, and heat transfer, are also derived.

  8. Photosensitized production of functionalized and unsaturated organic compounds at the air-sea interface

    NASA Astrophysics Data System (ADS)

    Ciuraru, Raluca; Fine, Ludovic; van Pinxteren, Manuela; D'Anna, Barbara; Herrmann, Hartmut; George, Christian

    2015-08-01

    The sea-surface microlayer (SML) has different physical, chemical and biological properties compared to the subsurface water, with an enrichment of organic matter i.e., dissolved organic matter including UV absorbing humic substances, fatty acids and many others. Here we present experimental evidence that dissolved organic matter, such as humic acids, when exposed to sunlight, can photosensitize the chemical conversion of linear saturated fatty acids at the air-water interface into unsaturated functionalized gas phase products (i.e. saturated and unsaturated aldehydes and acids, alkenes and dienes,…) which are known precursors of secondary organic aerosols. These functionalized molecules have previously been thought to be of biological origin, but here we demonstrate that abiotic interfacial photochemistry has the potential to produce such molecules. As the ocean is widely covered by the SML, this new understanding will impact on our ability to describe atmospheric chemistry in the marine environment.

  9. Photosensitized production of functionalized and unsaturated organic compounds at the air-sea interface

    PubMed Central

    Ciuraru, Raluca; Fine, Ludovic; van Pinxteren, Manuela; D’Anna, Barbara; Herrmann, Hartmut; George, Christian

    2015-01-01

    The sea-surface microlayer (SML) has different physical, chemical and biological properties compared to the subsurface water, with an enrichment of organic matter i.e., dissolved organic matter including UV absorbing humic substances, fatty acids and many others. Here we present experimental evidence that dissolved organic matter, such as humic acids, when exposed to sunlight, can photosensitize the chemical conversion of linear saturated fatty acids at the air-water interface into unsaturated functionalized gas phase products (i.e. saturated and unsaturated aldehydes and acids, alkenes and dienes,…) which are known precursors of secondary organic aerosols. These functionalized molecules have previously been thought to be of biological origin, but here we demonstrate that abiotic interfacial photochemistry has the potential to produce such molecules. As the ocean is widely covered by the SML, this new understanding will impact on our ability to describe atmospheric chemistry in the marine environment. PMID:26244712

  10. Electrokinetic extraction of chromate from unsaturated soils

    SciTech Connect

    Mattson, E.D.; Lindgren, E.R.

    1993-11-01

    Heavy-metal contamination of soil and groundwater is a widespread problem in industrial nations. Remediation by excavation of such sites may not be cost effective or politically acceptable. Electrokinetic remediation is one possible remediation technique for in situ removal of such contaminants from unsaturated soils. Previous papers discussing the work performed by researchers at Sandia National Laboratories (SNL) and Sat-Unsat, Inc. (SUI) (Lindgren et al., 1991, 1992, 1993) focused on the transport of contaminants and dyes by electrokinetics in unsaturated soils. These experiments were conducted with graphite electrodes with no extraction system. As the contaminants migrated through the soil, they increased in concentration at the electrode creating a diffusion flux in the opposite direction. This paper discusses a technique to remove the contaminants from unsaturated soils once they have reached an electrode.

  11. Pesticide fate and transport throughout unsaturated zones in five agricultural settings, USA

    USGS Publications Warehouse

    Hancock, T.C.; Sandstrom, M.W.; Vogel, J.R.; Webb, R.M.T.; Bayless, E.R.; Barbash, J.E.

    2008-01-01

    Pesticide transport through the unsaturated zone is a function of chemical and soil characteristics, application, and water recharge rate. The fate and transport of 82 pesticides and degradates were investigated at five different agricultural sites. Atrazine and metolachlor, as well as several of the degradates of atrazine, metolachlor, acetochlor, and alachlor, were frequently detected in soil water during the 2004 growing season, and degradates were generally more abundant than parent compounds. Metolachlor and atrazine were applied at a Nebraska site the same year as sampling, and focused recharge coupled with the short time since application resulted in their movement in the unsaturated zone 9 m below the surface. At other sites where the herbicides were applied 1 to 2 yr before sampling, only degradates were found in soil water. Transformations of herbicides were evident with depth and during the 4-mo sampling time and reflected the faster degradation of metolachlor oxanilic acid and persistence of metolachor ethanesulfonic acid. The fraction of metolachlor ethanesulfonic acid relative to metolachlor and metolachlor oxanilic acid increased from 0.3 to > 0.9 at a site in Maryland where the unsaturated zone was 5 m deep and from 0.3 to 0.5 at the shallowest depth. The flux of pesticide degradates from the deepest sites to the shallow ground water was greatest (3.0–4.9 μmol m−2 yr−1) where upland recharge or focused flow moved the most water through the unsaturated zone. Flux estimates based on estimated recharge rates and measured concentrations were in agreement with fluxes estimated using an unsaturated-zone computer model (LEACHM).

  12. Pesticide fate and transport throughout unsaturated zones in five agricultural settings, USA.

    PubMed

    Hancock, Tracy C; Sandstrom, Mark W; Vogel, Jason R; Webb, Richard M T; Bayless, E Randall; Barbash, Jack E

    2008-01-01

    Pesticide transport through the unsaturated zone is a function of chemical and soil characteristics, application, and water recharge rate. The fate and transport of 82 pesticides and degradates were investigated at five different agricultural sites. Atrazine and metolachlor, as well as several of the degradates of atrazine, metolachlor, acetochlor, and alachlor, were frequently detected in soil water during the 2004 growing season, and degradates were generally more abundant than parent compounds. Metolachlor and atrazine were applied at a Nebraska site the same year as sampling, and focused recharge coupled with the short time since application resulted in their movement in the unsaturated zone 9 m below the surface. At other sites where the herbicides were applied 1 to 2 yr before sampling, only degradates were found in soil water. Transformations of herbicides were evident with depth and during the 4-mo sampling time and reflected the faster degradation of metolachlor oxanilic acid and persistence of metolachor ethanesulfonic acid. The fraction of metolachlor ethanesulfonic acid relative to metolachlor and metolachlor oxanilic acid increased from 0.3 to >0.9 at a site in Maryland where the unsaturated zone was 5 m deep and from 0.3 to 0.5 at the shallowest depth. The flux of pesticide degradates from the deepest sites to the shallow ground water was greatest (3.0-4.9 micromol m(-2) yr(-1)) where upland recharge or focused flow moved the most water through the unsaturated zone. Flux estimates based on estimated recharge rates and measured concentrations were in agreement with fluxes estimated using an unsaturated-zone computer model (LEACHM). PMID:18453430

  13. Flow and Transport Through Unsaturated Fractured Rock

    NASA Astrophysics Data System (ADS)

    Evans, Daniel D.; Nicholson, Thomas J.; Rasmussen, Todd C.

    This monograph is an update and revision of the first edition, Geophysical Monograph 42, on ground-water flow and transport through unsaturated, fractured rock, published by AGU in 1987. The first edition evolved from a special symposium held during the American Geophysical Union fall meetings in San Francisco in December 1986. Invited and contributed papers at that AGU session, as well as panel presentations, focused on conceptualizing, measuring and modeling flow and transport through unsaturated fractured rock. As noted in the preface to the first edition, "the expanded interest in the topic (water flow and contaminant transport through unsaturated fractured rock) was initiated when the U.S. Geological Survey proposed that deep unsaturated zones in arid regions be considered in the site selection for the first high-level, commercially generated radioactive waste repository." Much of the research reported in that first edition was motivated by the U.S. Department of Energy's program to investigate Yucca Mountain at the Nevada Test Site as a possible geologic repository for commercially generated, high-level radioactive waste. As noted in the overview paper of the first edition, "characterization methods and modeling are in their developmental stage with the greatest lack of knowledge being the interaction between fracture and matrix flow and transport properties." Although the first edition of this monograph reflected the state-of-the science, laboratory and field experimental programs were novel and limited and, in general, followed from the principles and methods developed in the soil science community.

  14. FAST FLOW IN UNSATURATED COARSE SEDIMENTS

    EPA Science Inventory

    This research proposal was developed to improve our understanding of the physics of unsaturated flow in coarse- to very coarse-textured sediments, and through this meet practical needs related to contaminant transport in such vadose environments. This is a critical area for impr...

  15. Reactions of acyloxy carbocations with unsaturated hydrocarbons

    SciTech Connect

    Luk'yanov, S.M.; Borodaev, S.V.

    1986-03-01

    Under the influence of antimony pentachloride ..cap alpha..-chlorobenzyl benzoate forms an acyloxy carbocation which is stable at -90/sup 0/C. The latter reacts with a series of unsaturated compounds (cyclohexene, 2-butene, isobutylene, trimethylethylene, the enol acylates of isobutyraldehyde) to form 1,3-dioxolanium and 1,3-dioxanium hexachloroantimonates.

  16. 7-Chloro-5-(furan-3-yl)-3-methyl-4H-benzo[e][1,2,4]thiadiazine 1,1-Dioxide as Positive Allosteric Modulator of α-Amino-3-hydroxy-5-methyl-4-isoxazolepropionic Acid (AMPA) Receptor. The End of the Unsaturated-Inactive Paradigm?

    PubMed

    Citti, Cinzia; Battisti, Umberto M; Cannazza, Giuseppe; Jozwiak, Krzysztof; Stasiak, Natalia; Puja, Giulia; Ravazzini, Federica; Ciccarella, Giuseppe; Braghiroli, Daniela; Parenti, Carlo; Troisi, Luigino; Zoli, Michele

    2016-02-17

    5-Arylbenzothiadiazine type compounds acting as positive allosteric modulators of α-amino-3-hydroxy-5-methyl-4-isoxazolepropionic acid receptor (AMPA-PAMs) have received particular attention in the past decade for their nootropic activity and lack of the excitotoxic side effects of direct agonists. Recently, our research group has published the synthesis and biological activity of 7-chloro-5-(3-furanyl)-3-methyl-3,4-dihydro-2H-1,2,4-benzothiadiazine 1,1-dioxide (1), one of the most active benzothiadiazine-derived AMPA-PAMs in vitro to date. However, 1 exists as two stereolabile enantiomers, which rapidly racemize in physiological conditions, and only one isomer is responsible for the pharmacological activity. In the present work, experiments carried out with rat liver microsomes show that 1 is converted by hepatic cytochrome P450 to the corresponding unsaturated derivative 2 and to the corresponding pharmacologically inactive benzenesulfonamide 3. Surprisingly, patch-clamp experiments reveal that 2 displays an activity comparable to that of the parent compound. Molecular modeling studies were performed to rationalize these results. Furthermore, mice cerebral microdialysis studies suggest that 2 is able to cross the blood-brain barrier and increases acetylcholine and serotonin levels in the hippocampus. The experimental data disclose that the achiral hepatic metabolite 2 possesses the same pharmacological activity of its parent compound 1 but with an enhanced chemical and stereochemical stability, as well as an improved pharmacokinetic profile compared with 1. PMID:26580317

  17. Antioxidant activity of alkyl hydroxytyrosyl ethers in unsaturated lipids.

    PubMed

    Cert, Rosa; Madrona, Andrés; Espartero, José Luis; Pérez-Camino, M Carmen

    2015-06-01

    The antioxidant activity of ethyl and octyl hydroxytyrosyl ethers toward lipids was determined using the Rancimat and open cup methods at high temperatures and 50 °C, respectively. The effect of the unsaturation of the matrix was evaluated using sunflower, soya, and fish refined oils. The antioxidant activities of alkyl hydroxytyrosyl ethers (HTy ethers), hydroxytyrosyl esters, and free hydroxytyrosol are similar, and are much higher than that of α-tocopherol at the same millimolar concentration. The relationship between the induction period and the concentration of the HTy ethers is a sigmoidal curve; an accurate concentration of HTy ethers is necessary to achieve maximum activity, as it increases with the level of matrix unsaturation. The presence of tocopherols in commercial oils affects the antioxidant effect of HTy ethers. Thus, the addition of a low concentration of HTy ethers results in a positive effect, whereas the effect of the addition of high amounts of ethers is slightly less than that of the phenol alone. The addition of HTy ethers to commercial refined oils increases the stability of the oils and preserves tocopherols and polyunsaturated fatty acids from oxidation, enabling the oils to maintain their nutritional properties for longer periods of time. PMID:26018773

  18. Raman microspectroscopy based sensor of algal lipid unsaturation

    NASA Astrophysics Data System (ADS)

    Samek, Ota; Pilát, Zdeněk; Jonáš, Alexandr; Zemánek, Pavel; Šerý, Mojmír; Ježek, Jan; Bernatová, Silvie; Nedbal, Ladislav; Trtílek, Martin

    2011-05-01

    Raman spectroscopy is a powerful tool for chemical analysis. This technique can elucidate fundamental questions about the metabolic processes and intercellular variability on a single cell level. Therefore, Raman spectroscopy can significantly contribute to the study and use of microalgae in systems biology and biofuel technology. Raman spectroscopy can be combined with optical tweezers. We have employed microfluidic system to deliver the sampled microalgae to the Raman-tweezers. This instrument is able to measure chemical composition of cells and to track metabolic processes in vivo, in real-time and label-free making it possible to detect population variability in a wide array of traits. Moreover, employing an active sorting switch, cells can be separated depending on input parameters obtained from Raman spectra. We focus on algal lipids which are promising potential products for biofuel as well as for nutrition. Important parameter characterizing the algal lipids is the degree of unsaturation of the constituent fatty acids. We demonstrate the capacity of our Raman tweezers based sensor to sort cells according to the degree of unsaturation in lipid storage bodies of individual living algal cells.

  19. Effects of chronic exposure to soft, acidic water on gill development and chloride cell numbers in embryo-larval brook trout, Salvelinus fontinalis

    USGS Publications Warehouse

    Conklin, D.J.; Mowbray, R.C.; Gingerich, W.H.

    1992-01-01

    Recruitment failure is considered to be a major factor contributing to the decline of fish populations in soft, acidic waters; direct mortality of embryo-larval fishes has been postulated as a major cause of the decline. Little is understood of the physiological consequences to embryo-larval fishes of prolonged exposure to soft, acidic waters; however, dysfunction of respiratory and ionoregulatory processes is suspected. In order to evaluate the effects of acid exposure on the respiratory and ionoregulatory systems of developing brook trout, Salvelinus fontinalis, differences in gill morphology and numbers of chloride cells were compared between groups cf developing embryo-larval fish continuously exposed to moderately hard well water (130.0 mg.l-1 as CaCO3, pH 7.94) or to reconstituted soft, acidic water (4.4 mg.l-1 as CaCO3, pH 5.25) designed to mimic acidic waters of northern Wisconsin acidified lakes. Exposures were maintained for up to 48 days (82 days after fertilization) during critical periods of growth and differentiation of branchial structures. The second right gill arch of each fish was examined for changes in the development of filaments and lamellae and for differences in numbers of chloride cells. Gills of fish that developed in soft, acidic water contained greater numbers of normal and degenerating chloride cells, exhibited hyperplasia of primary epithelium and multiple fusions of adjacent filaments and lamellar epithelium than the gills of control fish. Filament and lamellar lengths and numbers of lamellae per filament were significantly less (P< 0.05) in fish that developed in soft, acidic water than in fish exposed to well water.

  20. Photocatalyzed multiple additions of amines to {alpha}, {beta}-unsaturated esters and nitriles

    SciTech Connect

    Das, S.; Kumar, J.S.D.; Thomas, K.G.; Shivaramayya, K.; George, M.V. |

    1994-02-11

    Photoelectron-transfer-catalyzed intermolecular carbon-carbon bond formation of primary, secondary, and tertiary amines with {alpha}, {beta}-unsaturated esters and nitriles using photosensitizers such as anthraquinone, acridone, and dicyanoanthracene has been investigated. The addition of {alpha}-aminoalkyl radicals, generated via photoelectron-transfer processes, to olefinic substrates and the subsequent 1,5-hydrogen abstraction reactions of the amine-olefin adduct radicals lead to a number of interesting multiple-olefin-added products. The adducts of the primary and secondary amines with {alpha}, {beta}-unsaturated esters undergo further cyclizations to give spiro and cyclic lactams, respectively.

  1. Molecular Formulas of Organic Compounds: The Nitrogen Rule and Degree of Unsaturation.

    ERIC Educational Resources Information Center

    Pellegrin, Valdo

    1983-01-01

    Demonstrates nitrogen rule and formula for calculating number of rings plus double bonds of any common organic compound. Calculation of degree of unsaturation (DU) by an empirical formula using successive modifications to the molecular formula, mathematical calculation of DU, and demonstration of the Euler formula are considered. (JN)

  2. Chemical resistance/thermal and mechanical properties of unsaturated polyester-based nanocomposites

    NASA Astrophysics Data System (ADS)

    Jaya Vinse Ruban, Y.; Ginil Mon, S.; Vetha Roy, D.

    2013-01-01

    Nanocomposites were synthesized using unsaturated polyester as the matrix and organically modified montmorillonite (CA-MMT) as the reinforcing agent. XRD pattern of the modified montmorillonite showed that the interlayer spacing expanded from 1.21 to 1.9 nm, indicating intercalation. TGA and DTA show loss of organic surfactant from interlayer galleries. Glass transition temperature (T g) of these composites increased from 71 °C in the unfilled unsaturated polyester to 79 °C in the composites with 5 % organically modified montmorillonite. Chemical resistance and mechanical properties of the UP/organo-clay nanocomposites were studied. Chemical resistance was studied under aqueous conditions in acetic acid, nitric acid, hydrochloric acid, sodium hydroxide, aqueous ammonia and sodium carbonate. Chemical resistance studies reveal maximum weight gain/loss with increasing clay content. Mechanical studies show maximum characteristics for the composites-clay filled 5 % (w/w).

  3. Hydraulic Conductivity Anisotropy of Heterogeneous Unsaturated Soils

    NASA Astrophysics Data System (ADS)

    Sun, Dongmin; Zhu, Jianting

    2010-05-01

    The effects of saturation degree (or capillary pressure) on hydraulic conductivity anisotropy in unsaturated soils have not been fully understood. This study developed an approach based on a conceptualization of combining the neural network based pedo-transfer function (PTF) results with the thin layer concept to explore the capillary pressure-dependent anisotropy in relation to soil texture and soil bulk density. The main objective is to examine how anisotropy characteristics are related to the relationships between hydraulic parameters and the basic soil attributes such as texture and bulk density. The hydraulic parameters are correlated with the texture and bulk density based on the pedo-transfer function (PTF) results. It is demonstrated that non-monotonic behavior of the unsaturated soil anisotropy in relation to the capillary pressure is only observed when the saturated hydraulic conductivity and the shape parameter are both related to the mean particle diameter. When only one hydraulic parameter is related to the grain diameter or when both are not related to the same attribute simultaneously, the unsaturated soil anisotropy increases monotonically with the increasing capillary pressure head. Therefore, it is suggested that this behavior is mainly due to the coupled dependence of the layer saturated hydraulic conductivities and the shape factors on the texture and bulk density. The correlation between the soil grain diameter and bulk density decreases the anisotropy effects of the unsaturated layered soils. The study illustrates that the inter-relationships of soil texture, bulk density, and hydraulic properties may cause vastly different characteristics of anisotropic unsaturated soils.

  4. Fish oil increases mitochondrial phospholipid unsaturation, upregulating reactive oxygen species and apoptosis in rat colonocytes.

    PubMed

    Hong, Mee Young; Chapkin, Robert S; Barhoumi, Rola; Burghardt, Robert C; Turner, Nancy D; Henderson, Cara E; Sanders, Lisa M; Fan, Yang-Yi; Davidson, Laurie A; Murphy, Mary E; Spinka, Christine M; Carroll, Raymond J; Lupton, Joanne R

    2002-11-01

    We have shown that a combination of fish oil (high in n-3 fatty acids) with the butyrate-producing fiber pectin, upregulates apoptosis in colon cells exposed to the carcinogen azoxymethane, protecting against colon tumor development. We now hypothesize that n-3 fatty acids prime the colonocytes such that butyrate can initiate apoptosis. To test this, 30 Sprague-Dawley rats were provided with diets differing in the fatty acid composition (corn oil, fish oil or a purified fatty acid ethyl ester diet). Intact colon crypts were exposed ex vivo to butyrate, and analyzed for reactive oxygen species (ROS), mitochondrial membrane potential (MMP), translocation of cytochrome C to the cytosol, and caspase-3 activity (early events in apoptosis). The fatty acid composition of the three major mitochondrial phospholipids was also determined, and an unsaturation index calculated. The unsaturation index in cardiolipin was correlated with ROS levels (R = 0.99; P = 0.02). When colon crypts from fish oil and FAEE-fed rats were exposed to butyrate, MMP decreased (P = 0.041); and translocation of cytochrome C to the cytosol (P = 0.037) and caspase-3 activation increased (P = 0.032). The data suggest that fish oil may prime the colonocytes for butyrate-induced apoptosis by enhancing the unsaturation of mitochondrial phospholipids, especially cardiolipin, resulting in an increase in ROS and initiating apoptotic cascade. PMID:12419841

  5. Fish oil increases mitochondrial phospholipid unsaturation, upregulating reactive oxygen species and apoptosis in rat colonocytes

    NASA Technical Reports Server (NTRS)

    Hong, Mee Young; Chapkin, Robert S.; Barhoumi, Rola; Burghardt, Robert C.; Turner, Nancy D.; Henderson, Cara E.; Sanders, Lisa M.; Fan, Yang-Yi; Davidson, Laurie A.; Murphy, Mary E.; Spinka, Christine M.; Carroll, Raymond J.; Lupton, Joanne R.

    2002-01-01

    We have shown that a combination of fish oil (high in n-3 fatty acids) with the butyrate-producing fiber pectin, upregulates apoptosis in colon cells exposed to the carcinogen azoxymethane, protecting against colon tumor development. We now hypothesize that n-3 fatty acids prime the colonocytes such that butyrate can initiate apoptosis. To test this, 30 Sprague-Dawley rats were provided with diets differing in the fatty acid composition (corn oil, fish oil or a purified fatty acid ethyl ester diet). Intact colon crypts were exposed ex vivo to butyrate, and analyzed for reactive oxygen species (ROS), mitochondrial membrane potential (MMP), translocation of cytochrome C to the cytosol, and caspase-3 activity (early events in apoptosis). The fatty acid composition of the three major mitochondrial phospholipids was also determined, and an unsaturation index calculated. The unsaturation index in cardiolipin was correlated with ROS levels (R = 0.99; P = 0.02). When colon crypts from fish oil and FAEE-fed rats were exposed to butyrate, MMP decreased (P = 0.041); and translocation of cytochrome C to the cytosol (P = 0.037) and caspase-3 activation increased (P = 0.032). The data suggest that fish oil may prime the colonocytes for butyrate-induced apoptosis by enhancing the unsaturation of mitochondrial phospholipids, especially cardiolipin, resulting in an increase in ROS and initiating apoptotic cascade.

  6. Amide groups switch selectivity: C-H trifluoromethylation of α,β-unsaturated amides and subsequent asymmetric transformation.

    PubMed

    Li, Lei; Guo, Jing-Yao; Liu, Xing-Guo; Chen, Su; Wang, Yong; Tan, Bin; Liu, Xin-Yuan

    2014-11-21

    The first direct C-H β-trifluoromethylation of unsubstituted or α-alkyl-substituted α,β-unsaturated carbonyl compounds under metal-free conditions was realized with excellent regio- and stereoselectivity as well as a very broad substrate scope. Both olefinic and allylic trifluoromethylation products are accessible with high selectivities by altering the substrate substitutions. The resultant olefinic products, namely (E)-β-trifluoromethyl (CF3) α,β-unsaturated hydroxamic acid derivatives, served as acceptors in organocatalytic asymmetric Michael addition reactions to give hydroxamic acid derivatives bearing a chiral CF3-substituted stereocenter with high enantioselectivities. PMID:25383919

  7. ESTIMATION OF BACTERIAL CELL NUMBERS IN HUMIC ACID-RICH SALT MARSH SEDIMENTS WITH PROBES DIRECTED TO 16S RIBOSOMAL DNA

    EPA Science Inventory

    The feasibility of using probes directed towards ribosomal DNAs (rDNAs) as a quantitative approach to estimating cell numbers was examined and applied to study the structure of a bacterial community in humic acid-rich salt marsh sediments. Hybridizations were performed with membr...

  8. Effective atomic numbers and electron densities of bacteriorhodopsin and its comprising amino acids in the energy range 1 keV-100 GeV

    NASA Astrophysics Data System (ADS)

    Ahmadi, Morteza; Lunscher, Nolan; Yeow, John T. W.

    2013-04-01

    Recently, there has been an interest in fabrication of X-ray sensors based on bacteriorhodopsin, a proton pump protein in cell membrane of Halobacterium salinarium. Therefore, a better understanding of interaction of X-ray photons with bacteriorhodopsin is required. We use WinXCom program to calculate the mass attenuation coefficient of bacteriorhodopsin and its comprising amino acids for photon energies from 1 keV to 100 GeV. These amino acids include alanine, arginine, asparagine, aspartic acid, glutamine, glutamic acid, glycine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, Asx1, Asx2, Glx1 and Glx2. We then use that data to calculate effective atomic number and electron densities for the same range of energy. We also emphasize on two ranges of energies (10-200 keV and 1-20 MeV) in which X-ray imaging and radiotherapy machines work.

  9. Comparative effects of n-3, n-6 and n-9 unsaturated fatty acid-rich diet consumption on lupus nephritis, autoantibody production and CD4+ T cell-related gene responses in the autoimmune NZBWF1 mouse.

    PubMed

    Pestka, James J; Vines, Laura L; Bates, Melissa A; He, Kaiyu; Langohr, Ingeborg

    2014-01-01

    Mortality from systemic lupus erythematosus (SLE), a prototypical autoimmune disease, correlates with the onset and severity of kidney glomerulonephritis. There are both preclinical and clinical evidence that SLE patients may benefit from consumption of n-3 polyunsaturated fatty acids (PUFA) found in fish oil, but the mechanisms remain unclear. Here we employed the NZBWF1 SLE mouse model to compare the effects of dietary lipids on the onset and severity of autoimmune glomerulonephritis after consuming: 1) n-3 PUFA-rich diet containing docosahexaenoic acid-enriched fish oil (DFO), 2) n-6 PUFA-rich Western-type diet containing corn oil (CRN) or 3) n-9 monounsaturated fatty acid (MUFA)-rich Mediterranean-type diet containing high oleic safflower oil (HOS). Elevated plasma autoantibodies, proteinuria and glomerulonephritis were evident in mice fed either the n-6 PUFA or n-9 MUFA diets, however, all three endpoints were markedly attenuated in mice that consumed the n-3 PUFA diet until 34 wk of age. A focused PCR array was used to relate these findings to the expression of 84 genes associated with CD4+ T cell function in the spleen and kidney both prior to and after the onset of the autoimmune nephritis. n-3 PUFA suppression of autoimmunity in NZBWF1 mice was found to co-occur with a generalized downregulation of CD4+ T cell-related genes in kidney and/or spleen at wk 34. These genes were associated with the inflammatory response, antigen presentation, T cell activation, B cell activation/differentiation and leukocyte recruitment. Quantitative RT-PCR of representative affected genes confirmed that n-3 PUFA consumption was associated with reduced expression of CD80, CTLA-4, IL-10, IL-18, CCL-5, CXCR3, IL-6, TNF-α and osteopontin mRNAs in kidney and/or spleens as compared to mice fed n-6 PUFA or n-9 MUFA diets. Remarkably, many of the genes identified in this study are currently under consideration as biomarkers and/or biotherapeutic targets for SLE and other autoimmune

  10. Automatic differentiation for PDES: Unsaturated flow case study

    SciTech Connect

    Corliss, G.F.; Bischof, C.; Griewank, A.; Wright, S.J.; Robey, T.

    1992-07-01

    The techniques of automatic differentiation are applied to an example partial differential equation arising from the modeling of unsaturated flow. One common paradigm for the numerical solution to some classes of two-, three-, or higher-dimensional partial differential equations is as follows: Given a PDE and boundary conditions, apply finite difference or finite element approximations on some appropriate (frequently nonuniform) grid, and enforce an approximate solution by solving a nonlinear system F(u)=0 for the residual by Newton`s method. The dimension of the nonlinear system F(u)=0 is proportional to the number of grid points. In current algorithms, the Jacobian J required by Newton`s method is computed by some combination of hand coding, divided differences, matrix coloring, and partial separability. We present a case study documenting the steps we took in analyzing a code provided by Robey for modeling unsaturated flow in porous media. Our purpose was to compute J by automatic differentiation using ADOL-C, a tool for automatic differentiation using overloaded operators in C++.

  11. Automatic differentiation for PDES: Unsaturated flow case study

    SciTech Connect

    Corliss, G.F.; Bischof, C.; Griewank, A.; Wright, S.J. ); Robey, T. )

    1992-01-01

    The techniques of automatic differentiation are applied to an example partial differential equation arising from the modeling of unsaturated flow. One common paradigm for the numerical solution to some classes of two-, three-, or higher-dimensional partial differential equations is as follows: Given a PDE and boundary conditions, apply finite difference or finite element approximations on some appropriate (frequently nonuniform) grid, and enforce an approximate solution by solving a nonlinear system F(u)=0 for the residual by Newton's method. The dimension of the nonlinear system F(u)=0 is proportional to the number of grid points. In current algorithms, the Jacobian J required by Newton's method is computed by some combination of hand coding, divided differences, matrix coloring, and partial separability. We present a case study documenting the steps we took in analyzing a code provided by Robey for modeling unsaturated flow in porous media. Our purpose was to compute J by automatic differentiation using ADOL-C, a tool for automatic differentiation using overloaded operators in C++.

  12. Flow dynamics and solute transport in unsaturated rock fractures

    SciTech Connect

    Su, G. W.

    1999-10-01

    Rock fractures play an important role in flow and contaminant transport in fractured aquifers, production of oil from petroleum reservoirs, and steam generation from geothermal reservoirs. In this dissertation, phenomenological aspects of flow in unsaturated fractures were studied in visualization experiments conducted on a transparent replica of a natural, rough-walled rock fracture for inlet conditions of constant pressure and flow rate over a range of angles of inclination. The experiments demonstrated that infiltrating liquid proceeds through unsaturated rock fractures along non-uniform, localized preferential flow paths. Even in the presence of constant boundary conditions, intermittent flow was a persistent flow feature observed, where portions of the flow channel underwent cycles of snapping and reforming. Two modes of intermittent flow were observed, the pulsating blob mode and the rivulet snapping mode. A conceptual model for the rivulet snapping mode was proposed and examined using idealized, variable-aperture fractures. The frequency of intermittent flow events was measured in several experiments and related to the capillary and Bond numbers to characterize this flow behavior.

  13. Oxidative dehydrogenation of alkanes to unsaturated hydrocarbons

    DOEpatents

    Kung, Harold H.; Chaar, Mohamed A.

    1988-01-01

    Oxidative dehydrogenation of alkanes to unsaturated hydrocarbons is carried out over metal vanadate catalysts under oxidizing conditions. The vanadate catalysts are represented by the formulas M.sub.3 (VO.sub.4).sub.2 and MV.sub.2 O.sub.6, M representing Mg, Zn, Ca, Pb, or Cd. The reaction is carried out in the presence of oxygen, but the formation of oxygenate by-products is suppressed.

  14. Oxidative dehydrogenation of alkanes to unsaturated hydrocarbons

    DOEpatents

    Kung, H.H.; Chaar, M.A.

    1988-10-11

    Oxidative dehydrogenation of alkanes to unsaturated hydrocarbons is carried out over metal vanadate catalysts under oxidizing conditions. The vanadate catalysts are represented by the formulas M[sub 3](VO[sub 4])[sub 2] and MV[sub 2]O[sub 6], M representing Mg, Zn, Ca, Pb, or Cd. The reaction is carried out in the presence of oxygen, but the formation of oxygenate by-products is suppressed.

  15. Effects of lauric acid on ruminal protozoal numbers and fermentation pattern and milk production in lactating dairy cows

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The objectives of this study were to evaluate lauric acid (LA) as a practical agent to suppress ruminal protozoa (RP), and to assess the effects of RP suppression on fermentation patterns and milk production in dairy cows. In experiment 1, six Holstein cows fitted with ruminal cannulae were used in ...

  16. Effects of feeding lauric acid on ruminal protozoa numbers, fermentation, and digestion and on milk production in dairy cows

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The objectives of this study were: (1) to determine the level of lauric acid (LA) addition to the diet necessary to effectively suppress ruminal protozoa (RP) to the extent observed when a single dose was given directly into the rumen; (2) to assess its effects on production and ruminal metabolism; ...

  17. Unsaturated compounds induce up-regulation of CD86 on dendritic cells in the in vitro sensitization assay LCSA.

    PubMed

    Frohwein, Thomas Armin; Sonnenburg, Anna; Zuberbier, Torsten; Stahlmann, Ralf; Schreiner, Maximilian

    2016-04-01

    Unsaturated compounds are known to cause false-positive reactions in the local lymph node assay (LLNA) but not in the guinea pig maximization test. We have tested a panel of substances (succinic acid, undecylenic acid, 1-octyn-3-ol, fumaric acid, maleic acid, linoleic acid, oleic acid, alpha-linolenic acid, squalene, and arachidonic acid) in the loose-fit coculture-based sensitization assay (LCSA) to evaluate whether unspecific activation of dendritic cells is a confounder for sensitization testing in vitro. Eight out of 10 tested substances caused significant up-regulation of CD86 on dendritic cells cocultured with keratinocytes and would have been classified as sensitizers; only succinic acid was tested negative, and squalene had to be excluded from data analysis due to poor solubility in cell culture medium. Based on human data, only undecylenic acid can be considered a true sensitizer. The true sensitizing potential of 1-octyn-3-ol is uncertain. Fumaric acid and its isomer maleic acid are not known as sensitizers, but their esters are contact allergens. A group of 18- to 20-carbon chain unsaturated fatty acids (linoleic acid, oleic acid, alpha-linolenic acid, and arachidonic acid) elicited the strongest reaction in vitro. This is possibly due to the formation of pro-inflammatory lipid mediators in the cell culture causing nonspecific activation of dendritic cells. In conclusion, both the LLNA and the LCSA seem to provide false-positive results for unsaturated fatty acids. The inclusion of T cells in dendritic cell-based in vitro sensitization assays may help to eliminate false-positive results due to nonspecific dendritic cell activation. This would lead to more accurate prediction of sensitizers, which is paramount for consumer health protection and occupational safety. PMID:25975990

  18. Unsaturated lipid matrices protect plant sterols from degradation during heating treatment.

    PubMed

    Barriuso, Blanca; Astiasarán, Iciar; Ansorena, Diana

    2016-04-01

    The interest in plant sterols enriched foods has recently enhanced due to their healthy properties. The influence of the unsaturation degree of different fatty acids methyl esters (FAME: stearate, oleate, linoletate and linolenate) on a mixture of three plant sterols (PS: campesterol, stigmasterol and β-sitosterol) was evaluated at 180 °C for up to 180 min. Sterols degraded slower in the presence of unsaturated FAME. Both PS and FAME degradation fit a first order kinetic model (R(2)>0.9). Maximum oxysterols concentrations were achieved at 20 min in neat PS and 120 min in lipid mixtures and this maximum amount decreased with increasing their unsaturation degree. In conclusion, the presence of FAME delayed PS degradation and postponed oxysterols formation. This protective effect was further promoted by increasing the unsaturation degree of FAME. This evidence could help industries to optimize the formulation of sterol-enriched products, so that they could maintain their healthy properties during cooking or processing. PMID:26593514

  19. Heterogeneous oxidation of unsaturated organic aerosols

    NASA Astrophysics Data System (ADS)

    Nah, T.; Kessler, S. H.; Daumit, K. E.; Kroll, J. H.; Leone, S.; Wilson, K. R.

    2011-12-01

    A significant mass fraction of atmospheric aerosols is composed of a variety of oxidized organic compounds with varying functional groups that may affect the rate at which they chemically age. Here we study the heterogeneous reaction of OH radicals with different sub-micron, alkenoic acid particles: Oleic acid (OA), Linoleic acid (LA), and Linolenic acid (LNA), in the presence of H2O2 and O2. This work explores how OH addition reactions initiate chain reactions that rapidly transform the chemical composition of an organic particle. Particles are chemically aged in a photochemical flow tube reactor where they are exposed to OH radicals (~ 1E11 molecule cm-3 s) that are produced by the photolysis of H2O2 at 254 nm. The aerosols are then sized and their composition analyzed via Atmospheric Pressure Chemical Ionization mass spectrometry (APCI-MS). Kinetic measurements, done by tracking the decay of the alkenoic acid parent ion with increasing OH exposure, show that the reactive uptake coefficient, which is defined as the fraction of gas-phase collisions that result in a reaction, is larger than 1, indicating the presence of secondary chain chemistry occurring within the aerosol. The reactive uptake coefficient is found to scale linearly with the number of double bonds present in the molecule. In addition, the reactive uptake coefficient is found to depend sensitively upon the concentrations of O2 and H2O2 in the photochemical flow tube reactor, indicating that O2 and H2O2 play roles as propagators and terminators in the secondary chain reactions. Elemental analysis and mechanistic pathways will also be presented herein.

  20. Sequential hydroformylation/aldol reactions: versatile and controllable access to functionalised carbocycles from unsaturated carbonyl compounds.

    PubMed

    Keränen, Mark D; Kot, Kinga; Hollmann, Christoph; Eilbracht, Peter

    2004-11-21

    Three different modes of hydroformylation/aldol reaction sequences involving either acid-catalysed aldol reactions, Mukaiyama aldol addition of pre-formed enolsilanes or aldol addition of in situ generated boron enolates can be applied to unsaturated ketones and ketoesters to afford the corresponding carbocyclic aldol adducts in good yields proceeding through the intermediate activated ketoaldehydes. In selected cases, complimentary, synthetically useful diastereoselectivities were observed in the products. PMID:15534717

  1. Docosahexaenoic acid and eicosapentaenoic acid induce changes in the physical properties of a lipid bilayer model membrane.

    PubMed

    Onuki, Yoshinori; Morishita, Mariko; Chiba, Yoshiyuki; Tokiwa, Shinji; Takayama, Kozo

    2006-01-01

    We investigated the effect of fatty acids such as stearic acid (SA, 18:0), oleic acid (OA, 18:1), eicosapentaenoic acid (EPA, 20:5), and docosahexaenoic acid (DHA, 22:6) on a dipalmitoylphosphatidylcholine (DPPC) bilayer by determining the phase transition temperature, fluorescence anisotropy of 1,6-diphenyl-1,3,5-hexatriene (DPH), and detergent insolubility. Treatment with unsaturated fatty acid broadened and shifted the phase transitions of the DPPC bilayer to a lower temperature. The phase transition temperature and the value of fluorescence anisotropy of DPH at 37 degrees C decreased progressively with increasing treatment amounts of unsaturated fatty acid. A large amount of the DPPC bilayer treated with unsaturated fatty acid was dissolved in Triton X-100, obtaining a low level of detergent insolubility. These modifications of the bilayer physical properties were most pronounced with DHA and EPA treatment. These data show that unsaturated fatty acids, particularly DHA and EPA, induce a marked change in the lipid bilayer structure. The composition of fatty acids in the DPPC bilayer was similar after treatment with various unsaturated fatty acids, suggesting that the different actions of unsaturated fatty acids are attributed to change in the molecular structure (e.g., kinked conformation by double bonds). We further explored the change in physical properties induced by fatty acids dispersed in a water-in-oil-in-water multiple emulsion and found that unsaturated fatty acids acted efficiently on the DPPC bilayer, even when incorporated in emulsion form. PMID:16394552

  2. Zeolite-Catalyzed Isomerization of Oleic Acid to Branched-Chain Isomers

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Branched-chain saturated fatty acids have potential as oleochemical intermediates since they have better oxidative stability than linear unsaturated fatty acids and have better low-temperature properties than linear saturated fatty acids. Previous studies in converting unsaturated fatty acids to br...

  3. The unsaturation of phosphatidylglycerol in thylakoid membrane alleviates PSII photoinhibition under chilling stress.

    PubMed

    Sun, Xiao-lin; Yang, Sha; Wang, Li-Yan; Zhang, Qiu-Yu; Zhao, Shi-Jie; Meng, Qing-Wei

    2011-10-01

    Over-expression of chloroplast glycerol-3-phosphate acyltransferase gene (LeGPAT) in tomato increased cis-unsaturated fatty acid content in phosphatidylglycerol (PG) of the thylakoid membrane. Under chilling stress, the oxygen evolving activity, the maximal photochemical efficiency of PSII (F (v)/F (m)), and superoxide dismutase (SOD) and ascorbate peroxidase (APX) activities decreased less in sense lines than in antisense lines compared to wild-type (WT) plants. Consistently, the relative electric conductivity, O⁻₂and H(2)O(2) contents in sense lines were lower than those of WT and antisense lines. The antisense lines with low level of unsaturated fatty acids in PG were extremely susceptible to photoinhibition of PSII and had a significant reduction in the D1 protein content of PSII reaction center under chilling stress. However, in the presence of streptomycin (SM), the degradation of D1 protein was faster in sense lines than in WT and antisense plants. These results suggested that, under chilling stress conditions, increasing cis-unsaturated fatty acids in PG through over-expression of LeGPAT can alleviate PSII photoinhibition by accelerating the repair of D1 protein and improving the activities of antioxidant enzymes in chloroplasts. PMID:21695527

  4. Effects of amino acids on egg number and egg mass of brown (heavy breed) and white (light breed) laying hens.

    PubMed

    Bonekamp, R P R T; Lemme, A; Wijtten, P J A; Sparla, J K W M

    2010-03-01

    Different types (light to heavy) of laying hens are used in practice. There are questions about the optimum level of balanced protein (BP) supply in feed for different types of hens. Therefore, a broad range of amino acids intake levels [550 to 800 mg of true fecal digestible (TFD) Lys/hen per d] was tested on heavy (Lohmann Brown Classic) and light (Lohmann LSL Classic) laying hens from 24 to 60 wk of age. The other indispensable amino acids were fed in fixed ratios to TFD Lys in all treatments. A total of 282 Lohmann Brown Classic and 282 Lohmann LSL Classic hens (24 wk of age) were divided into 12 experimental groups (individually housed) based on daily egg mass production and BW. Replicates of the heavy strain started with a similar average daily egg mass production (51.1 g/hen per d), laying percentage (95.9%), and hen weight (1,860 g). Replicates of the light strain started with a similar average daily egg mass production (52.0 g/hen per d), laying percentage (97.3%), and hen weight (1,478 g). Diets were fed restrictively with an aimed feed intake of 110 g/hen per day [308 kcal/hen per d of AME(n (layers))] and 100 g/hen per day [280 kcal/hen per d of AME(n (layers))] for heavy and light hens, respectively, to achieve the required BP intake levels. For light hens, a BP intake with 600 mg of TFD Lys was sufficient for optimal laying percentage, whereas maximum laying percentage was not achieved with the highest TFD Lys in heavy hens. For egg weight, daily egg mass production as well as feed conversion regression analysis revealed that asymptotes were not achieved with the highest amino acid levels in both layer strains. PMID:20181869

  5. C-H functionalization of cyclic amines: redox-annulations with α,β-unsaturated carbonyl compounds.

    PubMed

    Kang, YoungKu; Richers, Matthew T; Sawicki, Conrad H; Seidel, Daniel

    2015-07-01

    Cyclic amines such as pyrrolidine and 1,2,3,4-tetrahydroisoquinoline undergo redox-annulations with α,β-unsaturated aldehydes and ketones. Carboxylic acid promoted generation of a conjugated azomethine ylide is followed by 6π-electrocylization, and, in some cases, tautomerization. The resulting ring-fused pyrrolines are readily oxidized to the corresponding pyrroles or reduced to pyrrolidines. PMID:26051897

  6. Conformational preferences of a few enkephalin unsaturated analogs

    NASA Astrophysics Data System (ADS)

    Alagona, G.; Ciuffo, G. M.; Ghio, C.

    1994-07-01

    The conformational behavior of enkephalin analogs containing α-β unsaturated residues was studied employing a recent modification (G. Alagona, C. Ghio and C. Pratesi, J. Comput. Chem., 12 (1991) 934) of an existing force field for nucleic acids and proteins (S.J. Weiner, P.A. Kollman, D.A. Case, U. Chandra Singh, C. Ghio, G. Alagona, S. Profeta, Jr., and P. Weiner, J. Am. Chem. Soc., 106 (1984) 765) with molecular mechanics and molecular dynamics simulations. On the basis of the structures obtained, the rationale proposed for the morphine-like activity of enkephalins (i.e. the presence of β-turn of type II', considered important for the binding to opiate receptors) was checked and confirmed on the basis of topological features associated with a compact positioning of the aromatic side chains, tyrosine and phenylalanine or dehydrophenylalanine. The molecular electrostatic potential in the plane perpendicular to the α-β double bond may account only in part for the enhanced potency often observed in unsaturated compounds, and attributed to the intrinsic reactivity of the double bond toward nucleophilic sites on the opiate receptor or to a stronger binding to receptors. In the presence of the solvent, described as a continuous dielectric medium, most of the least stable conformations in vacuo are greatly stabilized, thus becoming even more favored than the gas-phase minimum-energy structures. Interestingly enough, the solvent stabilization is noticeable not only for the extended conformers, as expected, but also for several β-turn structures of type II'.

  7. Review and selection of unsaturated flow models

    SciTech Connect

    Reeves, M.; Baker, N.A.; Duguid, J.O.

    1994-04-04

    Since the 1960`s, ground-water flow models have been used for analysis of water resources problems. In the 1970`s, emphasis began to shift to analysis of waste management problems. This shift in emphasis was largely brought about by site selection activities for geologic repositories for disposal of high-level radioactive wastes. Model development during the 1970`s and well into the 1980`s focused primarily on saturated ground-water flow because geologic repositories in salt, basalt, granite, shale, and tuff were envisioned to be below the water table. Selection of the unsaturated zone at Yucca Mountain, Nevada, for potential disposal of waste began to shift model development toward unsaturated flow models. Under the US Department of Energy (DOE), the Civilian Radioactive Waste Management System Management and Operating Contractor (CRWMS M&O) has the responsibility to review, evaluate, and document existing computer models; to conduct performance assessments; and to develop performance assessment models, where necessary. This document describes the CRWMS M&O approach to model review and evaluation (Chapter 2), and the requirements for unsaturated flow models which are the bases for selection from among the current models (Chapter 3). Chapter 4 identifies existing models, and their characteristics. Through a detailed examination of characteristics, Chapter 5 presents the selection of models for testing. Chapter 6 discusses the testing and verification of selected models. Chapters 7 and 8 give conclusions and make recommendations, respectively. Chapter 9 records the major references for each of the models reviewed. Appendix A, a collection of technical reviews for each model, contains a more complete list of references. Finally, Appendix B characterizes the problems used for model testing.

  8. Characterizing Unsaturated Diffusion in Porous Tuff Gravel

    SciTech Connect

    Hu, Q; Kneafsey, T J; Roberts, J J; Tomutsa, L; Wang, J S

    2003-11-12

    Evaluation of solute diffusion in unsaturated porous gravel is very important for investigations of contaminant transport and remediation, risk assessment, and waste disposal (e.g., the potential high-level nuclear waste repository at Yucca Mountain, Nevada). For a porous aggregate medium such as granular tuff, the total water content is comprised of surface water and interior water. The surface water component (water film around grains and pendular water between the grain contacts) could serve as a predominant diffusion pathway. To investigate the extent of surface water films and contact points affect solute diffusion in unsaturated gravel, we examined the configuration of water using x-ray computed tomography in partially saturated gravel, and made quantitative measurements of diffusion at multiple water contents using two different techniques. In the first, diffusion coefficients of potassium chloride in 2-4 mm granular tuff at multiple water contents are calculated from electrical conductivity measurements using the Nernst-Einstein equation. In the second, we used laser ablation with inductively coupled plasma-mass spectrometry to perform micro-scale mapping, allowing the measurement of diffusion coefficients for a mixture of chemical tracers for tuff cubes and tetrahedrons having two contact geometries (cube-cube and cube-tetrahedron). The x-ray computed tomography images show limited contact between grains, and this could significantly hinder the pathways for diffusive transport. Experimental results show the critical role of surface water in controlling transport pathways and hence the magnitude of diffusion. Even with a bulk volumetric water content of 1.5%, the measured solute diffusion coefficient is as low as 1.5 x 10{sup -14} m{sup 2}/s. Currently used diffusion models relating diffusion coefficients to total volumetric water content inadequately describe unsaturated diffusion behavior in porous gravel.

  9. Characterizing unsaturated diffusion in porous tuff gravel

    SciTech Connect

    Hu, Qinhong; Kneafsey, Timothy J.; Roberts, Jeffery J.; Tomutsa, Liviu; Wang, Joseph, S.Y.

    2003-11-12

    Evaluation of solute diffusion in unsaturated porous gravel is very important for investigations of contaminant transport and remediation, risk assessment, and waste disposal (for example, the potential high-level nuclear waste repository at Yucca Mountain, Nevada). For a porous aggregate medium such as granular tuff, the total water content is comprised of surface water and interior water. The surface water component (water film around grains and pendular water between the grain contacts) could serve as a predominant diffusion pathway. To investigate the extent to which surface water films and contact points affect solute diffusion in unsaturated gravel, we examined the configuration of water using x-ray computed tomography in partially saturated gravel, and made quantitative measurements of diffusion at multiple water contents using two different techniques. In the first, diffusion coefficients of potassium chloride in 2-4 mm granular tuff at multiple water contents were calculated from electrical conductivity measurements using the Nernst-Einstein equation. In the second, we used laser ablation with inductively coupled plasma-mass spectrometry to perform micro-scale mapping, allowing the measurement of diffusion coefficients for a mixture of chemical tracers for tuff cubes and tetrahedrons having two contact geometries (cube-cube and cube-tetrahedron). The x-ray computed tomography images show limited contact between grains, and this could hinder the pathways for diffusive transport. Experimental results show the critical role of surface water in controlling transport pathways and hence the magnitude of diffusion. Even with a bulk volumetric water content of 1.5%, the measured solute diffusion coefficient is as low as 1.5 x 10{sup -14} m{sup 2}/s for tuff gravel. Currently used diffusion models relating diffusion coefficients to total volumetric water content inadequately describe unsaturated diffusion behavior in porous gravel at very low water contents.

  10. Nucleic acid amplification in vitro: detection of sequences with low copy numbers and application to diagnosis of human immunodeficiency virus type 1 infection.

    PubMed Central

    Guatelli, J C; Gingeras, T R; Richman, D D

    1989-01-01

    The enzymatic amplification of specific nucleic acid sequences in vitro has revolutionized the use of nucleic acid hybridization assays for viral detection. With this method, the copy number of a pathogen-specific sequence is increased several orders of magnitude before detection is attempted. The sensitivity and specificity of detection are thus markedly improved. Mullis and Faloona devised the first method of sequence amplification in vitro, the polymerase chain reaction (K.B. Mullis and F.A. Faloona, Methods Enzymol. 155:355-350, 1987). By this method, synthetic oligonucleotide primers direct repeated, target-specific, deoxyribonucleic acid-synthetic reactions, resulting in an exponential increase in the amount of the specific target sequence. The application of sequence amplification to viral detection was initially performed with human immunodeficiency virus type 1 and human T-cell lymphoma virus type I. In principle, however, this approach can be applied to the detection of any deoxyribonucleic or ribonucleic acid virus; the only requirement is that sufficient nucleotide sequence data exist to allow the synthesis of target-specific oligonucleotide primers. The use of target amplification in vitro will permit a variety of studies of viral pathogenesis which have not been feasible because of the low copy number of the viral nucleic acids in infected material. This approach is particularly applicable to the study of human retroviral infections, which are chronic and persistent and are characterized by low titers of virus in tissues. In addition, target amplification in vitro will facilitate the development of new methods of sequence detection, which will be useful for rapid viral diagnosis in the clinical laboratory. PMID:2650862

  11. It is all about fluidity: Fatty acids and macrophage phagocytosis.

    PubMed

    Schumann, Julia

    2016-08-15

    Phagocytosis is an early and fundamental step for the effective clearance of disease causing agents. The ability to engulf and kill pathogens is considered as a major effector function of macrophages. In their phagocytic role macrophages are part of the first line of innate immune defense. A number of studies investigating fatty acid effects on macrophage phagocytosis have been conducted over many years. In vitro-data consistently report that alterations in macrophage membrane fatty acid composition are linked to an altered phagocytic capacity, i.e. an increase in membrane unsaturated fatty acid content is associated with an increase in engulfment and killing rate. The mode of action of fatty acids seems to be the modulation of the physical nature of the macrophage plasma membrane. It appears that the saturated-to-unsaturated fatty acid ratio of macrophage membrane phospholipids is of importance in determining macrophage phagocytic capacity. Available in vivo-data are less clear. At present, there is a lack of systematic studies elucidating key factors such as fatty acid efficacy, effective dose or dosing intervals. Without this knowledge the targeted modulation of macrophage phagocytosis in vivo by fatty acids is still a distant possibility. PMID:25987422

  12. Plant fatty acid hydroxylases

    DOEpatents

    Somerville, Chris; Broun, Pierre; van de Loo, Frank

    2001-01-01

    This invention relates to plant fatty acyl hydroxylases. Methods to use conserved amino acid or nucleotide sequences to obtain plant fatty acyl hydroxylases are described. Also described is the use of cDNA clones encoding a plant hydroxylase to produce a family of hydroxylated fatty acids in transgenic plants. In addition, the use of genes encoding fatty acid hydroxylases or desaturases to alter the level of lipid fatty acid unsaturation in transgenic plants is described.

  13. Visible light-induced oxidation of unsaturated components of cutins: a significant process during the senescence of higher plants.

    PubMed

    Rontani, Jean-François; Rabourdin, Adélaïde; Pinot, Franck; Kandel, Sylvie; Aubert, Claude

    2005-02-01

    9-Hydroperoxy-18-hydroxyoctadec-10(trans)-enoic and 10-hydroperoxy-18-hydroxyoctadec-8(trans)-enoic acids deriving from type II (i.e. involving 1O2) photooxidation of 18-hydroxyoleic acid were detected after visible light-induced senescence experiments carried out with Petroselinum sativum and subsequent cutin depolymerisation. These results showed that in senescent plants, where the 1O2 formation rate exceeds the quenching capacity of the photoprotective system, 1O2 can migrate outside the chloroplasts and affect the unsaturated components of cutins. Significant amounts of 9,18-dihydroxyoctadec-10(trans)-enoic and 10,18-dihydroxyoctadec-8(trans)-enoic acids resulting from the reduction of these photoproducts of 18-hydroxyoleic acid were also detected in different natural samples. These results well support the significance of the photooxidation of the unsaturated components of higher plant cutins in the natural environment. PMID:15680988

  14. Effective atomic number and electron density of amino acids within the energy range of 0.122-1.330 MeV

    NASA Astrophysics Data System (ADS)

    More, Chaitali V.; Lokhande, Rajkumar M.; Pawar, Pravina P.

    2016-08-01

    Photon attenuation coefficient calculation methods have been widely used to accurately study the properties of amino acids such as n-acetyl-L-tryptophan, n-acetyl-L-tyrosine, D-tryptophan, n-acetyl-L-glutamic acid, D-phenylalanine, and D-threonine. In this study, mass attenuation coefficients (μm) of these amino acids for 0.122-, 0.356-, 0.511-, 0.662-, 0.884-, 1.170, 1.275-, 1.330-MeV photons are determined using the radio-nuclides Co57, Ba133, Cs137, Na22, Mn54, and Co60. NaI (Tl) scintillation detection system was used to detect gamma rays with a resolution of 8.2% at 0.662 MeV. The calculated attenuation coefficient values were then used to determine total atomic cross sections (σt), molar extinction coefficients (ε), electronic cross sections (σe), effective atomic numbers (Zeff), and effective electron densities (Neff) of the amino acids. Theoretical values were calculated based on the XCOM data. Theoretical and experimental values are found to be in a good agreement (error<5%). The variations of μm, σt, ε, σe, Zeff, and Neff with energy are shown graphically. The values of μm, σt, ε, σe are higher at lower energies, and they decrease sharply as energy increases; by contrast, Zeff and Neff were found to be almost constant.

  15. NaturAnalogs for the Unsaturated Zone

    SciTech Connect

    A. Simmons; A. Unger; M. Murrell

    2000-03-08

    The purpose of this Analysis/Model Report (AMR) is to document natural and anthropogenic (human-induced) analog sites and processes that are applicable to flow and transport processes expected to occur at the potential Yucca Mountain repository in order to build increased confidence in modeling processes of Unsaturated Zone (UZ) flow and transport. This AMR was prepared in accordance with ''AMR Development Plan for U0135, Natural Analogs for the UZ'' (CRWMS 1999a). Knowledge from analog sites and processes is used as corroborating information to test and build confidence in flow and transport models of Yucca Mountain, Nevada. This AMR supports the Unsaturated Zone (UZ) Flow and Transport Process Model Report (PMR) and the Yucca Mountain Site Description. The objectives of this AMR are to test and build confidence in the representation of UZ processes in numerical models utilized in the UZ Flow and Transport Model. This is accomplished by: (1) applying data from Boxy Canyon, Idaho in simulations of UZ flow using the same methodologies incorporated in the Yucca Mountain UZ Flow and Transport Model to assess the fracture-matrix interaction conceptual model; (2) Providing a preliminary basis for analysis of radionuclide transport at Pena Blanca, Mexico as an analog of radionuclide transport at Yucca Mountain; and (3) Synthesizing existing information from natural analog studies to provide corroborating evidence for representation of ambient and thermally coupled UZ flow and transport processes in the UZ Model.

  16. Unsaturated zone flow modeling for GWTT-95

    SciTech Connect

    Ho, C.K.; Altman, S.J.; McKenna, S.A.; Arnold, B.W.

    1995-12-31

    In accordance with the Nuclear Regulatory Commission regulation regarding groundwater travel times at geologic repositories, various models of unsaturated flow in fractured tuff have been developed and implemented to assess groundwater travel times at the potential repository at Yucca Mountain, Nevada. Kaplan used one-dimensional models to describe the uncertainty and sensitivity of travel times to various processes at Yucca Mountain. Robey and Arnold et al. used a two-dimensional equivalent continuum model (ECM) with inter- and intra-unit heterogeneity in an attempt to assess fast-flow paths through the unsaturated, fractured tuff at Yucca Mountain (GWTT-94). However, significant flow through the fractures in previous models was not simulated due to the characteristics of the ECM, which requires the matrix to be nearly saturated before flow through the fractures is initiated. In the current study (GWTT-95), four two-dimensional cross-sections at Yucca Mountain are simulated using both the ECM and dual-permeability (DK) models. The properties of both the fracture and matrix domains are geostatistically simulated, yielding completely heterogeneous continua. Then, simulations of flow through the four cross-sections are performed using spatially nonuniform infiltration boundary conditions. Steady-state groundwater travel times from the potential repository to the water table are calculated.

  17. Modeling of radon transport in unsaturated soil

    SciTech Connect

    Chen, C.; Thomas, D.M.; Green, R.

    1995-08-10

    This study applies a recently developed model, LEACHV, to simulate transport of radon through unsaturated soil and compares calculated soil radon activities against field-measured values. For volatile and gas phase transport, LEACHV is modified from LEACHP, a pesticide version of LEACHM, as well-documented one-dimensional model for water and chemical movement through unsaturated soil. LEACHV adds consideration of air temperature changes and air flow driven by barometric pressure change to the other soil variables currently used in LEACHP. It applies diurnal barometric pressure and air temperature changes to reflect more accurately the typical field conditions, Sensitivity analysis and simulated results have clearly demonstrated the relative importance of barometric pressure change, rainfall events, changes in water content, gas advection, and radon source term in radon transport process. Comparisons among simulated results illustrated that the importance of barometric pressure change and its pumping phenomenon produces both fluctuation in soil gas radon activities and an elevation of the long-term average radon activity in shallow soils of an equal magnitude to the disturbed source parameter. Comparisons between measured and simulated soil radon activities showed that LEACHV can provide realistic estimates of radon activity concentration in the soil profile. 41 refs., 10 figs., 2 tabs.

  18. Conversion of Cn-Unsaturated into Cn-2-Saturated LCFA Can Occur Uncoupled from Methanogenesis in Anaerobic Bioreactors.

    PubMed

    Cavaleiro, Ana J; Pereira, Maria Alcina; Guedes, Ana P; Stams, Alfons J M; Alves, M Madalena; Sousa, Diana Z

    2016-03-15

    Fat, oils, and grease present in complex wastewater can be readily converted to methane, but the energy potential of these compounds is not always recyclable, due to incomplete degradation of long chain fatty acids (LCFA) released during lipids hydrolysis. Oleate (C18:1) is generally the dominant LCFA in lipid-containing wastewater, and its conversion in anaerobic bioreactors results in palmitate (C16:0) accumulation. The reason why oleate is continuously converted to palmitate without further degradation via β-oxidation is still unknown. In this work, the influence of methanogenic activity in the initial conversion steps of unsaturated LCFA was studied in 10 bioreactors continuously operated with saturated or unsaturated C16- and C18-LCFA, in the presence or absence of the methanogenic inhibitor bromoethanesulfonate (BrES). Saturated Cn-2-LCFA accumulated both in the presence and absence of BrES during the degradation of unsaturated Cn-LCFA, and represented more than 50% of total LCFA. In the presence of BrES further conversion of saturated intermediates did not proceed, not even when prolonged batch incubation was applied. As the initial steps of unsaturated LCFA degradation proceed uncoupled from methanogenesis, accumulation of saturated LCFA can be expected. Analysis of the active microbial communities suggests a role for facultative anaerobic bacteria in the initial steps of unsaturated LCFA biodegradation. Understanding this role is now imperative to optimize methane production from LCFA. PMID:26810160

  19. Studies on mass attenuation coefficient, effective atomic number and electron density of some amino acids in the energy range 0.122-1.330 MeV

    NASA Astrophysics Data System (ADS)

    Pawar, Pravina P.; Bichile, Govind K.

    2013-11-01

    The total mass attenuation coefficients of some amino acids, such as Glycine (C2H5NO2), DL-Alanine (C3H7NO2), Proline (C5H9NO2), L-Leucine (C6H13NO2 ), L-Arginine (C6H14N4O2) and L-Arginine Monohydrochloride (C6H15ClN4O2), were measured at 122, 356, 511, 662, 1170, 1275 and 1330 keV photon energies using a well-collimated narrow beam good geometry set-up. The gamma rays were detected using NaI (Tl) scintillation detection system with a resolution of 10.2% at 662 keV. The attenuation coefficient data were then used to obtain the effective atomic numbers (Zeff) and effective electron densities (Neff) of amino acids. It was observed that the effective atomic number (Zeff) and effective electron densities (Neff) tend to be almost constant as a function of gamma-ray energy. The results show that, the experimental values of mass attenuation coefficients, effective atomic numbers and effective electron densities are in good agreement with the theoretical values with less than 1% error.

  20. Effects of feeding lauric acid or coconut oil on ruminal protozoa numbers, fermentation pattern, digestion, omasal nutrient flow, and milk production in dairy cows.

    PubMed

    Faciola, A P; Broderick, G A

    2014-01-01

    The objectives of this study were to evaluate the feeding of coconut oil (CO), in which lauric acid (La) comprises about 50% of the fatty acid composition, as a practical rumen protozoa (RP) suppressing agent, to assess whether the source of La affects ruminal fermentation and animal performance and to test whether suppressing RP improves N utilization, nutrient digestion, nutrient flow at the omasal canal, and milk production. Fifteen multiparous Holstein cows (3 fitted with ruminal cannulas) and 15 primiparous Holstein cows (3 fitted with ruminal cannulas) were used in a replicated 3×3 Latin square experiment with 14d of adaptation and 14d of sample collection. Diets were fed as total mixed ration and contained (dry matter basis) 10% corn silage, 50% alfalfa silage, and 40% concentrate. The control diet contained 3% (dry matter basis) calcium soaps of palm oil fatty acids (Megalac, Church & Dwight Co. Inc., Princeton, NJ) as a ruminally inert fat source and had no added La or CO. Diets with La and CO were formulated to contain equal amounts of La (1.3%, dry matter basis). Dry matter intake was not affected by treatment. Both CO and La reduced RP numbers by about 40%. Lauric acid reduced yield of milk and milk components; however, CO did not affect yield of milk and yields of milk components. Both La and CO caused small reductions in total VFA concentration; CO increased molar proportion of ruminal propionate, reduced ruminal ammonia and branched-chain volatile fatty acids, suggesting reduced protein degradation, and reduced milk urea N and blood urea N concentrations, suggesting improved protein efficiency. Lauric acid reduced total-tract apparent digestibility of neutral detergent fiber and acid detergent fiber as well as ruminal apparent digestibility of neutral detergent fiber and acid detergent fiber as measured at the omasal canal; however, CO did not alter fiber digestion. Microbial protein flow at the omasal canal, as well as the flow of N fractions at

  1. Developmental aspects of the rat brain insulin receptor: loss of sialic acid and fluctuation in number characterize fetal development

    SciTech Connect

    Brennan, W.A. Jr.

    1988-06-01

    In this study, I have investigated the structure of the rat brain insulin receptor during fetal development. There is a progressive decrease in the apparent molecular size of the brain alpha-subunit during development: 130K on day 16 of gestation, 126K at birth, and 120K in the adult. Glycosylation was investigated as a possible reason for the observed differences in the alpha-subunit molecular size. The results show that the developmental decrease in the brain alpha-subunit apparent molecular size is due to a parallel decrease in sialic acid content. This was further confirmed by measuring the retention of autophosphorylated insulin receptors on wheat germ agglutinin (WGA)-Sepharose. An inverse correlation between developmental age and retention of /sup 32/P-labeled insulin receptors on the lectin column was observed. Insulin binding increases 6-fold between 16 and 20 days of gestation (61 +/- 25 (+/- SE) fmol/mg protein and 364 +/- 42 fmol/mg, respectively). Thereafter, binding in brain membranes decreases to 150 +/- 20 fmol/mg by 2 days after birth, then reaches the adult level of 63 +/- 15 fmol/mg. In addition, the degree of insulin-stimulated autophosphorylation closely parallels the developmental changes in insulin binding. Between 16 and 20 days of fetal life, insulin-stimulated phosphorylation of the beta-subunit increases 6-fold. Thereafter, the extent of phosphorylation decreases rapidly, reaching adult values identical with those in 16-day-old fetal brain. These results suggest that the embryonic brain possesses competent insulin receptors whose expression changes markedly during fetal development. This information should be important in defining the role of insulin in the developing nervous system.

  2. Ni- and Fe-catalyzed Carboxylation of Unsaturated Hydrocarbons with CO2.

    PubMed

    Juliá-Hernández, Francisco; Gaydou, Morgane; Serrano, Eloisa; van Gemmeren, Manuel; Martin, Ruben

    2016-08-01

    The sustainable utilization of available feedstock materials for preparing valuable compounds holds great promise to revolutionize approaches in organic synthesis. In this regard, the implementation of abundant and inexpensive carbon dioxide (CO2) as a C1 building block has recently attracted considerable attention. Among the different alternatives in CO2 fixation, the preparation of carboxylic acids, relevant motifs in pharmaceuticals and agrochemicals, is particularly appealing, thus providing a rapid and unconventional entry to building blocks that are typically prepared via waste-producing protocols. While significant advances have been realized, the utilization of simple unsaturated hydrocarbons as coupling partners in carboxylation events is undoubtedly of utmost academic and industrial relevance, as two available feedstock materials can be combined in a catalytic fashion. This review article aims to describe the main achievements on the direct carboxylation of unsaturated hydrocarbons with CO2 by using cheap and available Ni or Fe catalytic species. PMID:27573397

  3. Stochastic analysis of bounded unsaturated flow in heterogeneous aquifers: Spectral/perturbation approach

    NASA Astrophysics Data System (ADS)

    Chang, Ching-Min; Yeh, Hund-Der

    2009-01-01

    This paper describes a stochastic analysis of steady state flow in a bounded, partially saturated heterogeneous porous medium subject to distributed infiltration. The presence of boundary conditions leads to non-uniformity in the mean unsaturated flow, which in turn causes non-stationarity in the statistics of velocity fields. Motivated by this, our aim is to investigate the impact of boundary conditions on the behavior of field-scale unsaturated flow. Within the framework of spectral theory based on Fourier-Stieltjes representations for the perturbed quantities, the general expressions for the pressure head variance, variance of log unsaturated hydraulic conductivity and variance of the specific discharge are presented in the wave number domain. Closed-form expressions are developed for the simplified case of statistical isotropy of the log hydraulic conductivity field with a constant soil pore-size distribution parameter. These expressions allow us to investigate the impact of the boundary conditions, namely the vertical infiltration from the soil surface and a prescribed pressure head at a certain depth below the soil surface. It is found that the boundary conditions are critical in predicting uncertainty in bounded unsaturated flow. Our analytical expression for the pressure head variance in a one-dimensional, heterogeneous flow domain, developed using a nonstationary spectral representation approach [Li S-G, McLaughlin D. A nonstationary spectral method for solving stochastic groundwater problems: unconditional analysis. Water Resour Res 1991;27(7):1589-605; Li S-G, McLaughlin D. Using the nonstationary spectral method to analyze flow through heterogeneous trending media. Water Resour Res 1995; 31(3):541-51], is precisely equivalent to the published result of Lu et al. [Lu Z, Zhang D. Analytical solutions to steady state unsaturated flow in layered, randomly heterogeneous soils via Kirchhoff transformation. Adv Water Resour 2004;27:775-84].

  4. Cation Effects on Nitrate Mobility in an Unsaturated Soil

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Transient, unsaturated, horizontal column experiments were carried out with a computer controlled syringe pump for the purpose of assessing counterion (accompanying cation) effects on nitrate (NO3-) mobility in unsaturated soil. A loam soil with calcium dominated cation exchange sites was used in al...

  5. 40 CFR 721.10578 - Unsaturated polyester imide (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Unsaturated polyester imide (generic... Specific Chemical Substances § 721.10578 Unsaturated polyester imide (generic). (a) Chemical substance and... polyester imide (PMN P-10-231) is subject to reporting under this section for the significant new...

  6. 40 CFR 721.10578 - Unsaturated polyester imide (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Unsaturated polyester imide (generic... Specific Chemical Substances § 721.10578 Unsaturated polyester imide (generic). (a) Chemical substance and... polyester imide (PMN P-10-231) is subject to reporting under this section for the significant new...

  7. Unsaturated hydraulic parameters determined from direct and indirect methods

    SciTech Connect

    Flint, Lorraine E.; Hudson, David B.; Flint, Alan L.

    1997-10-22

    Hydraulic parameters are required for numerical simulations of unsaturated flow at Yucca Mountain, a vertically heterogeneous volcanic site for a potential high-level waste repository in the desert southwest. In this paper, direct measurements of the unsaturated hydraulic conductivity using a centrifuge with a specialized rotor are compared to those estimated using a predictive conductivity equation and two methods of measuring moisture retention.

  8. Modeling water infiltration and pesticides transport in unsaturated zone of a sedimentary aquifer

    NASA Astrophysics Data System (ADS)

    Sidoli, Pauline; Angulo-Jaramillo, Rafael; Baran, Nicole; Lassabatère, Laurent

    2015-04-01

    Groundwater quality monitoring has become an important environmental, economic and community issue since increasing needs drinking water at the same time with high anthropic pressure on aquifers. Leaching of various contaminants as pesticide into the groundwater is closely bound to water infiltration in the unsaturated zone which whom solute transport can occur. Knowledge's about mechanisms involved in the transfer of pesticides in the deep unsaturated zone are lacking today. This study aims to evaluate and to model leaching of pesticides and metabolites in the unsaturated zone, very heterogeneous, of a fluvio-glacial aquifer, in the South-East of France, where contamination of groundwater resources by pesticides is frequently observed as a consequence of intensive agricultural activities. Water flow and pesticide transport were evaluated from column tests under unsaturated conditions and from adsorption batch experiments onto the predominant lithofacies collected, composed of a mixture of sand and gravel. A maize herbicide, S-metolachlor, applied on the study site and worldwide and its two major degradation products (metolachlor ethanesulfonic acid and metolachlor oxanilic acid) were studied here. A conservative tracer, bromide ion, was used to determine water dispersive parameters of porous media. Elution curves were obtained from pesticide concentrations analyzed by an ultra-performance liquid chromatography system interfaced to a triple quadrupole mass spectrometer and from bromide concentrations measured by ionic chromatography system. Experimental data were implemented into Hydrus to model flow and solute transfer through a 1D profile in the vadose zone. Nonequilibrium solute transport model based on dual-porosity model with mobile and immobile water is fitting correctly elution curves. Water dispersive parameters show flow pattern realized in the mobile phase. Exchanges between mobile and immobile water are very limited. Because of low adsorptions onto

  9. Modeling capillary barriers in unsaturated fractured rock

    NASA Astrophysics Data System (ADS)

    Wu, Yu-Shu; Zhang, W.; Pan, Lehua; Hinds, Jennifer; Bodvarsson, G. S.

    2002-11-01

    This work presents a series of numerical modeling studies that investigate the hydrogeologic conditions required to form capillary barriers and the effect that capillary barriers have on fluid flow and tracer transport processes in the unsaturated fractured rock of Yucca Mountain, Nevada, a potential site for storing high-level radioactive waste. The modeling approach is based on a dual-continuum formulation of coupled multiphase fluid and tracer transport through fractured porous rock. The numerical modeling results showed that effective capillary barriers can develop where both matrix and fracture capillary gradients tend to move water upward. Under the current hydrogeologic conceptualization of Yucca Mountain, strong capillary barrier effects exist for diverting a significant amount of moisture flow through the relatively shallow Paintbrush nonwelded unit, with major faults observed at the site serving as major downward pathways for laterally diverted percolation fluxes. In addition, we used observed field liquid saturation and goechemical isotopic data to check model results and found consistent agreement.

  10. Infiltration Flow Path Distributions in Unsaturated Rocks

    NASA Astrophysics Data System (ADS)

    Tokunaga, T. K.; Olson, K. R.; Wan, J.

    2004-12-01

    Spatial distributions of infiltration flow paths through rock formations are complex networks that determine flow velocities, control rates of natural geochemical reactions in the subsurface, as well as rates of contaminant transport to underlying groundwater. Despite these important consequences, distributions of infiltration paths and locally fast seepage rates through rocks are not well understood. Laboratory-based studies on fractured rocks cannot easily be conducted on systems large enough to include sufficient fracture network complexity, so that inferences of field-scale flux distributions cannot be reliably made. Field-based studies to date have permitted quantification of only a small fraction of the flow distribution, typically while imposing extremely high fluxes, and therefore have not allowed comprehensive delineation of flow distributions expected under natural recharge. Based on hydraulic scaling considerations, we hypothesize that unsaturated flow path distributions in rock deposits will be similar to those occurring in fractured rock formations under low overall infiltration rates. Talus rock deposits and mine waste rock piles control flow and transport into their respective underlying groundwaters. All of these reasons motivated infiltration experiments in rock packs. Experiments have been conducted on 4 different rock types and system scales ranging from 1 to 46 rock layers. Our experiments showed that infiltration through rocks conforms to no previously reported behavior in soils, and that flow paths do not progressively converge into fewer and fewer flow paths. Instead, a fundamentally different hydraulic structure develops, having an exponential (geometric) flux distribution, with the characteristic scale determined by the characteristic rock size. Although the phenomena are very different, the evolution of flow path distributions and local seepage rate distributions is predictable based on a statistical mechanical model for energy

  11. Effective atomic number of some sugars and amino acids for scattering of (241)Am and (137)Cs gamma rays at low momentum transfer.

    PubMed

    Vinaykumar, L; Umesh, T K

    2015-09-01

    In this paper, we report the effective atomic number of some H, C, N and O based sugars and amino acids. These have been determined by using a handy expression which is based on the theoretical angle integrated small angle (coherent+incoherent) scattering cross sections of seven elements of Z≤13 in four angular ranges of (0-4°), (0-6°), (0-8°) and (0-10°)for (241)Am (59.54 keV) and (137)Cs (661.6 keV) gamma rays. The theoretical scattering cross sections were computed by a suitable numerical integration of the atomic form factor and incoherent scattering function compilations of Hubbell et al. (1975) which make use of the non-relativistic Hartree-Fock (NRHF) model for the atomic charge distribution of the elements in the angular ranges of interest. The angle integrated small angle scattering cross sections of the H, C, N and O based sugars and amino acids measured by a new method reported recently by the authors were used in the handy expression to derive their effective atomic number. The results are compared with the other available data and discussed. Possible conclusions are drawn based on the present study. PMID:26073268

  12. Acrolein with an alpha, beta-unsaturated Carbonyl Group Inhibits LPS-induced Homodimerization of Toll-like Receptor 4

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Acrolein is a highly electrophilic a,ß-unsaturated aldehyde present in a number of environmental sources, especially cigarette smoke. It reacts strongly with the thiol groups of cysteine residues by Michael addition and has been reported to inhibit nuclear factor-kB (NF-kB) activation by lipopolysac...

  13. Alpha-Lipoic Acid Reduces LDL-Particle Number and PCSK9 Concentrations in High-Fat Fed Obese Zucker Rats

    PubMed Central

    Carrier, Bradley; Wen, Shin; Zigouras, Sophia; Browne, Richard W.; Li, Zhuyun; Patel, Mulchand S.; Williamson, David L.; Rideout, Todd C.

    2014-01-01

    We characterized the hypolipidemic effects of alpha-lipoic acid (LA, R-form) and examined the associated molecular mechanisms in a high fat fed Zucker rat model. Rats (n = 8) were assigned to a high fat (HF) diet or the HF diet with 0.25% LA (HF-LA) for 30 days and pair fed to remove confounding effects associated with the anorectic properties of LA. Compared with the HF controls, the HF-LA group was protected against diet-induced obesity (102.5±3.1 vs. 121.5±3.6,% change BW) and hypercholesterolemia with a reduction in total-C (−21%), non-HDL-C (−25%), LDL-C (−16%), and total LDL particle number (−46%) and an increase in total HDL particles (∼22%). This cholesterol-lowering response was associated with a reduction in plasma PCSK9 concentration (−70%) and an increase in hepatic LDLr receptor protein abundance (2 fold of HF). Compared with the HF-fed animals, livers of LA-supplemented animals were protected against TG accumulation (−46%), likely through multiple mechanisms including: a suppressed lipogenic response (down-regulation of hepatic acetyl-CoA carboxylase and fatty acid synthase expression); enhanced hepatic fat oxidation (increased carnitine palmitoyltransferase Iα expression); and enhanced VLDL export (increased hepatic diacylglycerol acyltransferase and microsomal triglyceride transfer protein expression and elevated plasma VLDL particle number). Study results also support an enhanced fatty acid uptake (2.8 fold increase in total lipase activity) and oxidation (increased CPT1β protein abundance) in muscle tissue in LA-supplemented animals compared with the HF group. In summary, in the absence of a change in caloric intake, LA was effective in protecting against hypercholesterolemia and hepatic fat accumulation under conditions of strong genetic and dietary predisposition toward obesity and dyslipidemia. PMID:24595397

  14. The Fatty Acid Profile Analysis of Cyperus laxus Used for Phytoremediation of Soils from Aged Oil Spill-Impacted Sites Revealed That This Is a C18:3 Plant Species.

    PubMed

    Rivera Casado, Noemí Araceli; Montes Horcasitas, María del Carmen; Rodríguez Vázquez, Refugio; Esparza García, Fernando José; Pérez Vargas, Josefina; Ariza Castolo, Armando; Ferrera-Cerrato, Ronald; Gómez Guzmán, Octavio; Calva Calva, Graciano

    2015-01-01

    The effect of recalcitrant hydrocarbons on the fatty acid profile from leaf, basal corm, and roots of Cyperus laxus plants cultivated in greenhouse phytoremediation systems of soils from aged oil spill-impacted sites containing from 16 to 340 g/Kg total hydrocarbons (THC) was assessed to investigate if this is a C18:3 species and if the hydrocarbon removal during the phytoremediation process has a relationship with the fatty acid profile of this plant. The fatty acid profile was specific to each vegetative organ and was strongly affected by the hydrocarbons level in the impacted sites. Leaf extracts of plants from uncontaminated soil produced palmitic acid (C16), octadecanoic acid (C18:0), unsaturated oleic acids (C18:1-C18:3), and unsaturated eichosanoic (C20:2-C20:3) acids with a noticeable absence of the unsaturated hexadecatrienoic acid (C16:3); this finding demonstrates, for the first time, that C. laxus is a C18:3 plant. In plants from the phytoremediation systems, the total fatty acid contents in the leaf and the corm were negatively affected by the hydrocarbons presence; however, the effect was positive in root. Interestingly, under contaminated conditions, unusual fatty acids such as odd numbered carbons (C15, C17, C21, and C23) and uncommon unsaturated chains (C20:3n6 and C20:4) were produced together with a remarkable quantity of C22:2 and C24:0 chains in the corm and the leaf. These results demonstrate that weathered hydrocarbons may drastically affect the lipidic composition of C. laxus at the fatty acid level, suggesting that this species adjusts the cover lipid composition in its vegetative organs, mainly in roots, in response to the weathered hydrocarbon presence and uptake during the phytoremediation process. PMID:26473488

  15. The Fatty Acid Profile Analysis of Cyperus laxus Used for Phytoremediation of Soils from Aged Oil Spill-Impacted Sites Revealed That This Is a C18:3 Plant Species

    PubMed Central

    Montes Horcasitas, María del Carmen; Rodríguez Vázquez, Refugio; Esparza García, Fernando José; Pérez Vargas, Josefina; Ariza Castolo, Armando; Ferrera-Cerrato, Ronald; Gómez Guzmán, Octavio

    2015-01-01

    The effect of recalcitrant hydrocarbons on the fatty acid profile from leaf, basal corm, and roots of Cyperus laxus plants cultivated in greenhouse phytoremediation systems of soils from aged oil spill-impacted sites containing from 16 to 340 g/Kg total hydrocarbons (THC) was assessed to investigate if this is a C18:3 species and if the hydrocarbon removal during the phytoremediation process has a relationship with the fatty acid profile of this plant. The fatty acid profile was specific to each vegetative organ and was strongly affected by the hydrocarbons level in the impacted sites. Leaf extracts of plants from uncontaminated soil produced palmitic acid (C16), octadecanoic acid (C18:0), unsaturated oleic acids (C18:1-C18:3), and unsaturated eichosanoic (C20:2-C20:3) acids with a noticeable absence of the unsaturated hexadecatrienoic acid (C16:3); this finding demonstrates, for the first time, that C. laxus is a C18:3 plant. In plants from the phytoremediation systems, the total fatty acid contents in the leaf and the corm were negatively affected by the hydrocarbons presence; however, the effect was positive in root. Interestingly, under contaminated conditions, unusual fatty acids such as odd numbered carbons (C15, C17, C21, and C23) and uncommon unsaturated chains (C20:3n6 and C20:4) were produced together with a remarkable quantity of C22:2 and C24:0 chains in the corm and the leaf. These results demonstrate that weathered hydrocarbons may drastically affect the lipidic composition of C. laxus at the fatty acid level, suggesting that this species adjusts the cover lipid composition in its vegetative organs, mainly in roots, in response to the weathered hydrocarbon presence and uptake during the phytoremediation process. PMID:26473488

  16. Fed-batch production of unsaturated medium-chain-length polyhydroxyalkanoates with controlled composition by Pseudomonas putida KT2440.

    PubMed

    Sun, Zhiyong; Ramsay, Juliana A; Guay, Martin; Ramsay, Bruce A

    2009-03-01

    Unsaturated medium-chain-length polyhydroxyalkanoates (MCL-PHA) were produced at a productivity of 0.63-1.09 g PHA l(-1) h(-1) with final PHA content ranging from 42.6 to 55.8% in single-stage, carbon-limited, fed-batch fermentations of Pseudomonas putida KT2440. A mixture of nonanoic acid (NA) and 10-undecenoic acid (UDA=) was fed exponentially to control growth rate. Varying the specific growth rate (0.14 h(-1) vs. 0.23 h(-1)) at similar substrate feed ratios (NA:UDA= = 5:1) had little effect on the final PHA content and relative composition. However, decreasing the NA:UDA= ratio decreased the final amount of PHA produced from 56% with NA:UDA= = 5.07:1 to only 42% at NA:UDA= = 2.47:1. The molar fraction of all 3-hydroxyalkanoate monomers in the PHA product was relatively constant throughout each fermentation, indicating that the final product was homogeneous rather than a mixture of different copolymers. A linear relationship between unsaturation of the PHA produced and unsaturation of the carbon feed was found, which demonstrates the feasibility of producing unsaturated MCL-PHAs with controlled polymeric composition in a fed-batch process. PMID:19050862

  17. Delivery of Polyunsaturated Fatty Acids from a Glycerol Polyester Matrix with Anti-oxidant Properties

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Awareness of the health benefits associated with the polyunsaturated acids such as alpha linolenic (ALA), eicosapentaenoic acid (EPA), and docosahexaenoic acid (DHA), has generated interest in formulating foods and dietary supplements with these compounds. However, the highly unsaturated structure o...

  18. Polymeric membrane and process for separation of aliphatically unsaturated hydrocarbons

    SciTech Connect

    Ho, W.S.W.

    1991-11-05

    This patent describes a process for separating at least one unsaturated hydrocarbon from a hydrocarbon feed steam containing the unsaturated hydrocarbon. It comprises contacting the feed stream against a first side of a solid, homogeneous membrane comprising a hydrophilic polymer selected from the group consisting of a polyvinylalcohol, polyvinylacetate, sulfonyl-containing polymers, polyvinylpyrrolidone, polyethylene oxide, polyacrylamide, copolymers thereof, and blends thereof a transition metal or transition metal ion capable of reversibly complexing with the unsaturated hydrocarbon, and a hydrophilic salt of a Group I metal; and withdrawing at a second side of the membrane a permeate comprising the unsaturated hydrocarbon in higher concentration than in the feed stream. This patent also describes a solid, homogeneous membrane for separating at least one unsaturated hydrocarbon from a hydrocarbon stream containing the unsaturated hydrocarbon. It comprises a hydrophilic polymer selected from the group consisting of polyvinylalcohol, polyvinylacetate, sulfonyl-containing polymers, polyvinylpyrrolidone, polyethylene oxide, polyacrylamide, copolymers thereof, and blends thereof, a transition metal or transition metal ion capable of reversibly complexing with the unsaturated hydrocarbon, and a hydrophilic salt of a Group I metal.

  19. Separation and isolation of saturated and unsaturated 5-n-alk(en)ylresorcinols from rye bran.

    PubMed

    Patzke, Hannes; Schulze-Kaysers, Nadine; Schieber, Andreas

    2016-03-18

    Alkylresorcinols (AR) are a class of phenolic lipids which are found in a number of plants and microorganisms and which are associated with various biological activities. In view of the very limited availability of reference compounds, we developed a process for the isolation of AR from rye bran. For this purpose, a crude extract was subjected to deep bed filtration at -80 °C, whereby the crystallized saturated AR were separated from the unsaturated homologues. Highly purified, individual compounds were subsequently isolated by semi-preparative HPLC. In contrast to previously published approaches, the method reported here is relatively easy to perform and allows the recovery of saturated and unsaturated AR of high purity. Furthermore, it is superior to argentation chromatography because it does not necessitate the removal of silver ions for subsequent bioassays. PMID:26895830

  20. Relationship between deoxyribonucleic acid content and nucleoli in human heart muscle cells and estimation of cell number during cardiac growth and hyperfunction.

    PubMed

    Adler, C P

    1975-01-01

    In the myocardium of 30 human hearts of all age groups quantitative deoxyribonucleic acid (DNA) measurements were performed and the results of the measurements were correlated with the pure myocardium weight. By means of the diphenylamine reaction the total amount of DNA (DNA concentration and DNA amount) in the myocardium was estimated. By means of Feulgen cytophotometry the DNA amount exclusively in the heart muscle cell nuclei was measured. With the use of myocardial tissue spread on slides, the nuclear areas of the heart muscle nuclei were planimetrically measured. After preparation with DNase and staining with gallocyanine chromalumn the nucleoli in heart muscle nuclei were specifically presented and their number per nucleus as well as their area values were demonstrated. From the biochemical and cytophotometric results of the myocardial DNA content it was possible to estimate the absolute cell number of the hearts, keeping the pure myocardium weight in consideration. The investigations led to the following results. In growing childrens' hearts the DNA concentration decreases to a constant level of 0.3-0.4 mg/g. The amount of DNA rises with increasing heart weight. During the growth of the heart of a child between the ages of 8 and 12 the DNA amount doubles in the heart muscle nuclei, and most of the muscle nuclei of an adult have a tetraploid DNA content. In pathological heart hypertrophy a further polyploidization of the heart muscle nuclei occurs. The areas of the nuclei increases with growing polyploidization. The nuclear areas form the same grouping as the ploidy classes. With growing nuclear areas, the total areas of the nucleoli and their number per nucleus also increase. Right after birth an increase in the number of connective tissue and heart muscle cells follows. A normal heart contains about 2 x 10(9) muscle cells. In hypertrophic hearts the number of muscle cells can double. PMID:129834

  1. Analysis of evaporation in nuclear waste boreholes in unsaturated tuff

    SciTech Connect

    Zhou, W.; Chambre, P.L.; Pigford, T.H.; Lee, W.W.L.

    1993-12-31

    We present an analysis of evaporation in a nuclear waste borehole in unsaturated tuff. In unsaturated tuff, water in contact with a waste container will evaporate due to the difference in vapor pressure between water in a flat film and water held in rock pores with curved interfaces. Decay heat will also enhance evaporation. It is important to study evaporation in a potential geologic repository of nuclear waste in unsaturated rock because the corrosion of waste containers is increased with liquid water. For radionuclides other than gaseous ones, their release from waste solids requires liquid water.

  2. Enzymatic Synthesis of l-Ascorbyl Fatty Acid Esters Under Ultrasonic Irradiation and Comparison of Their Antioxidant Activity and Stability.

    PubMed

    Jiang, Chen; Lu, Yuyun; Li, Zhuo; Li, Cunzhi; Yan, Rian

    2016-06-01

    A series of novel l-ascorbyl fatty acid esters were synthesized by catalization of Novozym(®) 435 under ultrasonic irradiation and characterized by infrared spectroscopy, electrospray ionization mass spectra, and nuclear magnetic resonance. Their properties especially antioxidant activity and stability were investigated. The results showed that the reducing power, the scavenging activity of hydroxyl radical and 2,2-diphenyl-1-picrylhydrazyl radical were decreased with the increase of the number of carbon atoms in fatty acid. The hydroxyl radical scavenging activity and reducing power of l-ascorbyl saturated fatty acid esters were better than that of tert-butylhydroquinone. The induction period in lipid oxidation of l-ascorbyl saturated fatty acid esters and tert-butylhydroquinone were longer than that of l-ascorbyl unsaturated fatty acid esters and l-ascorbic acid both in soybean oil and lard. Besides, the l-ascorbyl fatty acid esters showed different stabilities in different conditions by comparing with l-ascorbic acid, and the l-ascorbyl saturated fatty acid esters were more stable than l-ascorbyl unsaturated fatty acid esters in ethanol solution. PMID:27100741

  3. Mechanistic Insights on the Hydrogenation of α,β-Unsaturated Ketones and Aldehydes to Unsaturated Alcohols over Metal Catalysts

    SciTech Connect

    Ide, Matthew S.; Hao, Bing; Neurock, Matthew; Davis, Robert J.

    2012-04-06

    The selective hydrogenation of unsaturated ketones (methyl vinyl ketone and benzalacetone) and unsaturated aldehydes (crotonaldehyde and cinnamaldehyde) was carried out with H₂ at 2 bar absolute over Pd/C, Pt/C, Ru/C, Au/C, Au/TiO₂, or Au/Fe₂O₃ catalysts in ethanol or water solvent at 333 K. Comparison of the turnover frequencies revealed Pd/C to be the most active hydrogenation catalyst, but the catalyst failed to produce unsaturated alcohols, indicating hydrogenation of the C=C bond was highly preferred over the C=O bond on Pd. The Pt and Ru catalysts were able to produce unsaturated alcohols from unsaturated aldehydes, but not from unsaturated ketones. Although Au/ Fe₂O₃ was able to partially hydrogenate unsaturated ketones to unsaturated alcohols, the overall hydrogenation rate over gold was the lowest of all of the metals examined. First-principles density functional theory calculations were therefore used to explore the reactivity trends of methyl vinyl ketone (MVK) and benzalacetone (BA) hydrogenation over model Pt(111) and Ru(0001) surfaces. The observed selectivity over these metals is likely controlled by the significantly higher activation barriers to hydrogenate the C=O bond compared with those required to hydrogenate the C=C bond. Both the unsaturated alcohol and the saturated ketone, which are the primary reaction products, are strongly bound to Ru and can react further to the saturated alcohol. The lower calculated barriers for the hydrogenation steps over Pt compared with Ru account for the higher observed turnover frequencies for the hydrogenation of MVK and BA over Pt. The presence of a phenyl substituent α to the C=C bond in BA increased the barrier for C=C hydrogenation over those associated with the C=C bond in MVK; however, the increase in barriers with phenyl substitution was not adequate to reverse the selectivity trend.

  4. Numerical modeling of isothermal and nonisothermal flow in unsaturated fractured rock: A review

    NASA Astrophysics Data System (ADS)

    Pruess, K.; Wang, J. S. Y.

    In recent years, considerable efforts have been made to study the feasibility of geologic disposal of high-level nuclear wastes in deep unsaturated zones in desert environments. The tuff formations at and near the Nevada Test Site, which are under consideration for this purpose, are comprised of fractured-porous material, with hydrologic properties quite different from those encountered in most previous unsaturated flow studies dealing with soils. Another difference from "conventional" unsaturated flow is that in the vicinity of the waste packages, flow is driven by high temperatures (exceeding 100°C) and large temperature gradients. The approximations developed in soil science for weakly nonisothermal flow are not applicable to this situation, and a multiphase description of flow is required, similar to approaches used in modeling of geothermal reservoirs and thermally enhanced oil recovery. The conventional approach to unsaturated flow is applicable, however, to a variety of problems relating to natural (undisturbed) and far-field flow conditions. This paper reviews recent work on numerical modeling of unsaturated flow undertaken in the context of nuclear waste isolation studies. Concepts and applications of broader interest are summarized, including the role of fractures in partially saturated flow, the response of a fractured medium to infiltration events, and a simplified description of flow based on an effective continuum approximation. It is pointed out that the heat released from the waste packages gives rise to multi-phase flow with heat pipe effects, which may have a dramatic impact on thermal and hydrologic conditions. A number of important issues are identified which have not been adequately explored. These include the possibility that liquid water may flow along the rough walls of fractures, the bulk of which is drained. Pre-existing or induced fracture coatings may have significant hydrologic effects. Large-scale moisture movement may be important to

  5. Effect of Body Force on Consolidation in Unsaturated Soils

    NASA Astrophysics Data System (ADS)

    Chao, N. C.; Lo, W. C.; Lee, J. W.

    2015-12-01

    Soil consolidation is a transient process by which soil volume is decreased due to the coupling between deformation of a porous medium and interstitial fluid flows. The influence of body force has been conventionally ignored in the consolidation theory of poroelasticity for either saturated or unsaturated soils. In the current study, gravity effect is well taken into account in the coupled diffusion equations derived by Lo et al. (2014) for describing one-dimensional consolidation in unsaturated soils, thus leading to additional first-order time-derivative terms. Finite-difference approach is used to solve those equations. Numerical calculations are then conducted with respect to various initial water saturations and soil heights for unsaturated clays as illustrative examples. The result is compared to that typically obtained with neglecting body forces to quantify the impact of gravity on consolidation in unsaturated soils.

  6. Synthesis and study of novel silicon-based unsaturated polymers

    SciTech Connect

    Lin, J.

    1995-06-19

    Novel unsaturated polymers have been synthesized and studied as precursors to silicon carbide and third order nonlinear optical materials. X ray structures were obtained. Kinetic and mechanistic studies of the unique thermal isomerization of dimethylenedisilacyclobutane to a carbene were conducted.

  7. Polymeric membrane and process for separating aliphatically unsaturated hydrocarbons

    SciTech Connect

    Ho, W.S.W.

    1991-05-14

    This patent describes a process for separating at least one unsaturated hydrocarbon from a hydrocarbon feed stream containing. It comprises: contacting the feed stream against a first side of a solid, homogeneous membrane consisting essentially of a hydrophilic polymer selected from the group consisting of polyvinylalcohol, polyvinylacetate, sulfonyl containing polymers, polyvinylpyrrolidone, polyethylene oxide, polyacrylamide, copolymers thereof, and blends thereof, and a metal or metal ion capable of reversibly complexing with the unsaturated hydrocarbon, the metal or metal ion is distributed homogeneously in the hydrophilic polymer; and withdrawing at a second side of the membrane a permeate comprising the unsaturated hydrocarbon in higher concentration than in the feed stream; whereby the membrane provides high permeability and selectivity for unsaturated hydrocarbons and substantially increases the rate at which the permeate is withdrawn.

  8. IDENTIFICATION AND COMPILATION OF UNSATURATED/VADOSE ZONE MODELS

    EPA Science Inventory

    The present report contains the result of research and information processing activities supporting evaluation of the capabilities of various unsaturated zone flow and transport models in predicting the movement of hazardous chemicals through soils to ground water. t provides an ...

  9. Characterization of unsaturated hydraulic conductivity at the Hanford Site

    SciTech Connect

    Rockhold, M.L.; Fayler, M.J.; Gee, G.W.

    1988-07-01

    This report details some recent field measurements and compares predicted and measured values of hydraulic conductivities for three locations at the Hanford Site. Measurements from small (6-cm-dia) /open quotes/point/close quotes/ and large (2-m by 2-m) /open quotes/plot/close quotes/ areas utilized inflitration and drainage techniques to obtain in situ data for field-saturated and unsaturated hydraulic conductivity. The Guelph permeameter was used for point sampling, and the unsteady drainage-flux method was used on plots for field-saturated and unsaturated hydraulic conductivity measurements. Steady-state techniques were used to measure unsaturated hydraulic conductivities in small columns in the laboratory for one of the three soils tested to provide a comparison with data obtained from the field. Measured unsaturated hydraulic conductivities and those predicted from particle-size distribution and bulk density data agree within one-half to one and one-half orders of magnitude, depending on soil type. To use a particle-size distribution to estimate water retention characteristics and, subsequently, to predict unsaturated hydraulic conductivities, measurements of water-retention characteristics are necessary to determine a parameter value used in one of the models. No single method for measuring or calculating unsaturated hydraulic conductivities was found appropriate for all Hanford Site soils. Ideally, several methods should be used to take advantage of the strengths of each method, considering the data needs and resources available. 45 refs., 24 figs., 19 tabs.

  10. An air-water interfacial area based variable tortuosity model for unsaturated sands

    SciTech Connect

    Khaleel, Raziuddin; Saripalli, Prasad

    2006-05-01

    Based on Kozeny-Carman equation for saturated media permeability, a new model is developed for the prediction of unsaturated hydraulic conductivity, K as a function of moisture content, ?. The K(???) estimates are obtained using laboratory measurements of moisture retention and saturated hydraulic conductivity, and a saturation-dependent tortuosity based on the immiscible fluid (air-water) interfacial area. Tortuosity (?a) for unsaturated media is defined as aaw/aaw,o (ratio of the specific air-water interfacial area of a real and the corresponding idealized porous medium). A correspondence between the real and idealized media is established by using the laboratory-measured soil moisture retention curve to calculate the interfacial area. The general trend in prediction of ?a as a function water saturation is in agreement with similar recent predictions based on diffusion theory. Unsaturated hydraulic conductivities measured for a number of coarse-textured, repacked Hanford sediments agree well with predictions based on the modified Kozeny-Carman relation. Because of the use of saturated hydraulic conductivity, a slight bias is apparent in measured and predicted K at low ?. While the modified Kozeny-Carman relation was found to be reasonably accurate in predicting K(??) for the repacked, sandy soils considered in this study, a further testing of the new model for undisturbed sediments and other soil textures would be useful.

  11. Radiosensitivity of Human Fibroblasts is Associated With Amino Acid Substitution Variants in Susceptible Genes And Correlates With The Number of Risk Alleles

    SciTech Connect

    Alsbeih, Ghazi . E-mail: galsbeih@kfshrc.edu.sa; El-Sebaie, Medhat; Al-Harbi, Najla; Al-Buhairi, Muneera; Al-Hadyan, Khaled; Al-Rajhi, Nasser

    2007-05-01

    Purpose: Genetic predictive markers of radiosensitivity are being sought for stratifying radiotherapy for cancer patients and risk assessment of radiation exposure. We hypothesized that single nucleotide polymorphisms in susceptible genes are associated with, and the number of risk alleles has incremental effect on, individual radiosensitivity. Methods and Materials: Six amino acid substitution variants (ATM 1853 Asp/Asn G>A, p53 72 Arg/Pro G>C, p21 31 Ser/Arg C>A, XRCC1 399 Arg/Gln G>A, XRCC3 241 Thr/Met C>T, and TGF{beta}1 10 Leu/Pro T>C) were genotyped by direct sequencing in 54 fibroblast strains of different radiosensitivity. Results: The clonogenic survival fraction at 2 Gy range was 0.15-0.50 (mean, 0.34, standard deviation, 0.08). The mean survival fraction at 2 Gy divided the cell strains into radiosensitive (26 cases) and normal (28 controls). A significant association was observed between the survival fraction at 2 Gy and ATM 1853 Asn, XRCC3 241 Met, and TGF{beta}1 10 Leu alleles (p = 0.05, p = 0.02, and p = 0.02, respectively). The p53 72 Arg allele showed a borderline association (p = 0.07). The number of risk alleles increased with increasing radiosensitivity, and the group comparison showed a statistically significant difference between the radiosensitive and control groups (p {<=}0.001). Conclusion: The results of our study have shown that single nucleotide polymorphisms in susceptible genes influence cellular radiation response and that the number of risk alleles has a combined effect on radiosensitivity. Individuals with multiple risk alleles could be more susceptible to radiation effects than those with fewer risk alleles. These results may have implications in predicting normal tissue reactions to radiotherapy and risk assessment of radiation exposure.

  12. Assessment of groundwater quality by unsaturated zone study due to migration of leachate from Abloradjei waste disposal site, Ghana

    NASA Astrophysics Data System (ADS)

    Egbi, Courage Davidson; Akiti, Tetteh Thomas; Osae, Shiloh; Dampare, Samuel Boakye; Abass, Gibrilla; Adomako, Dickson

    2015-06-01

    Leachate generated by open solid waste disposal sites contains substances likely to contaminate groundwater. The impact of potential contaminants migrating from leachate on groundwater can be quantified by monitoring their concentration and soil properties at specific points in the unsaturated zone. In this study, physical and chemical analyses were carried out on leachate, soil and water samples within the vicinity of the municipal solid waste disposal site at Abloradjei, a suburb of Accra, Ghana. The area has seen a massive increase in population and the residents depend on groundwater as the main source of water supply. Results obtained indicate alkaline pH for leachate and acidic conditions for unsaturated zone water. High EC values were recorded for leachate and unsaturated zone water. Major ions (Ca2+, Na+, Mg2+, K+, NO3 -, SO4 2-, Cl-, PO4 3- were analysed in leachate, unsaturated zone water, soil solution and groundwater while trace metals (Al, Fe, Cu, Zn, Pb) were analysed in both soil and extracted soil solution. Concentrations of major ions were high in all samples indicating possible anthropogenic origin. Mean % gravel, % sand, % clay, bulk density, volumetric water content and porosity were 28.8, 63.93, 6.6, 1 g cm-3, 35 and 62.7 %, respectively. Distribution of trace elements showed Kd variation of Al > Cu > Fe > Pb > Zn in the order of sequential increasing solubility. It was observed that the quality of groundwater is not suitable for drinking.

  13. Unsaturated zone 14CO2: implications for groundwater dating

    NASA Astrophysics Data System (ADS)

    Wood, C.; Cook, P. G.; Harrington, G. A.; Meredith, K.; Kipfer, R.

    2013-12-01

    Quantitative interpretation of the carbon-14 activity (14C) of dissolved inorganic carbon (DIC) in groundwater requires an understanding of the various chemical and physical processes that can vary the initial 14C activity from that of the original atmospheric source (carbon dioxide, CO2). Such processes include radioactive decay, carbonate mineral dissolution, isotope exchange, decay of organic matter and molecular diffusion. Many geochemical correction models exist to account for some of these processes (e.g., Fontes and Garnier, 1979). However in most existing correction schemes, it is assumed that the 14C activity of CO2 in the unsaturated zone is in equilibrium with the atmosphere (i.e., 14C:12C is the same as the atmospheric ratio). This assumption is rarely tested and in several cases has been found to be inappropriate (eg. Bacon and Keller, 1998; Walvoord et al., 2005). Not accounting for the influence of unsaturated zone processes on 14C may lead to problems in determining residence time and estimating fluxes from measured 14C data in groundwater. In this study we examined carbon isotope processes in deep unsaturated zone profiles (up to 30m in depth) in arid central Australia. At five sites, multi-level samples of unsaturated zone gas and groundwater were collected for 14C analysis. Chlorofluorocarbon (CFC-11 and CFC-12) samples were also collected in unsaturated zone gas. At all sites we observed a decrease in the 14C activity of unsaturated zone gas with depth, from approximately 107 pmC near the ground surface to 50 - 80 pmC immediately above the water table. The measured 14C data was reproduced in a one-dimensional model using Hydrus, with CFC concentrations used to help constrain the gas transport parameters. Modelling showed that the decrease in 14C could be explained by CO2 production from different sources at different depths in the unsaturated zone (e.g. plant root respiration at shallower depths, oxidation of dead organic matter at greater

  14. Unsaturated Zone Flow Patterns and Analysis

    SciTech Connect

    C. Ahlers

    2001-10-17

    This Analysis/Model Report (AMR) documents the development of an expected-case model for unsaturated zone (UZ) flow and transport that will be described in terms of the representativeness of models of the natural system. The expected-case model will provide an evaluation of the effectiveness of the natural barriers, assess the impact of conservatism in the Total System Performance Assessment (TSPA), and support the development of further models and analyses for public confidence building. The present models used in ''Total System Performance Assessment for the Site Recommendation'' (Civilian Radioactive Waste Management System Management and Operating Contractor (CRWMS M&O) 2000 [1532461]) underestimate the natural-barrier performance because of conservative assumptions and parameters and do not adequately address uncertainty and alternative models. The development of an expected case model for the UZ natural barrier addresses issues regarding flow-pattern analysis and modeling that had previously been treated conservatively. This is in line with the Repository Safety Strategy (RSS) philosophy of treating conservatively those aspects of the UZ flow and transport system that are not important for achieving regulatory dose (CRWMS M&O 2000 [153246], Section 1.1.1). The development of an expected case model for the UZ also provides defense-in-depth in areas requiring further analysis of uncertainty and alternative models. In general, the value of the conservative case is to provide a more easily defensible TSPA for behavior of UZ flow and transport processes at Yucca Mountain. This AMR has been prepared in accordance with the ''Technical Work Plan for Unsaturated Zone (UZ) Flow and Transport Process Model Report'' (Bechtel SAIC Company (BSC) 2001 [155051], Section 1.3 - Work Package 4301213UMG). The work scope is to examine the data and current models of flow and transport in the Yucca Mountain UZ to identify models and analyses where conservatism may be reduced and

  15. Effect of unsaturation on the chain order of phosphatidylcholines in a dioleoylphosphatidylethanolamine matrix.

    PubMed Central

    Separovic, F; Gawrisch, K

    1996-01-01

    The properties of phosphatidylcholines (PCs) having a perdeuterated stearic acid, 18:0d35, in the sn-1 position and the fatty acid 18:0, 18:1 omega 9, 18:2 omega 6, 18:3 omega 3, 20:4 omega 6, 20:5 omega 3, or 22:6 omega 3 at the sn-2 position were investigated in a matrix of dioleoylphosphatidylethanolamine (DOPE) by 2H and 31P NMR spectroscopy. At a mole ratio of DOPE/PC = 5:1, the lipids form liquid crystalline lamellar phases below 40 degrees C and coexisting lamellar, inverse hexagonal (Hll), and cubic phases at higher temperatures. The sn-1 chain of the PCs in a DOPE matrix is appreciably more ordered than in pure PCs, corresponding to an increase in the hydrophobic bilayer thickness of approximately 1 A. Distearoylphosphatidylcholine in the DOPE matrix has a higher sn-1 chain order than the unsaturated PCs. We observed distinct differences in the lipid order of upper and lower sections of the hydrocarbon chains caused by changes of temperature, unsaturation, headgroups, and ethanol. Unsaturation lowers chain order, mostly in the lower third of the hydrocarbon chains. By contrast, the increase in chain order caused by the DOPE matrix and the decrease in order with increasing temperature have a constant magnitude for the upper two-thirds of the chain and are smaller for the lower third. Addition of 2 M ethanol reduced order parameters, in effect reversing the increase in chain order caused by the DOPE matrix. PMID:8804610

  16. Biological variability of transferrin saturation and unsaturated iron binding capacity

    PubMed Central

    Adams, PC; Reboussin, DM; Press, RD; Barton, JC; Acton, RT; Moses, GC; Leiendecker-Foster, C; McLaren, GD; Dawkins, FW; Gordeuk, VR; Lovato, L; Eckfeldt, JH

    2007-01-01

    Background Transferrin saturation is widely considered the preferred screening test for hemochromatosis. Unsaturated iron binding capacity has similar performance at lower cost. However, the within-person biological variability of both these tests may limit their ability at commonly used cut points to detect HFE C282Y homozygous patients. Methods The Hemochromatosis and Iron Overload Screening (HEIRS) Study screened 101,168 primary care participants for iron overload using tansferrin saturation, unsaturated iron binding capacity, ferritin and HFE C282Y and H63D genotyping. Transferrin saturation and unsaturated iron binding capacity were performed at initial screening and again when selected participants and controls returned for a clinical examination several months later. A missed case was defined as a C282Y homozygote who had transferrin saturation below cut point (45 % women, 50 % men) or unsaturated iron binding capacity above cut point (150 μmol/L women, 125 μmol/L men) at either the initial screening or clinical examination, or both, regardless of serum ferritin. Results There were 209 C282Y previously undiagnosed homozygotes with transferrin saturation and unsaturated iron binding capacity testing done at initial screening and clinical examination. Sixty-eight C282Y homozygotes (33%) would have been missed at these transferrin saturation cut points (19 men, 49 women, median SF 170 μg/L, first and third quartiles 50 and 474 μg/L), and 58 homozygotes (28 %) would have been missed at the unsaturated iron binding capacity cut points (20 men, 38 women, median SF 168 μg/L, quartiles 38 and 454 μg/L). There was no advantage to using fasting samples. Conclusions The within-person biological variability of transferrin saturation and unsaturated iron binding capacity limit their usefulness as an initial screening test for expressing C282Y homozygotes. PMID:17976429

  17. Effect of monoglycerides and fatty acids on a ceramide bilayer.

    PubMed

    Akinshina, Anna; Das, Chinmay; Noro, Massimo G

    2016-07-14

    Monoglycerides and unsaturated fatty acids, naturally present in trace amounts in the stratum corneum (top layer of skin) lipid matrix, are commonly used in pharmaceutical, cosmetic and health care formulations. However, a detailed molecular understanding of how the oil additives get incorporated into the skin lipids from topical application and, once incorporated, how they affect the properties and integrity of the lipid matrix remains unexplored. Using ceramide 2 bilayers as skin lipid surrogates, we use a series of molecular dynamics simulations with six different natural oil ingredients at multiple concentrations to investigate the effect of the oils on the properties and stability of the bilayers. The six oils: monoolein, monostearin, monoelaidin, oleic acid, stearic acid and linoleic acid - all having the same length of the alkyl chain, C18, but a varying degree of saturation, allow us to systematically address the effect of unsaturation in the additives. Our results show that at low oil concentration (∼5%) the mixed bilayers containing any of the oils and ceramide 2 (CER2) become more rigid than pure CER2 bilayers due to more efficient lipid packing. Better packing also results in the formation of larger numbers of hydrogen bonds between the lipids, which occurs at the expense of the hydrogen bonds between lipids and water. The mixed bilayers with saturated or trans-unsaturated oils remain stable over the whole range of oil concentration. In contrast, the presence of the oils with at least one cis-double bond leads to bilayer instability and complete loss of bilayer structure at the oil content of about 50-65%. Two cis-double bonds in the lipid tail induce bilayer disruption at even lower concentration (∼30%). The mixed bilayers remain in the gel phase (without melting to a fluid phase) until the phase transition to a non-bilayer phase occurs. We also demonstrate that the stability of the bilayer strongly correlates with the order parameter of the lipid

  18. Natural weathering in dry disposed ash dump: Insight from chemical, mineralogical and geochemical analysis of fresh and unsaturated drilled cores.

    PubMed

    Akinyemi, S A; Akinlua, A; Gitari, W M; Khuse, N; Eze, P; Akinyeye, R O; Petrik, L F

    2012-07-15

    encapsulate the salt or act as a sustainable salt sink due to over time reduction in pore water pH. The leaching behaviours of Ca, Mg, Na+, K+, Se, Cr and Sr are controlled by the pH of the leachant in both fresh and unsaturated weathered ash. Other trace metals like As, Mo and Pb showed amphoteric behaviour with respect to the pH of the leachant. The precipitation of minor quantities of secondary mineral phases in the unsaturated weathered ash has significant effects on the acid susceptibility and leaching patterns of chemical species in comparison with fresh ash. The unsaturated weathered ash had lower buffering capacity at neutral pH (7.94-8.00) compared to fresh (unweathered) ash. This may be due to the initial high leaching/flushing of soluble basic buffering constituents from fly ash after disposal. The overall results of the acid susceptibility tests suggest that both fresh ash and unsaturated weathered ash would release a large percentage of their chemical species when in contact with slightly acidified rain. Proper management of ash dumps is therefore essential to safeguard the environmental risks of water percolation in different fly ashes behaviour. PMID:22446137

  19. Synthesis of Unsaturated Polyester Resins from Various Bio-Derived Platform Molecules.

    PubMed

    Farmer, Thomas J; Castle, Rachael L; Clark, James H; Macquarrie, Duncan J

    2015-01-01

    Utilisation of bio-derived platform molecules in polymer synthesis has advantages which are, broadly, twofold; to digress from crude oil dependence of the polymer industry and secondly to reduce the environmental impact of the polymer synthesis through the inherent functionality of the bio-derived platform molecules. Bulk polymerisation of bio-derived unsaturated di-acids has been employed to produce unsaturated polyester (UPEs) which have been analysed by GPC, TGA, DSC and NMR spectroscopy, advancing on the analysis previously reported. UPEs from the diesters of itaconic, succinic, and fumaric acids were successfully synthesised with various diols and polyols to afford resins of MN 480-477,000 and Tg of -30.1 to -16.6 °C with solubilities differing based on starting monomers. This range of properties allows for many applications and importantly due to the surviving Michael acceptor moieties, solubility and cross-linking can be specifically tailored, post polymerisation, to the desired function. An improved synthesis of itaconate and succinate co-polymers, via the initial formation of an itaconate bis-diol, is also demonstrated for the first time, resulting in significantly improved itaconate incorporation. PMID:26147423

  20. Synthesis of Unsaturated Polyester Resins from Various Bio-Derived Platform Molecules

    PubMed Central

    Farmer, Thomas J.; Castle, Rachael L.; Clark, James H.; Macquarrie, Duncan J.

    2015-01-01

    Utilisation of bio-derived platform molecules in polymer synthesis has advantages which are, broadly, twofold; to digress from crude oil dependence of the polymer industry and secondly to reduce the environmental impact of the polymer synthesis through the inherent functionality of the bio-derived platform molecules. Bulk polymerisation of bio-derived unsaturated di-acids has been employed to produce unsaturated polyester (UPEs) which have been analysed by GPC, TGA, DSC and NMR spectroscopy, advancing on the analysis previously reported. UPEs from the diesters of itaconic, succinic, and fumaric acids were successfully synthesised with various diols and polyols to afford resins of MN 480–477,000 and Tg of −30.1 to −16.6 °C with solubilities differing based on starting monomers. This range of properties allows for many applications and importantly due to the surviving Michael acceptor moieties, solubility and cross-linking can be specifically tailored, post polymerisation, to the desired function. An improved synthesis of itaconate and succinate co-polymers, via the initial formation of an itaconate bis-diol, is also demonstrated for the first time, resulting in significantly improved itaconate incorporation. PMID:26147423

  1. Toluene Diffusion and Reaction in Unsaturated Pseudomonas putida Biofilms

    PubMed Central

    Holden, Patricia A.; Hunt, James R.; Firestone, Mary K.

    2010-01-01

    Biofilms are frequently studied in the context of submerged or aquatic systems. However, much less is known about biofilms in unsaturated systems, despite their importance to such processes as food spoilage, terrestrial nutrient cycling, and biodegradation of environmental pollutants in soils. Using modeling and experimentation, we have described the biodegradation of toluene in unsaturated media by bacterial biofilms as a function of matric water potential, a dominant variable in unsaturated systems. We experimentally determined diffusion and kinetic parameters for Pseudomonas putida biofilms, then predicted biodegradation rates over a range of matric water potentials. For validation, we measured the rate of toluene depletion by intact biofilms and found the results to reasonably follow the model predictions. The diffusion coefficient for toluene through unsaturated P. putida biofilm averaged 1.3 × 10−7 cm2/s, which is approximately two orders of magnitude lower than toluene diffusivity in water. Our studies show that, at the scale of the microbial biofilm, the diffusion of toluene to biodegrading bacteria can limit the overall rate of biological toluene depletion in unsaturated systems. PMID:18642338

  2. Analysis of rainfall infiltration law in unsaturated soil slope.

    PubMed

    Zhang, Gui-rong; Qian, Ya-jun; Wang, Zhang-chun; Zhao, Bo

    2014-01-01

    In the study of unsaturated soil slope stability under rainfall infiltration, it is worth continuing to explore how much rainfall infiltrates into the slope in a rain process, and the amount of rainfall infiltrating into slope is the important factor influencing the stability. Therefore, rainfall infiltration capacity is an important issue of unsaturated seepage analysis for slope. On the basis of previous studies, rainfall infiltration law of unsaturated soil slope is analyzed. Considering the characteristics of slope and rainfall, the key factors affecting rainfall infiltration of slope, including hydraulic properties, water storage capacity (θs - θr), soil types, rainfall intensities, and antecedent and subsequent infiltration rates on unsaturated soil slope, are discussed by using theory analysis and numerical simulation technology. Based on critical factors changing, this paper presents three calculation models of rainfall infiltrability for unsaturated slope, including (1) infiltration model considering rainfall intensity; (2) effective rainfall model considering antecedent rainfall; (3) infiltration model considering comprehensive factors. Based on the technology of system response, the relationship of rainfall and infiltration is described, and the prototype of regression model of rainfall infiltration is given, in order to determine the amount of rain penetration during a rain process. PMID:24672332

  3. Toluene diffusion and reaction in unsaturated Pseudomonas putida biofilms

    SciTech Connect

    Holden, P.A.; Hunt, J.R.; Firestone, M.K.

    1997-12-20

    Biofilms are frequently studied in the context of submerged or aquatic systems. However, much less is known about biofilms in unsaturated systems, despite their importance to such processes as food spoilage, terrestrial nutrient cycling, and biodegradation of environmental pollutants in soils. Using modeling and experimentation, the authors have described the biodegradation of toluene in unsaturated media by bacterial biofilms as a function of matric water potential, a dominant variable in unsaturated systems. They experimentally determined diffusion and kinetic parameters for Pseudomonas putida biofilms, then predicted biodegradation rates over a range of matric water potentials. For validation, the authors measured the rate of toluene depletion by intact biofilms and found the results to reasonably follow the model predictions. The diffusion coefficient for toluene through unsaturated P. putida biofilm averaged 1.3 {times} 10{sup {minus}7} cm{sup 2}/s, which is approximately two orders of magnitude lower than toluene diffusivity in water. Their studies show that, at the scale of the microbial biofilm, the diffusion of toluene to biodegrading bacteria can limit the overall rate of biological toluene depletion in unsaturated systems.

  4. Analysis of Rainfall Infiltration Law in Unsaturated Soil Slope

    PubMed Central

    Zhang, Gui-rong; Qian, Ya-jun; Wang, Zhang-chun; Zhao, Bo

    2014-01-01

    In the study of unsaturated soil slope stability under rainfall infiltration, it is worth continuing to explore how much rainfall infiltrates into the slope in a rain process, and the amount of rainfall infiltrating into slope is the important factor influencing the stability. Therefore, rainfall infiltration capacity is an important issue of unsaturated seepage analysis for slope. On the basis of previous studies, rainfall infiltration law of unsaturated soil slope is analyzed. Considering the characteristics of slope and rainfall, the key factors affecting rainfall infiltration of slope, including hydraulic properties, water storage capacity (θs - θr), soil types, rainfall intensities, and antecedent and subsequent infiltration rates on unsaturated soil slope, are discussed by using theory analysis and numerical simulation technology. Based on critical factors changing, this paper presents three calculation models of rainfall infiltrability for unsaturated slope, including (1) infiltration model considering rainfall intensity; (2) effective rainfall model considering antecedent rainfall; (3) infiltration model considering comprehensive factors. Based on the technology of system response, the relationship of rainfall and infiltration is described, and the prototype of regression model of rainfall infiltration is given, in order to determine the amount of rain penetration during a rain process. PMID:24672332

  5. Hydraulic properties of adsorbed water films in unsaturated porous media

    SciTech Connect

    Tokunaga, Tetsu K.

    2009-03-01

    Adsorbed water films strongly influence residual water saturations and hydraulic conductivities in porous media at low saturations. Hydraulic properties of adsorbed water films in unsaturated porous media were investigated through combining Langmuir's film model with scaling analysis, without use of any adjustable parameters. Diffuse double layer influences are predicted to be important through the strong dependence of adsorbed water film thickness (f) on matric potential ({Psi}) and ion charge (z). Film thickness, film velocity, and unsaturated hydraulic conductivity are predicted to vary with z{sup -1}, z{sup -2}, and z{sup -3}, respectively. In monodisperse granular media, the characteristic grain size ({lambda}) controls film hydraulics through {lambda}{sup -1} scaling of (1) the perimeter length per unit cross sectional area over which films occur, (2) the critical matric potential ({Psi}{sub c}) below which films control flow, and (3) the magnitude of the unsaturated hydraulic conductivity when {Psi} < {Psi}{sub c}. While it is recognized that finer textured sediments have higher unsaturated hydraulic conductivities than coarser sands at intermediate {Psi}, the {lambda}{sup -1} scaling of hydraulic conductivity predicted here extends this understanding to very low saturations where all pores are drained. Extremely low unsaturated hydraulic conductivities are predicted under adsorbed film-controlled conditions (generally < 0.1 mm y{sup -1}). On flat surfaces, the film hydraulic diffusivity is shown to be constant (invariant with respect to {Psi}).

  6. Endocannabinoid signaling in the gut mediates preference for dietary unsaturated fats

    PubMed Central

    DiPatrizio, Nicholas V.; Joslin, Alexandra; Jung, Kwang-Mook; Piomelli, Daniele

    2013-01-01

    Dietary fat exerts a potent stimulatory effect on feeding. This effect is mediated, at least in part, by a cephalic mechanism that involves recruitment of the vagus nerve and subsequent activation of endocannabinoid signaling in the gut. Here, we used a sham-feeding protocol in rats to identify fatty-acid constituents of dietary fat that might be responsible for triggering small-intestinal endocannabinoid signaling. Sham feeding rats with a corn oil emulsion increased endocannabinoid levels in jejunum, relative to animals that received either mineral oil (which contains no fatty acids) or no oil. Sham-feeding emulsions containing oleic acid (18:1) or linoleic acid (18:2) caused, on average, a nearly 2-fold accumulation of jejunal endocannabinoids, whereas emulsions containing stearic acid (18:0) or linolenic acid (18:3) had no such effect. In a 2-bottle-choice sham-feeding test, rats displayed strong preference for emulsions containing 18:2, which was blocked by pretreatment with the peripherally restricted CB1 cannabinoid receptor antagonists, AM6546 and URB447. Our results suggest that oral exposure to the monoenoic and dienoic fatty acid component of dietary fat selectively initiates endocannabinoid mobilization in the gut, and that this local signaling event is essential for fat preference.—DiPatrizio, N. V., Joslin, A., Jung, K.-M., Piomelli, D. Endocannabinoid signaling in the gut mediates preference for dietary unsaturated fats. PMID:23463697

  7. Reaction Mechanism of Oxygen Atoms with Unsaturated Hydrocarbons by the Crossed-Molecular-Beams Method

    DOE R&D Accomplishments Database

    Buss, R. J.; Baseman, R. J.; Guozhong, H.; Lee, Y. T.

    1982-04-01

    From a series of studies of the reaction of oxygen atoms with unsaturated hydrocarbons using the crossed molecular beam method, the dominant reaction mechanisms were found to be the simple substitution reactions with oxygen atoms replacing H, Cl, Br atom or alkyl groups. Complication due to secondary reaction was avoided by carrying out experiments under single collisions and observing primary products directly. Primary products were identified by measuring the angular and velocity distributions of products at all the mass numbers which could be detected by the mass spectrometer, and from comparison of these distributions, applying the requirement of energy and momentum conservation.

  8. Fatty Acid Structure and Degradation Analysis in Fingerprint Residues.

    PubMed

    Pleik, Stefanie; Spengler, Bernhard; Schäfer, Thomas; Urbach, Dieter; Luhn, Steven; Kirsch, Dieter

    2016-09-01

    GC-MS investigations were carried out to elucidate the aging behavior of unsaturated fatty acids in fingerprint residues and to identify their degradation products in aged samples. For this purpose, a new sample preparation technique for fingerprint residues was developed that allows producing N-methyl-N-trimethylsilyl-trifluoroacetamide (MSTFA) derivatives of the analyzed unsaturated fatty acids and their degradation products. MSTFA derivatization catalyzed by iodotrimethylsilane enables the reliable identification of aldehydes and oxoacids as characteristic MSTFA derivatives in GCMS. The obtained results elucidate the degradation pathway of unsaturated fatty acids. Our study of aged fingerprint residues reveals that decanal is the main degradation product of the observed unsaturated fatty acids. Furthermore, oxoacids with different chain lengths are detected as specific degradation products of the unsaturated fatty acids. The detection of the degradation products and their chain length is a simple and effective method to determine the double bond position in unsaturated compounds. We can show that the hexadecenoic and octadecenoic acids found in fingerprint residues are not the pervasive fatty acids Δ9-hexadecenoic (palmitoleic acid) and Δ9-octadecenoic (oleic acid) acid but Δ6-hexadecenoic acid (sapienic acid) and Δ8-octadecenoic acid. The present study focuses on the structure identification of human sebum-specific unsaturated fatty acids in fingerprint residues based on the identification of their degradation products. These results are discussed for further investigations and method developments for age determination of fingerprints, which is still a tremendous challenge because of several factors affecting the aging behavior of individual compounds in fingerprints. Graphical Abstract ᅟ. PMID:27324649

  9. Fatty Acid Structure and Degradation Analysis in Fingerprint Residues

    NASA Astrophysics Data System (ADS)

    Pleik, Stefanie; Spengler, Bernhard; Schäfer, Thomas; Urbach, Dieter; Luhn, Steven; Kirsch, Dieter

    2016-09-01

    GC-MS investigations were carried out to elucidate the aging behavior of unsaturated fatty acids in fingerprint residues and to identify their degradation products in aged samples. For this purpose, a new sample preparation technique for fingerprint residues was developed that allows producing N-methyl- N-trimethylsilyl-trifluoroacetamide (MSTFA) derivatives of the analyzed unsaturated fatty acids and their degradation products. MSTFA derivatization catalyzed by iodotrimethylsilane enables the reliable identification of aldehydes and oxoacids as characteristic MSTFA derivatives in GCMS. The obtained results elucidate the degradation pathway of unsaturated fatty acids. Our study of aged fingerprint residues reveals that decanal is the main degradation product of the observed unsaturated fatty acids. Furthermore, oxoacids with different chain lengths are detected as specific degradation products of the unsaturated fatty acids. The detection of the degradation products and their chain length is a simple and effective method to determine the double bond position in unsaturated compounds. We can show that the hexadecenoic and octadecenoic acids found in fingerprint residues are not the pervasive fatty acids Δ9-hexadecenoic (palmitoleic acid) and Δ9-octadecenoic (oleic acid) acid but Δ6-hexadecenoic acid (sapienic acid) and Δ8-octadecenoic acid. The present study focuses on the structure identification of human sebum-specific unsaturated fatty acids in fingerprint residues based on the identification of their degradation products. These results are discussed for further investigations and method developments for age determination of fingerprints, which is still a tremendous challenge because of several factors affecting the aging behavior of individual compounds in fingerprints.

  10. Determination of unsaturation grade and trans isomers generated during thermal oxidation of edible oils and fats by FTIR

    NASA Astrophysics Data System (ADS)

    Moya Moreno, M. C. M.; Mendoza Olivares, D.; Amézquita López, F. J.; Gimeno Adelantado, J. V.; Bosch Reig, F.

    1999-05-01

    The oxidative deterioration of culinary oils and fats during episodes of heating associated with normal usage (80°C-300°C, 20-40 min) was monitored by FTIR spectroscopy. The thermal oxidation of polyunsaturated fatty acids during heating was studied by the determination of unsaturation percentage and trans isomers at various temperatures and heating times. Oils frequently used in food frying such as olive oil, sunflower oil, corn oil and seeds oil (sunflower, safflower and canola seed), and lard were studied. The Absorbance Correction Method is proposed to correct the spectral interference and allows the analytic use of signal which would not be initially valid for quantitative analysis. The results show that there is a decrease in unsaturation and an increase in trans isomers starting at 150°C and becomes more pronounced at temperatures around 250°C. This variation in unsaturation grade and conformation provides evidence of the transformation of essential polyunsaturated fatty acids and subsequent decrease in the oils' nutritional value.

  11. Process for making unsaturated hydrocarbons using microchannel process technology

    SciTech Connect

    Tonkovich, Anna Lee; Yuschak, Thomas; LaPlante, Timothy J.; Rankin, Scott; Perry, Steven T.; Fitzgerald, Sean Patrick; Simmons, Wayne W.; Mazanec, Terry Daymo, Eric

    2011-04-12

    The disclosed invention relates to a process for converting a feed composition comprising one or more hydrocarbons to a product comprising one or more unsaturated hydrocarbons, the process comprising: flowing the feed composition and steam in contact with each other in a microchannel reactor at a temperature in the range from about 200.degree. C. to about 1200.degree. C. to convert the feed composition to the product, the process being characterized by the absence of catalyst for converting the one or more hydrocarbons to one or more unsaturated hydrocarbons. Hydrogen and/or oxygen may be combined with the feed composition and steam.

  12. Story Numbers.

    ERIC Educational Resources Information Center

    Swafford, Jane; McGinty, Robert

    1978-01-01

    A concrete approach to prime numbers is presented using rectangles and triangles to construct a building for each number so that each story represents a pair of factors and the triangular-shaped roof represents the number. (MP)

  13. Adaptive modification of membrane phospholipid fatty acid composition and metabolic thermosuppression of brown adipose tissue in heat-acclimated rats

    NASA Astrophysics Data System (ADS)

    Saha, S. K.; Ohno, T.; Tsuchiya, K.; Kuroshima, A.

    Thermogenesis, especially facultative thermogenesis by brown adipose tissue (BAT), is less important in high ambient temperature and the heat-acclimated animals show a lower metabolic rate. Adaptive changes in the metabolic activity of BAT are generally found to be associated with a modification of membrane phospholipid fatty acid composition. However, the effect of heat acclimation on membrane phospholipid fatty acid composition is as yet unknown. In this study, we examined the thermogenic activity and phospholipid fatty acid composition of interscapular BAT from heat-acclimated rats (control: 25+/-1°C, 50% relative humidity and heat acclimation: 32+/-0.5°C, 50% relative humidity). Basal thermogenesis and the total thermogenic capacity after noradrenaline stimulation, as estimated by in vitro oxygen consumption of BAT (measured polarographically using about 1-mm3 tissue blocks), were smaller in the heat-acclimated group than in the control group. There was no difference in the tissue content of phospholipids between the groups when expressed per microgram of DNA. The phospholipid fatty acid composition was analyzed by a capillary gas chromatograph. The state of phospholipid unsaturation, as estimated by the number of double bonds per fatty acid molecule, was similar between the groups. The saturated fatty acid level was higher in the heat-acclimated group. Among the unsaturated fatty acids, heat acclimation decreased docosahexaenoic acid and oleic acid levels, and increased the arachidonic acid level. The tissue level of docosahexaenoic acid correlated with the basal oxygen consumption of BAT (r=0.6, P<0.01) and noradrenaline-stimulated maximum values of oxygen consumption (r=0.5, P<0.05). Our results show that heat acclimation modifies the BAT phospholipid fatty acids, especially the n-3 polyunsaturated fatty acid docosahexaenoic acid, which is possibly involved in the metabolic thermosuppression.

  14. STRUCTURE TOXICITY IN RELATIONSHIPS FOR A,B-UNSATURATED ALCOHOLS IN FISH

    EPA Science Inventory

    Previous toxicity testing with fathead minnows (Pimephales promelas) indicated that some unsaturated acetylenic and allylic alcohols can be metabolically activated, via alcohol dehydrogenase, to highly toxic a,B-unsaturated aldehydes and ketones or allene derivatives. lthough sev...

  15. Essential fatty acid deficiency in patients with lesions of the gastrointestinal tract

    PubMed Central

    Wapnick, Simon; Norden, Daphne A.; Venturas, Dawn J.

    1974-01-01

    The relative amounts of unsaturated fatty acids in the serum lipids of 14 patients who have undergone small bowel resection have been investigated. These results are compared with those from control subjects and also from patients suffering from cancer of the oesophagus. Both groups of patients showed patterns of unsaturated fatty acids suggesting essential fatty acid deficiency. In the resection patients there was no correlation between the extent of intestinal removal and the extent of the change in the unsaturated fatty acid pattern. PMID:18668845

  16. Heat and mass transfer in unsaturated porous media. Final report

    SciTech Connect

    Childs, S.W.; Malstaff, G.

    1982-02-01

    A preliminary study of heat and water transport in unsaturated porous media is reported. The project provides background information regarding the feasibility of seasonal thermal energy storage in unconfined aquifers. A parametric analysis of the factors of importance, and an annotated bibliography of research findings pertinent to unconfined aquifer thermal energy storage (ATES) are presented. This analysis shows that heat and mass transfer of water vapor assume dominant importance in unsaturated porous media at elevated temperature. Although water vapor fluxes are seldom as large as saturated medium liquid water fluxes, they are important under unsaturated conditions. The major heat transport mechanism for unsaturated porous media at temperatures from 50 to 90/sup 0/C is latent heat flux. The mechanism is nonexistent under saturated conditions but may well control design of unconfined aquifer storage systems. The parametric analysis treats detailed physical phenomena which occur in the flow systems study and demonstrates the temperature and moisture dependence of the transport coefficients of importance. The question of design of an unconfined ATES site is also addressed by considering the effects of aquifer temperature, depth to water table, porous medium flow properties, and surface boundary conditions. Recommendations are made for continuation of this project in its second phase. Both scientific and engineering goals are considered and alternatives are presented.

  17. Electropositive bivalent metallic ion unsaturated polyester complexed polymer concrete

    DOEpatents

    Sugama, Toshifumi; Kukacka, Lawrence E.; Horn, William H.

    1985-01-01

    Quick setting polymer concrete compositions with excellent structural properties are disclosed; these polymer concrete compositions are mixtures of unsaturated polyesters and crosslinking monomers together with appropriate initiators and promoters in association with aggregate, which may be wet, and with a source of bivalent metallic ions.

  18. Electropositive bivalent metallic ion unsaturated polyester complexed polymer concrete

    DOEpatents

    Sugama, T.; Kukacka, L.E.; Horn, W.H.

    1981-11-04

    Quick setting polymer concrete compositions which are mixtures of unsaturated polyesters and crosslinking monomers together with appropriate initiators and promoters in association with aggregate which may be wet and a source of bivalent metallic ions which will set to polymer concrete with excellent structural properties.

  19. Electropositive bivalent metallic ion unsaturated polyester complexed polymer concrete

    DOEpatents

    Sugama, T.; Kukacka, L.E.; Horn, W.H.

    1983-05-13

    Quick setting polymer concrete compositions are described which are mixtures of unsaturated polyesters and crosslinking monomers together with appropriate initiators and promoters in association with aggregate which may be wet and a source of bivalent metallic ions which will set to polymer concrete with excellent structural properties.

  20. Heuristical Strategies on the Study Theme "The Unsaturated Hydrocarbons -- Alkenes"

    ERIC Educational Resources Information Center

    Naumescu, Adrienne Kozan; Pasca, Roxana-Diana

    2011-01-01

    The influence of heuristical strategies upon the level of two experimental classes is studied in this paper. The didactic experiment took place at secondary school in Cluj-Napoca, in 2008-2009 school year. The study theme "The Unsaturated Hydrocarbons--Alkenes" has been efficiently learned by using the most active methods: laboratory…

  1. 40 CFR 264.278 - Unsaturated zone monitoring.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... or operator must monitor the soil and soil-pore liquid to determine whether hazardous constituents... unsaturated zone monitoring system that includes soil monitoring using soil cores and soil-pore liquid... the quality of background soil-pore liquid quality and the chemical make-up of soil that has not...

  2. 40 CFR 264.278 - Unsaturated zone monitoring.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... or operator must monitor the soil and soil-pore liquid to determine whether hazardous constituents... unsaturated zone monitoring system that includes soil monitoring using soil cores and soil-pore liquid... the quality of background soil-pore liquid quality and the chemical make-up of soil that has not...

  3. Colloid Bound Transport of Contaminats In The Unsaturated Zone

    NASA Astrophysics Data System (ADS)

    Hofmann, T.; Christ, A.

    Colloids can play a major role in the relocation of contaminants in the unsaturated zone. The amount of colloid driven transport is defined by soil chemistry, soil water chemistry and water flow velocity as well as colloid composition and formation. In a current research project we investigate the filtration and mobilization of colloids in unsaturated column studies. We use different soil types, chosen by a wide range of mean grain size and heterogeneity. Particle tracers are polystyrene solids with a de- fined negative surface charge and defined size from 50 nm to 10 µm. In addition, we use natural colloids extracted from a wide range of contaminated and uncontaminated land. Experimental conditions are exactly controlled throughout all the time. We alter mainly flow velocity ionic strength in order to study the filtration behaviour of the soils. In addition, Pyrene and Lead are are used as model contaminants. First results show the colloids are not retarded in many coarse structured soil types. Preferential colloid flow shows a major impact in breakthrough behaviour. Colloid bound lead is relocated significant through the unsaturated zone, whereas non colloid bound lead species are strongly retarded. In the presentation we will show results of contami- nant processes and present new results on the filtration behaviour of colloids in the unsaturated zone depending on flow velocity, soil type and colloid size.

  4. Review of Upscaling Methods for Describing Unsaturated Flow

    SciTech Connect

    Wood, Brian D.

    2000-09-26

    Representing samll-scale features can be a challenge when one wants to model unsaturated flow in large domains. In this report, the various upscaling techniques are reviewed. The following upscaling methods have been identified from the literature: stochastic methods, renormalization methods, volume averaging and homogenization methods. In addition, a final technique, full resolution numerical modeling, is also discussed.

  5. Unsaturated and Saturated Permeabilities of Fiber Reinforcement: Critics and Suggestions

    NASA Astrophysics Data System (ADS)

    Park, Chung Hae; Krawczak, Patricia

    2015-04-01

    In general, permeability measurement results show a strong scattering according to the measurement method, the type of test fluid and the fluid injection condition, even though permeability is regarded as a unique property of porous medium. In particular, the discrepancy between the unsaturated and saturated permeabilities for the same fabric has been widely reported. In the literature, relative permeability has been adopted to model the unsaturated flow. This approach has some limits in the modeling of double-scale porosity medium. We address this issue of permeability measurement by rigorously examining the mass conservation condition. Finally, we identify that the pressure gradient is non-linear with positive curvature in the unsaturated flow and a misinterpretation of pressure gradient is the main reason for the difference between the saturated and unsaturated permeabilities of the same fiber reinforcement. We propose to use a fixed value of permeability and to modify the mass conservation equation if there are air voids which are entrapped inside the fiber tow. Finally, we also suggest some guidelines and future perspectives to obtain more consistent permeability measurement results.

  6. BIODEGRADATION OF HYDROCARBON VAPORS IN THE UNSATURATED ZONE

    EPA Science Inventory

    The time-averaged concentration of hydrocarbon and oxygen vapors were measured in the unsaturated zone above the residually contaminated capillary fringe at the U.S. Coast Guard Air Station in Traverse City, Michigan. Total hydrocarbon and oxygen vapor concentrations were observe...

  7. ENGINEERING ISSUE: IN SITU BIOREMEDIATION OF CONTAMINATED UNSATURATED SUBSURFACE SOILS

    EPA Science Inventory

    An emerging technology for the remediation of unsaturated subsurface soils involves the use of microorganisms to degrade contaminants which are present in such soils. Understanding the processes which drive in situ bioremediation, as well as the effectiveness and efficiency of th...

  8. Unsaturated soil hydraulic conductivity: The field infiltrometer method

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Theory: Field methods to measure the unsaturated soil hydraulic conductivity assume presence of steady-state water flow. Soil infiltrometers are desired to apply water onto the soil surface at constant negative pressure. Water is applied to the soil from the Marriott device through a porous membrane...

  9. Ultralong C100 Mycolic Acids Support the Assignment of Segniliparus as a New Bacterial Genus

    PubMed Central

    Layre, Emilie; Sweet, Lindsay; Young, David C.; Posey, James E.; Butler, W. Ray; Moody, D. Branch

    2012-01-01

    Mycolic acid-producing bacteria isolated from the respiratory tract of human and non-human mammals were recently assigned as a distinct genus, Segniliparus, because they diverge from rhodococci and mycobacteria in genetic and chemical features. Using high accuracy mass spectrometry, we determined the chemical composition of 65 homologous mycolic acids in two Segniliparus species and separately analyzed the three subclasses to measure relative chain length, number and stereochemistry of unsaturations and cyclopropyl groups within each class. Whereas mycobacterial mycolate subclasses are distinguished from one another by R groups on the meromycolate chain, Segniliparus species synthesize solely non-oxygenated α-mycolates with high levels of cis unsaturation. Unexpectedly Segniliparus α-mycolates diverge into three subclasses based on large differences in carbon chain length with one bacterial culture producing mycolates that range from C58 to C100. Both the overall chain length (C100) and the chain length diversity (C42) are larger than previously seen for mycolic acid-producing organisms and provide direct chemical evidence for assignment of Segniliparus as a distinct genus. Yet, electron microscopy shows that the long and diverse mycolates pack into a typical appearing membrane. Therefore, these new and unexpected extremes of mycolic acid chemical structure raise questions about the modes of mycolic acid packing and folding into a membrane. PMID:22720018

  10. α,β-Unsaturated aldehyde of hyaluronan--Synthesis, analysis and applications.

    PubMed

    Buffa, Radovan; Šedová, Petra; Basarabová, Ivana; Moravcová, Martina; Wolfová, Lucie; Bobula, Tomáš; Velebný, Vladimír

    2015-12-10

    Hyaluronic acid (HA) modified with an aldehyde group (HA-CHO or HA-aldehyde) has been extensively used for various biomedical applications. The main advantage of the aldehyde moieties is the ability to react with a wide range of amino compounds under physiological conditions. Reactions of aldehydes with primary amines in water are reversible and equilibrium is thoroughly shifted towards starting aldehyde and amine. This work presents an unique modification of HA: α,β-unsaturated aldehyde of HA (4,5-anhydro-6(GlcNAc)-oxo HA or ΔHA-CHO), which allows the primary amines to be attached to HA more effectively in comparison to the saturated HA-CHO. Higher hydrolytic stability is caused by the conjugation of imine with an adjacent --C=C-- double bond. Two strategies for the preparation of unsaturated HA-aldehyde were developed and chemical structures were studied in details. Cross-linked materials prepared from this precursor are biocompatible and suitable for applications in drug delivery and regenerative medicine. PMID:26428127

  11. Process for separating an ethylenically unsaturated hydrocarbon from a hydrocarbon mixture

    SciTech Connect

    vanEijl, A.T.

    1986-06-24

    A process is described for separating an ethylenically unsaturated hydrocarbon from a hydrocarbon mixture characterized by: (a) distilling a hydrocarbon mixture containing the unsaturated hydrocarbon with an N-(aminoalkyl) piperazine; and (b) separating the amine/hydrocarbon mixture into at least two factions, one of which contains the amine and the unsaturated hydrocarbon.

  12. Cytochromes P450 Catalyze the Reduction of α,β-Unsaturated Aldehydes

    PubMed Central

    Amunom, Immaculate; Dieter, Laura J.; Tamasi, Viola; Cai, Jan; Conklin, Daniel J.; Srivastava, Sanjay; Martin, Martha V.; Guengerich, F. Peter; Prough, Russell A.

    2011-01-01

    The metabolism of α,β-unsaturated aldehydes, e.g. 4-hydroxynonenal, involves oxidation to carboxylic acids, reduction to alcohols, and glutathionylation to eventually form mercapturide conjugates. Recently we demonstrated that P450s can oxidize aldehydes to carboxylic acids, a reaction previously thought to involve aldehyde dehydrogenase. When recombinant cytochrome P450 3A4 was incubated with 4-hydroxynonenal, O2, and NADPH, several products were produced, including 1,4-dihydroxynonene (DHN), 4-hydroxy-2-nonenoic acid (HNA), and an unknown metabolite. Several P450s catalyzed the reduction reaction in the order (human) P450 2B6 ≅ P450 3A4 > P450 1A2 > P450 2J2 > (mouse) P450 2c29. Other P450s did not catalyze the reduction reaction (human P450 2E1 & rabbit P450 2B4). Metabolism by isolated rat hepatocytes showed that HNA formation was inhibited by cyanamide, while DHN formation was not affected. Troleandomycin increased HNA production 1.6-fold while inhibiting DHN formation, suggesting that P450 3A11 is a major enzyme involved in rat hepatic clearance of 4-HNE. A fluorescent assay was developed using 9-anthracenealdehyde to measure both reactions. Feeding mice diet containing t-butylated hydroxyanisole increased the level of both activities with hepatic microsomal fractions, but not proportionally. Miconazole (0.5 mM) was a potent inhibitor of these microsomal reduction reactions, while phenytoin and α-naphthoflavone (both at 0.5 mM) were partial inhibitors, suggesting the role of multiple P450 enzymes. The oxidative metabolism of these aldehydes was inhibited >90% in an Ar or CO atmosphere, while the reductive reactions were not greatly affected. These results suggest that P450s are significant catalysts of reduction of α,β-unsaturated aldehydes in liver. PMID:21766881

  13. Groundwater recharge dynamics in unsaturated fractured chalk: a case study

    NASA Astrophysics Data System (ADS)

    Cherubini, Claudia; Pastore, Nicola; Giasi, Concetta I.; Allegretti, Nicolaetta M.

    2016-04-01

    The heterogeneity of the unsaturated zone controls its hydraulic response to rainfall and the extent to which pollutants are delayed or attenuated before reaching groundwater. It plays therefore a very important role in the recharge of aquifers and the transfer of pollutants because of the presence of temporary storage zones and preferential flows. A better knowledge of the physical processes in the unsaturated zone would allow an improved assessment of the natural recharge in a heterogeneous aquifer and of its vulnerability to surface-applied pollution. The case study regards the role of the thick unsaturated zone of the Cretaceous chalk aquifer in Picardy (North of France) that controls the hydraulic response to rainfall. In the North Paris Basin, much of the recharge must pass through a regional chalk bed that is composed of a porous matrix with embedded fractures. Different types of conceptual models have been formulated to explain infiltration and recharge processes in the unsaturated fractured rock. The present study analyses the episodic recharge in fractured Chalk aquifer using the kinematic diffusion theory to predict water table fluctuation in response to rainfall. From an analysis of the data, there is the evidence of 1) a seasonal behavior characterized by a constant increase in the water level during the winter/spring period and a recession period, 2) a series of episodic behaviors during the summer/autumn. Kinematic diffusion models are useful for predict preferential fluxes and dynamic conditions. The presented approach conceptualizes the unsaturated flow as a combination of 1) diffusive flow refers to the idealized portion of the pore space of the medium within the flow rate is driven essentially by local gradient of potential; 2) preferential flow by which water moves across macroscopic distances through conduits of macropore length.

  14. Influence of surfactants on unsaturated water flow and solute transport

    NASA Astrophysics Data System (ADS)

    Karagunduz, Ahmet; Young, Michael H.; Pennell, Kurt D.

    2015-04-01

    Surfactants can reduce soil water retention by changing the surface tension of water and the contact angle between the liquid and solid phases. As a result, water flow and solute transport in unsaturated soil may be altered in the presence of surfactants. In this study, the effects of a representative nonionic surfactant, Triton X-100, on coupled water flow and nonreactive solute transport during unsaturated flow conditions were evaluated. Batch reactor experiments were conducted to measure the surfactant sorption characteristics, while unsaturated transport experiments were performed in columns packed with 40-270 mesh Ottawa sand at five initial water contents. Following the introduction of surfactant solution, the rate of water percolation through the sand increased; however, this period of rapid water drainage was followed by decreased water percolation due to the reduction in soil water content and the corresponding decrease in unsaturated hydraulic conductivity behind the surfactant front. The observed changes in water percolation occurred sequentially, and resulted in faster nonreactive solute transport than was observed in the absence of surfactant. A one-dimensional mathematical model accurately described coupled water flow, surfactant, and solute transport under most experimental conditions. Differences between model predictions and experimental data were observed in the column study performed at the lowest water content (0.115 cm3/cm3), which was attributed to surfactant adsorption at the air-water interface. These findings demonstrate the potential influence of surfactants additives on unsaturated water flow and solute transport in soils, and demonstrate a methodology to couple these processes in a predictive modeling tool.

  15. Transport of citrate-coated silver nanoparticles in unsaturated sand.

    PubMed

    Kumahor, Samuel K; Hron, Pavel; Metreveli, George; Schaumann, Gabriele E; Vogel, Hans-Jörg

    2015-12-01

    Chemical factors and physical constraints lead to coupled effects during particle transport in unsaturated porous media. Studies on unsaturated transport as typical for soils are currently scarce. In unsaturated porous media, particle mobility is determined by the existence of an air-water interface in addition to a solid-water interface. To this end, we measured breakthrough curves and retention profiles of citrate-coated Ag nanoparticles in unsaturated sand at two pH values (5 and 9) and three different flow rates corresponding to different water contents with 1 mM KNO3 as background electrolyte. The classical DLVO theory suggests unfavorable deposition conditions at the air-water and solid-water interfaces. The breakthrough curves indicate modification in curve shapes and retardation of nanoparticles compared to inert solute. Retention profiles show sensitivity to flow rate and pH and this ranged from almost no retention for the highest flow rate at pH=9 to almost complete retention for the lowest flow rate at pH=5. Modeling of the breakthrough curves, thus, required coupling two parallel processes: a kinetically controlled attachment process far from equilibrium, responsible for the shape modification, and an equilibrium sorption, responsible for particle retardation. The non-equilibrium process and equilibrium sorption are suggested to relate to the solid-water and air-water interfaces, respectively. This is supported by the DLVO model extended for hydrophobic interactions which suggests reversible attachment, characterized by a secondary minimum (depth 3-5 kT) and a repulsive barrier at the air-water interface. In contrast, the solid-water interface is characterized by a significant repulsive barrier and the absence of a secondary minimum suggesting kinetically controlled and non-equilibrium interaction. This study provides new insights into particle transport in unsaturated porous media and offers a model concept representing the relevant processes. PMID

  16. Biophysical studies of cholesterol in unsaturated phospholipid model membranes

    NASA Astrophysics Data System (ADS)

    Williams, Justin Adam

    Cellular membranes contain a staggering diversity of lipids. The lipids are heterogeneously distributed to create regions, or domains, whose physical properties differ from the bulk membrane and play an essential role in modulating the function of resident proteins. Many basic questions pertaining to the formation of these lateral assemblies remain. This research employs model membranes of well-defined composition to focus on the potential role of polyunsaturated fatty acids (PUFAs) and their interaction with cholesterol (chol) in restructuring the membrane environment. Omega-3 (n-3) PUFAs are the main bioactive components of fish oil, whose consumption alleviates a variety of health problems by a molecular mechanism that is unclear. We hypothesize that the incorporation of PUFAs into membrane lipids and the effect they have on molecular organization may be, in part, responsible. Chol is a major constituent in the plasma membrane of mammals. It determines the arrangement and collective properties of neighboring lipids, driving the formation of domains via differential affinity for different lipids. The molecular organization of 1-[2H31]palmitoyl-2-eicosapentaenoylphosphatidylcholine (PEPC-d31) and 1-[2H31]palmitoyl-2-docosahexaenoylphosphatidylcholine (PDPC-d31) in membranes with sphingomyelin (SM) and chol (1:1:1 mol) was compared by solid-state 2H NMR spectroscopy. Eicosapentaenoic (EPA) and docosahexaenoic (DHA) acids are the two major n-3 PUFAs found in fish oil, while PEPC-d31 and PDPC-d31 are phospholipids containing the respective PUFAs at the sn-2 position and a perdeuterated palmitic acid at the sn-1 position. Analysis of spectra recorded as a function of temperature indicates that in both cases, formation of PUFA-rich (less ordered) and SM-rich (more ordered) domains occurred. A surprisingly substantial proportion of PUFA was found to infiltrate the more ordered domain. There was almost twice as much DHA (65%) as EPA (30%). The implication is that n-3

  17. Number relativity

    NASA Astrophysics Data System (ADS)

    Shin, Philip

    Number relativity 1.Every equation of the relativity is just the way to understand through to solve one question of the math problem. We just add the hypothesis into the number. 2. Sequence of number is the machine physics for software(computer) as the number order is program equation as calculator. 3. When zero is denominator, it is not existing as it is doing something by nothing. So nothing means time as we put zero denominator into time. My personal physics imagine.

  18. Leftist Numbers

    ERIC Educational Resources Information Center

    Rich, Andrew

    2008-01-01

    The leftist number system consists of numbers with decimal digits arranged in strings to the left, instead of to the right. This system fails to be a field only because it contains zerodivisors. The same construction with prime base yields the p-adic numbers.

  19. Glucosylceramide having a novel tri-unsaturated long-chain base from the spermatozoa of the starfish, Asterias amurensis.

    PubMed

    Irie, A; Kubo, H; Hoshi, M

    1990-04-01

    Glucosylceramide (Glc beta 1-1Cer) was isolated from the spermatozoa of the starfish, Asterias amurensis. The long-chain bases of the glycolipid consisted of dihydroxy (d18:2, d18:3, d19:3, and d22:2), and trihydroxy (t22:1) types. Long-chain aldehydes derived from them were analyzed mainly by proton nuclear-magnetic resonance to determine the detailed structures. Two of the tri-unsaturated bases were identified as (4E,8E,10E)-2-amino-4,8,10-octadecatriene-1,3-di ol (d18:3) and (4E,8E,10E)-2-amino-9-methyl-4,8,10-octadecatriene+ ++-1,3-diol (d19:3), which is a novel base. Both d22:2 and t22:1 had a cis double bond at the C9 or C13 position. All fatty acids were 2-hydroxylated (C14-C25): Most of them were saturated and unbranched. About 10% was mono-unsaturated and unbranched (C22-C25), while saturated but branched (iso- and anteiso-types) C15-C18 acids were found as minor components. The main fatty acids, which summed up to more than 93% of the fatty acids in the glucosylceramide, were n-14h:0, n-15h:0, n-16h:0, n-17h:0, n-18h:0, and n-24h:1. PMID:2358431

  20. A Novel Unsaturated β-Glucuronyl Hydrolase Involved in Ulvan Degradation Unveils the Versatility of Stereochemistry Requirements in Family GH105*

    PubMed Central

    Collén, Pi Nyvall; Jeudy, Alexandra; Sassi, Jean-François; Groisillier, Agnès; Czjzek, Mirjam; Coutinho, Pedro M.; Helbert, William

    2014-01-01

    Ulvans are cell wall matrix polysaccharides in green algae belonging to the genus Ulva. Enzymatic degradation of the polysaccharide by ulvan lyases leads to the production of oligosaccharides with an unsaturated β-glucuronyl residue located at the non-reducing end. Exploration of the genomic environment around the Nonlabens ulvanivorans (previously Percicivirga ulvanivorans) ulvan lyase revealed a gene highly similar to known unsaturated uronyl hydrolases classified in the CAZy glycoside hydrolase family 105. The gene was cloned, the protein was overexpressed in Escherichia coli, and enzymology experiments demonstrated its unsaturated β-glucuronyl activity. Kinetic analysis of purified oligo-ulvans incubated with the new enzyme showed that the full substrate specificity is attained by three subsites that preferentially bind anionic residues (sulfated rhamnose, glucuronic/iduronic acid). The three-dimensional crystal structure of the native enzyme reveals that a trimeric organization is required for substrate binding and recognition at the +2 binding subsite. This novel unsaturated β-glucuronyl hydrolase is part of a previously uncharacterized subgroup of GH105 members and exhibits only a very limited sequence similarity to known unsaturated β-glucuronyl sequences previously found only in family GH88. Clan-O formed by families GH88 and GH105 was singular in the fact that it covered families acting on both axial and equatorial glycosidic linkages, respectively. The overall comparison of active site structures between enzymes from these two families highlights how that within family GH105, and unlike for classical glycoside hydrolysis, the hydrolysis of vinyl ether groups from unsaturated saccharides occurs independently of the α or β configuration of the cleaved linkage. PMID:24407291

  1. Linoleic acid suppresses cholesterol efflux and ATP-binding cassette transporters in murine bone marrow-derived macrophages

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Individuals with type 2 diabetes mellitus (T2DM) are at increased risk of developing cardiovascular disease (CVD), possibly associated with elevated plasma free fatty acid concentrations. Paradoxically, evidence suggests that unsaturated, compared to saturated fatty acids, suppress macrophage chole...

  2. Superharmonic numbers

    NASA Astrophysics Data System (ADS)

    Cohen, Graeme L.

    2009-03-01

    Let tau(n) denote the number of positive divisors of a natural number n>1 and let sigma(n) denote their sum. Then n is superharmonic if sigma(n)mid n^ktau(n) for some positive integer k . We deduce numerous properties of superharmonic numbers and show in particular that the set of all superharmonic numbers is the first nontrivial example that has been given of an infinite set that contains all perfect numbers but for which it is difficult to determine whether there is an odd member.

  3. 21 CFR 184.1065 - Linoleic acid.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Linoleic acid. 184.1065 Section 184.1065 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) DIRECT FOOD...-33-3)), a straight chain unsaturated fatty acid with a molecular weight of 280.5, is a colorless...

  4. Lipid and fatty acid analysis of the Plodia interpunctella granulosis virus (PiGV) envelope

    NASA Technical Reports Server (NTRS)

    Shastri-Bhalla, K.; Funk, C. J.; Consigli, R. A.; Spooner, B. S. (Principal Investigator)

    1993-01-01

    Virus envelope was isolated from Plodia interpunctella granulosis virus, produced in early fourth-instar larvae. Both polar and neutral lipids were analyzed by two-dimensional thin-layer chromatography. Fatty acid composition of various individual neutral and polar lipids was determined by gas-liquid chromatography. The major components of envelope neutral lipid were diacylglycerols. Palmitic acid and stearic acid were the major saturated fatty acids in both polar and neutral lipids. Whereas palmitoleic acid was the major unsaturated fatty acids in neutral lipids, oleic acid was the major unsaturated fatty acid in the polar lipids.

  5. Effect of extracellular fatty acids on lipid metabolism in cultured rabbit articular chondrocytes

    SciTech Connect

    Nagao, M.; Ishii, S.; Murata, Y.; Akino, T. )

    1991-05-01

    Rabbit articular chondrocytes were cultured for 8 h in the presence of various concentrations (5-500 microM) of {sup 14}C oleic, {sup 14}C linoleic, and {sup 3H} arachidonic acids. The radioactive unsaturated fatty acids were incorporated into triacylglycerol (TG) and phosphatidylcholine (PC) in a concentration-dependent manner; more fatty acids were incorporated into TG than into PC, at higher concentrations of extracellular fatty acids. Among these fatty acids, arachidonic acid was incorporated into TG much more than into PC, in spite of a very low concentration of arachidonic acid in TG. After transfer of the labeled cells to maintenance medium, the radioactivity in TG declined rapidly and {sup 3}H arachidonic acid radioactivity in PC increased continuously during the chase time periods. Palmitoyl-unsaturated species were mainly formed in PC when cultured at a concentration of 5 microM of each fatty acid. However, when cultured at 500 microM, unsaturated-unsaturated species, specific for each unsaturated fatty acid were actively formed. These findings indicate that (1) fatty acid composition of TG and PC in articular chondrocytes is influenced by the degree of fatty acid supply, (2) formation and turnover of TG plays a role in fatty acid metabolism of cells, and (3) fatty acid pairing in PC is modulated by extracellular fatty acid concentrations.

  6. Mutant fatty acid desaturase

    DOEpatents

    Shanklin, John; Cahoon, Edgar B.

    2004-02-03

    The present invention relates to a method for producing mutants of a fatty acid desaturase having a substantially increased activity towards fatty acid substrates with chains containing fewer than 18 carbons relative to an unmutagenized precursor desaturase having an 18 carbon atom chain length substrate specificity. The method involves inducing one or more mutations in the nucleic acid sequence encoding the precursor desaturase, transforming the mutated sequence into an unsaturated fatty acid auxotroph cell such as MH13 E. coli, culturing the cells in the absence of supplemental unsaturated fatty acids, thereby selecting for recipient cells which have received and which express a mutant fatty acid desaturase with an elevated specificity for fatty acid substrates having chain lengths of less than 18 carbon atoms. A variety of mutants having 16 or fewer carbon atom chain length substrate specificities are produced by this method. Mutant desaturases produced by this method can be introduced via expression vectors into prokaryotic and eukaryotic cells and can also be used in the production of transgenic plants which may be used to produce specific fatty acid products.

  7. Effects of unsaturated zone on ground-water mounding

    USGS Publications Warehouse

    Sumner, D.M.; Rolston, D.E.; Marino, M.A.

    1999-01-01

    The design of infiltration basins used to dispose of treated wastewater or for aquifer recharge often requires estimation of ground-water mounding beneath the basin. However, the effect that the unsaturated zone has on water-table response to basin infiltration often has been overlooked in this estimation. A comparison was made between two methods used to estimate ground-water mounding-an analytical approach that is limited to the saturated zone and a numerical approach that incorporates both the saturated and the unsaturated zones. Results indicate that the error that is introduced by a method that ignores the effects of the unsaturated zone on ground-water mounding increases as the basin-loading period is shortened; as the depth to the water table increases, with increasing subsurface anisotropy; and with the inclusion of fine-textured strata. Additionally, such a method cannot accommodate the dynamic nature of basin infiltration, the finite transmission time of the infiltration front to the water table, or the interception of the basin floor by the capillary fringe.The design of infiltration basins used to dispose of treated wastewater or for aquifer recharge often requires estimation of ground-water mounding beneath the basin. However, the effect that the unsaturated zone has on water-table response to basin infiltration often has been overlooked in this estimation. A comparison was made between two methods used to estimate ground-water mounding - an analytical approach that is limited to the saturated zone and a numerical approach that incorporates both the saturated and the unsaturated zones. Results indicate that the error that is introduced by a method that ignores the effects of the unsaturated zone on ground-water mounding increases as the basin-loading period is shortened; as the depth to the water table increases, with increasing subsurface anisotropy; and with the inclusion of fine-textured strata. Additionally, such a method cannot accommodate the

  8. Dietary Lipid Type, Rather Than Total Number of Calories, Alters Outcomes of Enteric Infection in Mice.

    PubMed

    DeCoffe, Daniella; Quin, Candice; Gill, Sandeep K; Tasnim, Nishat; Brown, Kirsty; Godovannyi, Artem; Dai, Chuanbin; Abulizi, Nijiati; Chan, Yee Kwan; Ghosh, Sanjoy; Gibson, Deanna L

    2016-06-01

    Dietary lipids modulate immunity, yet the means by which specific fatty acids affect infectious disease susceptibility remains unclear. Deciphering lipid-induced immunity is critical to understanding the balance required for protecting against pathogens while avoiding chronic inflammatory diseases. To understand how specific lipids alter susceptibility to enteric infection, we fed mice isocaloric, high-fat diets composed of corn oil (rich in n-6 polyunsaturated fatty acids [n-6 PUFAs]), olive oil (rich in monounsaturated fatty acids), or milk fat (rich in saturated fatty acids) with or without fish oil (rich in n-3 PUFAs). After 5 weeks of dietary intervention, mice were challenged with Citrobacter rodentium, and pathological responses were assessed. Olive oil diets resulted in little colonic pathology associated with intestinal alkaline phosphatase, a mucosal defense factor that detoxifies lipopolysaccharide. In contrast, while both corn oil and milk fat diets resulted in inflammation-induced colonic damage, only milk fat induced compensatory protective responses, including short chain fatty acid production. Fish oil combined with milk fat, unlike unsaturated lipid diets, had a protective effect associated with intestinal alkaline phosphatase activity. Overall, these results reveal that dietary lipid type, independent of the total number of calories associated with the dietary lipid, influences the susceptibility to enteric damage and the benefits of fish oil during infection. PMID:27067195

  9. Unsaturation of very-long-chain ceramides protects plant from hypoxia-induced damages by modulating ethylene signaling in Arabidopsis.

    PubMed

    Xie, Li-Juan; Chen, Qin-Fang; Chen, Mo-Xian; Yu, Lu-Jun; Huang, Li; Chen, Liang; Wang, Feng-Zhu; Xia, Fan-Nv; Zhu, Tian-Ren; Wu, Jian-Xin; Yin, Jian; Liao, Bin; Shi, Jianxin; Zhang, Jian-Hua; Aharoni, Asaph; Yao, Nan; Shu, Wensheng; Xiao, Shi

    2015-03-01

    Lipid remodeling is crucial for hypoxic tolerance in animals, whilst little is known about the hypoxia-induced lipid dynamics in plants. Here we performed a mass spectrometry-based analysis to survey the lipid profiles of Arabidopsis rosettes under various hypoxic conditions. We observed that hypoxia caused a significant increase in total amounts of phosphatidylserine, phosphatidic acid and oxidized lipids, but a decrease in phosphatidylcholine (PC) and phosphatidylethanolamine (PE). Particularly, significant gains in the polyunsaturated species of PC, PE and phosphatidylinositol, and losses in their saturated and mono-unsaturated species were evident during hypoxia. Moreover, hypoxia led to a remarkable elevation of ceramides and hydroxyceramides. Disruption of ceramide synthases LOH1, LOH2 and LOH3 enhanced plant sensitivity to dark submergence, but displayed more resistance to submergence under light than wild type. Consistently, levels of unsaturated very-long-chain (VLC) ceramide species (22:1, 24:1 and 26:1) predominantly declined in the loh1, loh2 and loh3 mutants under dark submergence. In contrast, significant reduction of VLC ceramides in the loh1-1 loh3-1 knockdown double mutant and lacking of VLC unsaturated ceramides in the ads2 mutants impaired plant tolerance to both dark and light submergences. Evidence that C24:1-ceramide interacted with recombinant CTR1 protein and inhibited its kinase activity in vitro, enhanced ER-to-nucleus translocation of EIN2-GFP and stabilization of EIN3-GFP in vivo, suggests a role of ceramides in modulating CTR1-mediated ethylene signaling. The dark submergence-sensitive phenotypes of loh mutants were rescued by a ctr1-1 mutation. Thus, our findings demonstrate that unsaturation of VLC ceramides is a protective strategy for hypoxic tolerance in Arabidopsis. PMID:25822663

  10. Unsaturation of Very-Long-Chain Ceramides Protects Plant from Hypoxia-Induced Damages by Modulating Ethylene Signaling in Arabidopsis

    PubMed Central

    Yu, Lu-Jun; Huang, Li; Chen, Liang; Wang, Feng-Zhu; Xia, Fan-Nv; Zhu, Tian-Ren; Wu, Jian-Xin; Yin, Jian; Liao, Bin; Shi, Jianxin; Zhang, Jian-Hua; Aharoni, Asaph; Yao, Nan; Shu, Wensheng; Xiao, Shi

    2015-01-01

    Lipid remodeling is crucial for hypoxic tolerance in animals, whilst little is known about the hypoxia-induced lipid dynamics in plants. Here we performed a mass spectrometry-based analysis to survey the lipid profiles of Arabidopsis rosettes under various hypoxic conditions. We observed that hypoxia caused a significant increase in total amounts of phosphatidylserine, phosphatidic acid and oxidized lipids, but a decrease in phosphatidylcholine (PC) and phosphatidylethanolamine (PE). Particularly, significant gains in the polyunsaturated species of PC, PE and phosphatidylinositol, and losses in their saturated and mono-unsaturated species were evident during hypoxia. Moreover, hypoxia led to a remarkable elevation of ceramides and hydroxyceramides. Disruption of ceramide synthases LOH1, LOH2 and LOH3 enhanced plant sensitivity to dark submergence, but displayed more resistance to submergence under light than wild type. Consistently, levels of unsaturated very-long-chain (VLC) ceramide species (22:1, 24:1 and 26:1) predominantly declined in the loh1, loh2 and loh3 mutants under dark submergence. In contrast, significant reduction of VLC ceramides in the loh1-1 loh3-1 knockdown double mutant and lacking of VLC unsaturated ceramides in the ads2 mutants impaired plant tolerance to both dark and light submergences. Evidence that C24:1-ceramide interacted with recombinant CTR1 protein and inhibited its kinase activity in vitro, enhanced ER-to-nucleus translocation of EIN2-GFP and stabilization of EIN3-GFP in vivo, suggests a role of ceramides in modulating CTR1-mediated ethylene signaling. The dark submergence-sensitive phenotypes of loh mutants were rescued by a ctr1-1 mutation. Thus, our findings demonstrate that unsaturation of VLC ceramides is a protective strategy for hypoxic tolerance in Arabidopsis. PMID:25822663

  11. Demospongic Acids Revisited

    PubMed Central

    Kornprobst, Jean-Michel; Barnathan, Gilles

    2010-01-01

    The well-known fatty acids with a Δ5,9 unsaturation system were designated for a long period as demospongic acids, taking into account that they originally occurred in marine Demospongia sponges. However, such acids have also been observed in various marine sources with a large range of chain-lengths (C16–C32) and from some terrestrial plants with short acyl chains (C18–C19). Finally, the Δ5,9 fatty acids appear to be a particular type of non-methylene-interrupted fatty acids (NMA FAs). This article reviews the occurrence of these particular fatty acids in marine and terrestrial organisms and shows the biosynthetic connections between Δ5,9 fatty acids and other NMI FAs. PMID:21116406

  12. N-Alkylated dinitrones from isosorbide as cross-linkers for unsaturated bio-based polyesters.

    PubMed

    Goerz, Oliver; Ritter, Helmut

    2014-01-01

    Isosorbide was esterified with acryloyl chloride and crotonic acid yielding isosorbide diacrylate (9a) and isosorbide dicrotonate (9b), which were reacted with benzaldehyde oxime in the presence of zinc(II) iodide and boron triflouride etherate as catalysts to obtain N-alkylated dinitrones 10a/b. Poly(isosorbide itaconite -co- succinate) 13 as a bio-based unsaturated polyester was cross-linked by a 1,3-dipolar cycloaddition with the received dinitrones 10a/b. The 1,3-dipolar cycloaddition led to a strong change of the mechanical properties which were investigated by rheological measurements. Nitrones derived from methyl acrylate (3a) and methyl crotonate (3b) were used as model systems and reacted with dimethyl itaconate to further characterize the 1,3-dipolaric cycloaddition. PMID:24991239

  13. N-Alkylated dinitrones from isosorbide as cross-linkers for unsaturated bio-based polyesters

    PubMed Central

    Goerz, Oliver

    2014-01-01

    Summary Isosorbide was esterified with acryloyl chloride and crotonic acid yielding isosorbide diacrylate (9a) and isosorbide dicrotonate (9b), which were reacted with benzaldehyde oxime in the presence of zinc(II) iodide and boron triflouride etherate as catalysts to obtain N-alkylated dinitrones 10a/b. Poly(isosorbide itaconite -co- succinate) 13 as a bio-based unsaturated polyester was cross-linked by a 1,3-dipolar cycloaddition with the received dinitrones 10a/b. The 1,3-dipolar cycloaddition led to a strong change of the mechanical properties which were investigated by rheological measurements. Nitrones derived from methyl acrylate (3a) and methyl crotonate (3b) were used as model systems and reacted with dimethyl itaconate to further characterize the 1,3-dipolaric cycloaddition. PMID:24991239

  14. Phenotypic population screen identifies a new mutation in bovine DGAT1 responsible for unsaturated milk fat

    PubMed Central

    Lehnert, Klaus; Ward, Hamish; Berry, Sarah D.; Ankersmit-Udy, Alex; Burrett, Alayna; Beattie, Elizabeth M.; Thomas, Natalie L.; Harris, Bevin; Ford, Christine A.; Browning, Sharon R.; Rawson, Pisana; Verkerk, Gwyneth A.; van der Does, Yvonne; Adams, Linda F.; Davis, Stephen R.; Jordan, T. William; MacGibbon, Alastair K. H.; Spelman, Richard J.; Snell, Russell G.

    2015-01-01

    Selective breeding has strongly reduced the genetic diversity in livestock species, and contemporary breeding practices exclude potentially beneficial rare genetic variation from the future gene pool. Here we test whether important traits arising by new mutations can be identified and rescued in highly selected populations. We screened milks from 2.5 million cows to identify an exceptional individual which produced milk with reduced saturated fat content, and improved unsaturated and omega-3 fatty acid concentrations. The milk traits were transmitted dominantly to her offspring, and genetic mapping and genome sequencing revealed a new mutation in a previously unknown splice enhancer of the DGAT1 gene. Homozygous carriers show features of human diarrheal disorders, and may be useful for the development of therapeutic strategies. Our study demonstrates that high-throughput phenotypic screening can uncover rich genetic diversity even in inbred populations, and introduces a novel strategy to develop novel milks with improved nutritional properties. PMID:25719731

  15. Data assimilation for unsaturated flow models with restart adaptive probabilistic collocation based Kalman filter

    NASA Astrophysics Data System (ADS)

    Man, Jun; Li, Weixuan; Zeng, Lingzao; Wu, Laosheng

    2016-06-01

    The ensemble Kalman filter (EnKF) has gained popularity in hydrological data assimilation problems. As a Monte Carlo based method, a sufficiently large ensemble size is usually required to guarantee the accuracy. As an alternative approach, the probabilistic collocation based Kalman filter (PCKF) employs the polynomial chaos expansion (PCE) to represent and propagate the uncertainties in parameters and states. However, PCKF suffers from the so-called "curse of dimensionality". Its computational cost increases drastically with the increasing number of parameters and system nonlinearity. Furthermore, PCKF may fail to provide accurate estimations due to the joint updating scheme for strongly nonlinear models. Motivated by recent developments in uncertainty quantification and EnKF, we propose a restart adaptive probabilistic collocation based Kalman filter (RAPCKF) for data assimilation in unsaturated flow problems. During the implementation of RAPCKF, the important parameters are identified and active PCE basis functions are adaptively selected at each assimilation step; the "restart" scheme is utilized to eliminate the inconsistency between updated model parameters and states variables. The performance of RAPCKF is systematically tested with numerical cases of unsaturated flow models. It is shown that the adaptive approach and restart scheme can significantly improve the performance of PCKF. Moreover, RAPCKF has been demonstrated to be more efficient than EnKF with the same computational cost.

  16. Unsaturated water flow at the Hanford site: a review of literature and annotated bibliography

    SciTech Connect

    Gee, G.W.; Heller, P.R.

    1985-05-01

    As an initial part of a performance assessment task for the Hanford Waste Management Plan, we have reviewed research done over a number of years on unsaturated water flow at the Hanford site near Richland, Washington. This work will be helpful in assessing the probability that water infiltrating the ground surface may eventually contribute to ground-water recharge at the site. Reports done primarily by Atlantic Richfield Hanford, Rockwell Hanford Operations, and Pacific Northwest Laboratory were reviewed for their pertinence to unsaturated water flow and specifically for information that could help resolve the question of whether recharge of the unconfined aquifer by natural precipitation (meteoric water) is occurring on the Hanford site and, if so, what are the expected ranges of recharge. The reports that we reviewed are primarily technical reports detailing the physical and hydrologic characteristics of soils and sediments at specific locations on the Hanford site, or describing studies that have either monitored or simulated such parameters as surface evaporation, soil moisture storage, and deep drainage (recharge). The appendix of this report provides abstracts and annotations on 24 key technical reports on subjects related to estimation of recharge at Hanford. 66 refs.

  17. Optimizing the experimental design of soil columns in saturated and unsaturated transport experiments

    NASA Astrophysics Data System (ADS)

    Lewis, Jeffrey; Sjöstrom, Jan

    2010-06-01

    Soil column experiments in both the saturated and unsaturated regimes are widely used for applied and theoretical studies in such diverse fields as transport model evaluation, fate and transport of pesticides, explosives, microbes, heavy metals and non aqueous phase liquids, and for evapotranspiration studies. The apparent simplicity of constructing soil columns conceals a number of technical issues which can seriously affect the outcome of an experiment, such as the presence or absence of macropores, artificial preferential flow paths, non-ideal infiltrate injection and unrealistic moisture regimes. This review examines the literature to provide an analysis of the state of the art for constructing both saturated and unsaturated soil columns. Common design challenges are discussed and best practices for potential solutions are presented. This article discusses both basic principles and the practical advantages and disadvantages of various experimental approaches. Both repacked and monolith-type columns are discussed. The information in this review will assist soil scientists, hydrogeologists and environmental professionals in optimizing the construction and operation of soil column experiments in order to achieve their objectives, while avoiding serious design flaws which can compromise the integrity of their results.

  18. An Integrated Modeling Analysis of Unsaturated Flow Patterns inFractured Rock

    SciTech Connect

    Wu, Yu-Shu; Lu, Guoping; Zhang, Keni; Pan, Lehua; Bodvarsson,Gudmundur S.

    2005-03-21

    Characterizing percolation patterns in unsaturated zones hasposed a greater challenge to numerical modeling investigations thancomparable saturated zone studies, because of the heterogeneous nature ofunsaturated media as well as the great number of variables impactingunsaturated zone flow. This paper presents an integrated modelingmethodology for quantitatively characterizing percolation patterns in theunsaturated zone of Yucca Mountain, Nevada, a proposed undergroundrepository site for storing high-level radioactive waste. It takes intoaccount the multiple coupled processes of air, water, heat flow andchemical isotopic transport in Yucca Mountain s highly heterogeneous,unsaturated fractured tuffs. The modeling approach integrates a widevariety of moisture, pneumatic, thermal, and isotopic geochemical fielddata into a comprehensive three-dimensional numerical model for modelinganalyses. Modeling results are examined against different types offield-measured data and then used to evaluate different hydrogeologicalconceptual models and their results of flow patterns in the unsaturatedzone. In particular, this integration model provides a much clearerunderstanding of percolation patterns and flow behavior through theunsaturated zone, both crucial issues in assessing repositoryperformance. The integrated approach for quantifying Yucca Mountain sflow system is also demonstrated to provide a comprehensive modeling toolfor characterizing flow and transport processes in complex subsurfacesystems.

  19. Alpha chain unsaturated derivatives of misoprostol.

    PubMed

    Collins, P W; Gasiecki, A F; Weier, R M; Kramer, S W; Jones, P H; Gullikson, G W; Bianchi, R G; Bauer, R F

    1987-01-01

    Misoprostol, a 15-deoxy-16-hydroxy-16-methyl analog of PGE1, is an effective agent for the treatment of peptic ulcer disease. Efforts to impede metabolic degradation of the alpha chain of misoprostol led to the discovery of a second clinical candidate in this series. Enisoprost, a delta 4Z derivative of misoprostol, is more potent as a gastric antisecretory agent and longer acting than misoprostol. These findings prompted further work to determine the effects that two double bonds in the alpha chain might have on the activity profile of misoprostol. The most promising structure in this series was a 1:1 mixture of 3E,5Z and 3Z,5Z dienes which was about three times more potent than misoprostol in inhibiting gastric secretion in dogs, while the separation of the diarrheogenic effect was significantly improved. Chromatographic separation of the mixture was very difficult, but small amounts of each isomer were obtained by HPLC, and preliminary antisecretory studies indicated that most of the activity resided in the 3E,5Z isomer. A stereospecific synthesis of the 3E,5Z isomer was carried out to provide sufficient quantities for complete pharmacological assessment. The 3E,5Z diene was about three times more potent than misoprostol in inhibiting gastric acid secretion in dogs and also in producing diarrhea in rats. PMID:3122273

  20. Unsaturated FAs prevent palmitate-induced LOX-1 induction via inhibition of ER stress in macrophages

    PubMed Central

    Ishiyama, Junichi; Taguchi, Ryoko; Akasaka, Yunike; Shibata, Saiko; Ito, Minoru; Nagasawa, Michiaki; Murakami, Koji

    2011-01-01

    Palmitic acid (PA) upregulates oxidized LDL receptor-1 (LOX-1), a scavenger receptor responsible for uptake of oxidized LDL (oxLDL), and enhances oxLDL uptake in macrophages. However, the precise underlying mechanism remains to be elucidated. PA is known to induce endoplasmic reticulum (ER) stress in various cell types. Therefore, we investigated whether ER stress is involved in PA-induced LOX-1 upregulation. PA induced ER stress, as determined by phosphorylation of PERK, eIF2α, and JNK, as well as induction of CHOP in macrophage-like THP-1 cells. Inhibitors [4-phenylbutyric acid (PBA), sodium tauroursodeoxycholate (TUDCA), and salubrinal] and small interfering RNA (siRNA) for the ER stress response decreased PA-induced LOX-1 upregulation. Thapsigargin, an ER stress inducer, upregulated LOX-1, which was decreased by PBA and TUDCA. We next examined whether unsaturated FAs could counteract the effect of PA. Both oleic acid (OA) and linoleic acid (LA) suppressed PA-induced LOX-1. Activation of the ER stress response observed in the PA-treated cells was markedly attenuated when the cells were cotreated with OA or LA. In addition, OA and LA suppressed thapsigargin-induced LOX-1 upregulation with reduced activation of ER stress markers. Our results indicate that activation of ER stress is involved in PA-induced LOX-1 upregulation in macrophages, and that OA and LA inhibit LOX-1 induction through suppression of ER stress. PMID:21078775

  1. Genetic resources of the functional food, teramnus labialis (L.f.) spreng for improving seed number, flavonol content, oil %, and fatty acid compositions

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Teramnus labialis is used as food in India and has potential to be used as a functional food vegetable in the U.S.A. Photoperiod-sensitive T. labialis accessions were grown in the greenhouse from 2010 to 2011 and evaluated for flavonol content, oil %, and fatty acid compositions. Significant variati...

  2. Increased catabolism and decreased unsaturation of ganglioside in patients with inflammatory bowel disease

    PubMed Central

    Miklavcic, John J; Hart, Tasha DL; Lees, Gordon M; Shoemaker, Glen K; Schnabl, Kareena L; Larsen, Bodil MK; Bathe, Oliver F; Thomson, Alan BR; Mazurak, Vera C; Clandinin, M Tom

    2015-01-01

    AIM: To investigate whether accelerated catabolism of ganglioside and decreased ganglioside content contribute to the etiology of pro-inflammatory intestinal disease. METHODS: Intestinal mucosa from terminal ileum or colon was obtained from patients with ulcerative colitis or inflammatory Crohn’s disease (n = 11) undergoing bowel resection and compared to control samples of normal intestine from patients with benign colon polyps (n = 6) and colorectal cancer (n = 12) in this observational case-control study. Gangliosides and phospholipids of intestinal mucosa were characterized by class and ceramide or fatty acid composition using liquid chromatography triple-quad mass spectrometry. Content and composition of ganglioside classes GM1, GM3, GD3, GD1a, GT1 and GT3 were compared among subject groups. Content and composition of phospholipid classes phosphatidylcholine (PC) and phosphatidylethanolamine were compared among subject groups. Unsaturation index of individual ganglioside and phospholipid classes was computed and compared among subject groups. Ganglioside catabolism enzymes beta-hexosaminidase A (HEXA) and sialidase-3 (NEU3) were measured in intestinal mucosa using western blot and compared among subject groups. RESULTS: Relative GM3 ganglioside content was 2-fold higher (P < 0.05) in intestine from patients with inflammatory bowel disease (IBD) compared to control intestine. The quantity of GM3 and ratio of GM3/GD3 was also higher in IBD intestine than control tissue (P < 0.05). Control intestine exhibited 3-fold higher (P < 0.01) relative GD1a ganglioside content than IBD intestine. GD3 and GD1a species of ganglioside containing three unsaturated bonds were present in control intestine, but were not detected in IBD intestine. The relative content of PC containing more than two unsaturated bonds was 30% lower in IBD intestine than control intestine (P < 0.05). The relative content of HEXA in IBD intestine was increased 1.7-fold (P < 0.05) and NEU3 was

  3. Enhancement of lipid production and fatty acid profiling in Chlamydomonas reinhardtii, CC1010 for biodiesel production.

    PubMed

    Karpagam, R; Preeti, R; Ashokkumar, B; Varalakshmi, P

    2015-11-01

    Lipid from microalgae is one of the putative oil resources to facilitate the biodiesel production during this era of energy dissipation and environmental pollution. In this study, the key parameters such as biomass productivity, lipid productivity and lipid content were evaluated at the early stationary phase of Chlamydomonas reinhardtii, CC1010 cultivated in nutrient starved (nitrogen, phosphorous), glucose (0.05%, 0.1%, 0.15% and 0.2%) and vitamin B12 supplementation (0.001%, 0.002% and 0.003%) in Tris-Acetate-Phosphate (TAP) medium. The lipid content in nitrogen starved media was 61% which is 2.34 folds higher than nutrient sufficient TAP medium. Glucose supplementation has lead to proportional increase in biomass productivity with the increasing concentration of glucose whereas vitamin B12 supplementations had not shown any influence in lipid and biomass production. Further, fatty acid methyl ester (FAME) profiling of C. reinhardtii, CC 1010 has revealed more than 80% of total SFA (saturated fatty acid) and MUFA (mono unsaturated fatty acid) content. Quality checking parameters of biodiesel like cetane number, saponification value, iodine number and degree of unsaturation were analyzed and the biodiesel fuel properties were found to be appropriate as per the international standards, EN 14214 and ASTM D6751. Conclusively, among all the treatments, nitrogen starvation with 0.1% glucose supplementation had yielded high lipid content in C. reinhardtii, CC 1010. PMID:25838071

  4. Discovery of essential fatty acids

    PubMed Central

    Spector, Arthur A.; Kim, Hee-Yong

    2015-01-01

    Dietary fat was recognized as a good source of energy and fat-soluble vitamins by the first part of the 20th century, but fatty acids were not considered to be essential nutrients because they could be synthesized from dietary carbohydrate. This well-established view was challenged in 1929 by George and Mildred Burr who reported that dietary fatty acid was required to prevent a deficiency disease that occurred in rats fed a fat-free diet. They concluded that fatty acids were essential nutrients and showed that linoleic acid prevented the disease and is an essential fatty acid. The Burrs surmised that other unsaturated fatty acids were essential and subsequently demonstrated that linolenic acid, the omega-3 fatty acid analog of linoleic acid, is also an essential fatty acid. The discovery of essential fatty acids was a paradigm-changing finding, and it is now considered to be one of the landmark discoveries in lipid research. PMID:25339684

  5. Mobility of Metal Tracers in Unsaturated Tuffs of Busted Butte, Nevada

    SciTech Connect

    A.R. Groffman; H.J. Turin; J. Roach; C.L. Jones; W.E. Soll

    2003-09-20

    A complex tracer mixture was injected continuously for over two years into a 10 m x 10 m x 7 m block of unsaturated tuff as part of the Busted Butte unsaturated-zone tracer test at Yucca Mountain. The test was designed to measure tracer transport within the Topopah Springs and Calico Hills tuffs, units that occur between the potential high-level nuclear waste repository at Yucca Mountain and the water table below. The mixture included nonreactive (Br, I, and fluorinated benzoic acids (FBAs)) and reactive tracers (Li, Ce, Sm, Ni, Co, and Mn). Bromide, I, FBAs, and Li were detected during the test on absorbent pads emplaced in a series of solute collection boreholes located beneath the injectors but the more strongly sorbing metals did not reach the collection boreholes during this period. To determine the distribution and mobility of these metals, tracer constituents were extracted from tuff samples collected during overcoring and mineback of the test block. Tracers were extracted from the tuff samples by leaching with a 5% nitric acid solution for metals and a bicarbonate-carbonate buffer for anions. Results from the overcore sample suite show that metals have migrated through the tuff in the region adjacent to and immediately below the tracer injectors. Consistent with laboratory sorption measurements and observed breakthrough in the collection boreholes, rock analyses showed that Li is the most mobile of the metals. Co and Ni behave similarly, traveling tens of cm from the injection sites, while Sm and Ce moved far less, possibly due to precipitation reactions in addition to sorption. Determination of Mn transport is complicated by high background concentrations in the tuff; additional background samples are currently being evaluated. As expected, the rock analyses show that the nonreactive tracers Br and FBAs have moved beyond the overcore region, corroborating results from collection boreholes.

  6. Effect of fatty acids on self-assembly of soybean lecithin systems.

    PubMed

    Godoy, C A; Valiente, M; Pons, R; Montalvo, G

    2015-07-01

    With the increasing interest in natural formulations for drug administration and functional foods, it is desirable a good knowledge of the phase behavior of lecithin/fatty acid formulations. Phase structure and properties of ternary lecithin/fatty acids/water systems are studied at 37°C, making emphasis in regions with relatively low water and fatty acid content. The effect of fatty acid saturation degree on the phase microstructure is studied by comparing a fully saturated (palmitic acid, C16:0), monounsaturated (oleic acid, C18:1), and diunsaturated (linoleic acid, C18:2) fatty acids. Phase determinations are based on a combination of polarized light microscopy and small-angle X-ray scattering measurements. Interestingly, unsaturated (oleic acid and linoleic acid) fatty acid destabilizes the lamellar bilayer. Slight differences are observed between the phase diagrams produced by the unsaturated ones: small lamellar, medium cubic and large hexagonal regions. A narrow isotropic fluid region also appears on the lecithin-fatty acid axis, up to 8wt% water. In contrast, a marked difference in phase microsctructure was observed between unsaturated and saturated systems in which the cubic and isotropic fluid phases are not formed. These differences are, probably, a consequence of the high Krafft point of the C16 saturated chains that imply rather rigid chains. However, unsaturated fatty acids result in more flexible tails. The frequent presence of, at least, one unsaturated chain in phospholipids makes it very likely a better mixing situation than in the case of more rigid chains. This swelling potential favors the formation of reverse hexagonal, cubic, and micellar phases. Both unsaturated fatty acid systems evolve by aging, with a reduction of the extension of reverse hexagonal phase and migration of the cubic phase to lower fatty acid and water contents. The kinetic stability of the systems seems to be controlled by the unsaturation of fatty acids. PMID:25938851

  7. Transport of Polycyclic Aromatic Hydrocarbons in Unsaturated Porous Media

    NASA Astrophysics Data System (ADS)

    Chahal, Maninder; Flury, Markus

    2016-04-01

    Polycyclic aromatic hydrocarbons (PAHs) are complex organic molecules containing 2 or more fused benzene rings. Being hydrophobic and non-polar, PAHs tend to partition to the organic matter in the soil from bulk aqueous phase. Though transport of these contaminants has been well studied in saturated environment, interactive mechanisms of these fluorescent compounds in unsaturated (identified by presence of air-water interface) porous media is still not well understood. We studied is the transport of fluoranthene in unsaturated porous media as facilitated by moving air-water interfaces. Confocal microscopy was used to visualize the interactions of fluoranthene particles in a glass channel packed with quartz glass beads. The packed glass channel was used to mimic a porous media and effects of an advancing and receding capillary fringe on the detachment of fluoranthene.

  8. Comparison of Measured and Estimated Unsaturated Hydraulic Conductivity

    NASA Astrophysics Data System (ADS)

    Parkes, M. E.; Waters, P. A.

    1980-08-01

    Most studies of empirical estimates of unsaturated hydraulic conductivity functions do not account for water which may be relatively immobile under the conditions in which field measurements of conductivity are made. To investigate this, unsaturated hydraulic conductivity data were obtained for three monolith lysimeters, 80 cm in diameter by 135 cm deep, using the instantaneous profile technique. The lysimeters contained well-structured, freely draining loam soil and moisture measurements were made using a neutron probe. Conductivity estimates were also obtained from laboratory measurements of soil moisture characteristics using the modified Millington and Quirk computational method. Ratios of the calculated to measured conductivities at a matching point near saturation were so large as to suggest that only a minor proportion of the soil pore space was contributing to flow through the whole profile.

  9. Flow focusing in unsaturated fracture networks: A numerical investigation

    SciTech Connect

    Zhang, Keni; Wu, Yu-Shu; Bodvarsson, G.S.; Liu, Hui-Hai

    2003-04-17

    A numerical modeling study is presented to investigate flow-focusing phenomena in a large-scale fracture network, constructed using field data collected from the unsaturated zone of Yucca Mountain, Nevada, the proposed repository site for high-level nuclear waste. The two-dimensional fracture network for an area of 100 m x 150 m contains more than 20,000 fractures. Steady-state unsaturated flow in the fracture network is investigated for different boundary conditions and rock properties. Simulation results indicate that flow paths are generally vertical, and that horizontal fractures mainly provide pathways between neighboring vertical paths. In addition to fracture properties, flow-focusing phenomena are also affected by rock-matrix permeability, with lower matrix permeability leading to a high degree of flow focusing. The simulation results further indicate that the average spacing between flow paths in a layered system tends to increase and flow tends to becomes more focused, with depth.

  10. Fractal Analysis of Permeability of Unsaturated Fractured Rocks

    PubMed Central

    Jiang, Guoping; Shi, Wei; Huang, Lili

    2013-01-01

    A physical conceptual model for water retention in fractured rocks is derived while taking into account the effect of pore size distribution and tortuosity of capillaries. The formula of calculating relative hydraulic conductivity of fractured rock is given based on fractal theory. It is an issue to choose an appropriate capillary pressure-saturation curve in the research of unsaturated fractured mass. The geometric pattern of the fracture bulk is described based on the fractal distribution of tortuosity. The resulting water content expression is then used to estimate the unsaturated hydraulic conductivity of the fractured medium based on the well-known model of Burdine. It is found that for large enough ranges of fracture apertures the new constitutive model converges to the empirical Brooks-Corey model. PMID:23690746

  11. Synthesis of phenoxy ethers of methyl lesquerolate over solid acid catalysts

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Lesquerolic acid is the primary fatty acid found in Lesquerella. The seeds are 33% oil of which about 55% is the 20 carbon unsaturated hydroxyl fatty acid, lesquerolic acid. A simple derivatization of this fatty acid could expand its potential as an industrial oil. We have used a heterogeneous Le...

  12. Potential Approach of Microbial Conversion to Develop New Antifungal Products of Omega-3 Fatty Acids

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Omega-3/('-3) or n-3 fatty acids are a family of unsaturated fatty acids that have in common a final carbon-carbon double bond in the n-3 position. n-3 Fatty acids which are important in human nutrition are: a-linolenic acid (18:3, n-3; ALA), eicosapentaenoic acid (20:5, n-3; EPA), and docosahexaen...

  13. Volatile organic compounds in the unsaturated zone from radioactive wastes.

    PubMed

    Baker, Ronald J; Andraski, Brian J; Stonestrom, David A; Luo, Wentai

    2012-01-01

    Volatile organic compounds (VOCs) are often comingled with low-level radioactive wastes (LLRW), but little is known about subsurface VOC emanations from LLRW landfills. The current study systematically quantified VOCs associated with LLRW over an 11-yr period at the USGS Amargosa Desert Research Site (ADRS) in southwestern Nevada. Unsaturated-zone gas samples of VOCs were collected by adsorption on resin cartridges and analyzed by thermal desorption and GC/MS. Sixty of 87 VOC method analytes were detected in the 110-m-thick unsaturated zone surrounding a LLRW disposal facility. Chlorofluorocarbons (CFCs) were detected in 100% of samples collected. Chlorofluorocarbons are powerful greenhouse gases, deplete stratospheric ozone, and are likely released from LLRW facilities worldwide. Soil-gas samples collected from a depth of 24 m and a horizontal distance 100 m south of the nearest waste-disposal trench contained >60,000 ppbv total VOCs, including >37,000 ppbv CFCs. Extensive sampling in the shallow unsaturated zone (0-2 m deep) identified areas where total VOC concentrations exceeded 5000 ppbv at the 1.5-m depth. Volatile organic compound concentrations exceeded background levels up to 300 m from the facility. Maximum vertical diffusive fluxes of total VOCs were estimated to be 1 g m yr. Volatile organic compound distributions were similar but not identical to those previously determined for tritium and elemental mercury. To our knowledge, this study is the first to characterize the unsaturated zone distribution of VOCs emanating from a LLRW landfill. Our results may help explain anomalous transport of radionuclides at the ADRS and elsewhere. PMID:22751077

  14. Do Karstic Unsaturated Zones Have the Fastest Preferential Flow?

    NASA Astrophysics Data System (ADS)

    Nimmo, J. R.; Perkins, K. S.

    2013-12-01

    There is strong evidence that unsaturated-zone travel times for preferential flow, unlike those for diffuse flow, mostly fall within a relatively small range, even for a wide variety of media and conditions [Nimmo, 2007, Water Resources Research]. We have calculated travel times for preferential flow observations published in the last seven years, finding a range of travel velocities with a greater maximum than was previously recognized. The instances of faster transport, however, are predominantly for karst or other materials in which water flow may strongly influence the creation and development of preferential flow paths. These findings motivate a hypothesis: in media where the matrix is soluble, erodible, or otherwise vulnerable to enlargement by flowing water, this flow acts to reduce flow impediments within a macropore network. This might be thought of as a sculpting process in which water carves its conduit into a smoother, larger, less constrictive shape, as discussed in connection with soil pipes [Jones, 2010, Hydrological Processes]. Known developmental processes of karst and epikarst are consistent with this hypothesis. Its acceptance would open doors to expanded use of optimality and thermodynamic principles to understand and predict preferential flow. It also could lead to new modes of hydraulic characterization of subsurface media with regard to unsaturated flow, which are much needed as the difficulty of measuring hydraulic properties of the unsaturated zone is a major barrier to the advance of hydrologic science. In practical terms, a new guideline may be justified: in unsaturated karst or other materials in which flowing water may enhance flowpaths, preferential transport rates in general may be several times faster than through media without such pore-developmental processes.

  15. Artificial recharge through a thick, heterogeneous unsaturated zone.

    PubMed

    Izbicki, John A; Flint, Alan L; Stamos, Christina L

    2008-01-01

    Thick, heterogeneous unsaturated zones away from large streams in desert areas have not previously been considered suitable for artificial recharge from ponds. To test the potential for recharge in these settings, 1.3 x 10(6) m(3) of water was infiltrated through a 0.36-ha pond along Oro Grande Wash near Victorville, California, between October 2002 and January 2006. The pond overlies a regional pumping depression 117 m below land surface and is located where thickness and permeability of unsaturated deposits allowed infiltration and saturated alluvial deposits were sufficiently permeable to allow recovery of water. Because large changes in water levels caused by nearby pumping would obscure arrival of water at the water table, downward movement of water was measured using sensors in the unsaturated zone. The downward rate of water movement was initially as high as 6 m/d and decreased with depth to 0.07 m/d; the initial time to reach the water table was 3 years. After the unsaturated zone was wetted, water reached the water table in 1 year. Soluble salts and nitrate moved readily with the infiltrated water, whereas arsenic and chromium were less mobile. Numerical simulations done using the computer program TOUGH2 duplicated the downward rate of water movement, accumulation of water on perched zones, and its arrival at the water table. Assuming 10 x 10(6) m(3) of recharge annually for 20 years, a regional ground water flow model predicted water level rises of 30 m beneath the ponds, and rises exceeding 3 m in most wells serving the nearby urban area. PMID:18194322

  16. Artificial recharge through a thick, heterogeneous unsaturated zone

    USGS Publications Warehouse

    Izbicki, J.A.; Flint, A.L.; Stamos, C.L.

    2008-01-01

    Thick, heterogeneous unsaturated zones away from large streams in desert areas have not previously been considered suitable for artificial recharge from ponds. To test the potential for recharge in these settings, 1.3 ?? 10 6 m3 of water was infiltrated through a 0.36-ha pond along Oro Grande Wash near Victorville, California, between October 2002 and January 2006. The pond overlies a regional pumping depression 117 m below land surface and is located where thickness and permeability of unsaturated deposits allowed infiltration and saturated alluvial deposits were sufficiently permeable to allow recovery of water. Because large changes in water levels caused by nearby pumping would obscure arrival of water at the water table, downward movement of water was measured using sensors in the unsaturated zone. The downward rate of water movement was initially as high as 6 m/d and decreased with depth to 0.07 m/d; the initial time to reach the water table was 3 years. After the unsaturated zone was wetted, water reached the water table in 1 year. Soluble salts and nitrate moved readily with the infiltrated water, whereas arsenic and chromium were less mobile. Numerical simulations done using the computer program TOUGH2 duplicated the downward rate of water movement, accumulation of water on perched zones, and its arrival at the water table. Assuming 10 ?? 10 6 m3 of recharge annually for 20 years, a regional ground water flow model predicted water level rises of 30 m beneath the ponds, and rises exceeding 3 m in most wells serving the nearby urban area.

  17. Hydrogeology of the unsaturated zone, Yucca Mountain, Nevada

    SciTech Connect

    Montazer, P.; Wilson, W.E.

    1985-12-31

    The unsaturated volcanic tuff beneath Yucca Mountain, Nevada, is being evaluated by the US Department of Energy as a host rock for a potential mined geologic repository for high-level radioactive waste. Assessment of site suitability needs an efficient and focused investigative program. A conceptual hydrogeologic model that simulates the flow of fluids through the unsaturated zone at Yucca Mountain was developed to guide the program and to provide a basis for preliminary assessment of site suitability. The study was made as part of the Nevada Nuclear Waste Storage Investigations Project of the US Department of Energy. Thickness of the unsaturated zone is about 1640 to 2460 feet (500 to 750 meters). Based on physical properties, the rocks in the unsaturated zone are grouped for the purpose of this paper into five informal hydrogeologic units. From top to bottom these units are: Tiva Canyon welded unit, Paintbrush nonwelded unit. Topopah Spring welded unit, Calico Hills nonwelded unit, and Crater Flat unit. Welded units have a mean fracture density of 8 to 40 fractures per unit cubic meter, mean matrix porosities of 12 to 23%, matrix hydraulic conductivities with geometric means ranging from 6.5 x 10{sup -6} to 9.8 x 10{sup -6} foot per day (2 x 10{sup -6} to 3 x 10{sup -6} meter per day), and bulk hydraulic conductivities of 0.33 to 33 feet per day (0.1 to 10 meters per day). The nonwelded units have a mean fracture density of 1 to 3 fractures per unit cubic meter, mean matrix porosities of 31 to 46%, and saturated hydraulic conductivities with geometric means ranging from 2.6 x 10{sup -5} to 2.9 x 10{sup -2} foot per day (8 x 10{sup -6} to 9 x 10{sup -3} meter per day). 15 refs., 4 figs., 1 tab.

  18. Number Time

    ERIC Educational Resources Information Center

    Herrera, Terese A.

    2004-01-01

    This article features Number Time, a site developed by the British Broadcasting Corporation (BBC) for young mathematics learners, located at www.bbc.co.uk/schools/numbertime. The site uses interactive animation to help children in pre-K through grade 2 understand and practice number basics. Users will find online games, videos that tell number…

  19. LNAPL Removal from Unsaturated Porous Media using Surfactant Infiltration

    SciTech Connect

    Zhong, Lirong; Oostrom, Martinus

    2012-11-19

    A series of unsaturated column experiments was performed to evaluate light non-aqueous phase liquid (LNAPL) fate and removal during surfactant solution infiltration. Surfactant-LNAPL phase behavior tests were conducted to optimize the remedial solutions. Packed sand and site sediment columns were first processed to establish representative LNAPL smear zone under unsaturated conditions. Infiltration of low-concentration surfactant was then applied in a stepwise flush mode, with 0.3 column pore volume (PV) of solution in each flush. The influence of infiltrated surfactant solution volume and pH on LNAPL removal was assessed. A LNAPL bank was observed at the very front of the first surfactant infiltration in each column, indicating that a very low surfactant concentration is needed to reduce the LNAPL-water interfacial tension sufficiently enough to mobilize trapped LNAPL under unsaturated conditions. More LNAPL was recovered as additional steps of surfactant infiltration were applied. Up to 99% LNAPL was removed after six infiltration steps, with less than 2.0 PV of total surfactant solution application, suggesting surfactant infiltration may be an effective method for vadose zone LNAPL remediation. The influence of pH tested in this study (3.99~10.85) was insignificant because the buffering capacity of the sediment kept the pH in the column higher than the zero point charge, pHzpc, of the sediment and therefore the difference between surfactant sorption was negligible.

  20. A quasilinear model for solute transport under unsaturated flow

    SciTech Connect

    Houseworth, J.E.; Leem, J.

    2009-05-15

    We developed an analytical solution for solute transport under steady-state, two-dimensional, unsaturated flow and transport conditions for the investigation of high-level radioactive waste disposal. The two-dimensional, unsaturated flow problem is treated using the quasilinear flow method for a system with homogeneous material properties. Dispersion is modeled as isotropic and is proportional to the effective hydraulic conductivity. This leads to a quasilinear form for the transport problem in terms of a scalar potential that is analogous to the Kirchhoff potential for quasilinear flow. The solutions for both flow and transport scalar potentials take the form of Fourier series. The particular solution given here is for two sources of flow, with one source containing a dissolved solute. The solution method may easily be extended, however, for any combination of flow and solute sources under steady-state conditions. The analytical results for multidimensional solute transport problems, which previously could only be solved numerically, also offer an additional way to benchmark numerical solutions. An analytical solution for two-dimensional, steady-state solute transport under unsaturated flow conditions is presented. A specific case with two sources is solved but may be generalized to any combination of sources. The analytical results complement numerical solutions, which were previously required to solve this class of problems.

  1. Role of unsaturated soil in a waste containment system

    SciTech Connect

    Lim, P.C.; Tay, J.H.

    1996-12-31

    The role of the unsaturated properties of sand as a drainage layer in a composite liner system for landfills is investigated. The effect of the unsaturated properties of coarse-grained soil on contaminant migration was evaluated by means of a series of simulations using a one-dimensional model of a two- and a three-layer soil liner system for advection and diffusion, respectively. The results showed that under seepage conditions, the effect of an unsaturated sand layer on the advancement of the concentration front was quite insignificant. The arrival time of the C/C{sub o} = 0.5 concentration front increased from 651 days for the case with no sand layer to approximately 951 days for the case with a 1.0-m sand layer. A steady-state flow condition was ultimately established in the sand, and this fact suggests that the capillary action might not be effective. For diffusion, the arrival time of the concentration front increased nonlinearly with a decrease in the degree of saturation and linearly with increasing depths of the sand layer. At a residual degree of saturation, the arrival times of the C/C{sub o} = 0.01 and 0.5 concentration front at the base of the 1-m sand layer were 26.9 and 877.4 years as compared to 1.52 and 2.62 years by advection, respectively. 17 refs., 11 figs.

  2. Saturated vs. unsaturated hydrocarbon interactions with carbon nanostructures

    PubMed Central

    Umadevi, Deivasigamani; Sastry, G. Narahari

    2014-01-01

    The interactions of various acyclic and cyclic hydrocarbons in both saturated and unsaturated forms with the carbon nanostructures (CNSs) have been explored by using density functional theory (DFT) calculations. Model systems representing armchair and zigzag carbon nanotubes (CNTs) and graphene have been considered to investigate the effect of chirality and curvature of the CNSs toward these interactions. Results of this study reveal contrasting binding nature of the acyclic and cyclic hydrocarbons toward CNSs. While the saturated molecules show stronger binding affinity in acyclic hydrocarbons; the unsaturated molecules exhibit higher binding affinity in cyclic hydrocarbons. In addition, acyclic hydrocarbons exhibit stronger binding affinity toward the CNSs when compared to their corresponding cyclic counterparts. The computed results excellently corroborate the experimental observations. The interaction of hydrocarbons with graphene is more favorable when compared with CNTs. Bader's theory of atoms in molecules has been invoked to characterize the noncovalent interactions of saturated and unsaturated hydrocarbons. Our results are expected to provide useful insights toward the development of rational strategies for designing complexes with desired noncovalent interaction involving CNSs. PMID:25232539

  3. Analysis of pumping-induced unsaturated regions beneath aperennial river

    SciTech Connect

    Su, G.W.; Jasperse, J.; Seymour, D.; Constantz, J.; Zhou, Q.

    2007-05-15

    The presence of an unsaturated region beneath a streambedduring groundwater pumping near streams reduces the pumping capacity whenit reaches the well screens, changes flow paths, and alters the types ofbiological transformations in the streambed sediments. Athree-dimensional, multi-phase flow model of two horizontal collectorwells along the Russian River near Forestville, California was developedto investigate the impact of varying the ratio of the aquifer tostreambed permeability on (1) the formation of an unsaturated regionbeneath the stream, (2) the pumping capacity, (3) stream-water fluxesthrough the streambed, and (4) stream-water travel times to the collectorwells. The aquifer to streambed permeability ratio at which theunsaturated region was initially observed ranged from 10 to 100. The sizeof the unsaturated region beneath the streambed increased as the aquiferto streambed permeability ratio increased. The simulations also indicatedthat for a particular aquifer permeability, decreasing the streambedpermeability by only a factor of 2-3 from the permeability wheredesaturation initially occurred resulted in reducing the pumpingcapacity. In some cases, the stream-water fluxes increased as thestreambed permeability decreased. However, the stream water residencetimes increased and the fraction of stream water that reached that thewells decreased as the streambed permeability decreased, indicating thata higher streambed flux does not necessarily correlate to greaterrecharge of stream water around the wells.

  4. Selenite transport in unsaturated tuff from Yucca Mountain

    SciTech Connect

    Conca, J.L.; Triay, I.R.

    1994-04-01

    Direct measurements of unsaturated selenite retardation coefficients and unsaturated hydraulic conductivity were obtained on two tuff samples from Yucca Mountain using the UFA{trademark} technology. The retardation factor for the selenite species was only 2.5 in both Yucca Mountain vitric member at 62.6% saturation and zeolitized nonwelded tuff from G-tunnel at 52.8% saturation with respect to J-13 well water from the Nevada Test Site contaminated with selenium at 1.31 mg/l (ppm). In batch tests on the same material using 1.2 mg/l (ppm), the average K{sub d} was determined to be 13, giving retardation factors higher than the UFA column breakthrough tests by an order of magnitude. The difference could result from preferential flow paths in the UFA column as might occur in the field or differences in residence times between the two types of test. The unsaturated hydraulic conductivities during the experiments were 2.49 {times} 10{sup {minus}8} cm/s for the Yucca Mountain vitric member and 1.16 {times} 10{sup {minus}8} cm/s for the zeolitized nonwelded tuff.

  5. The geometry of nonwetting liquids in the unsaturated zone

    SciTech Connect

    Hartz, M.J.; Overcamp, T.J.

    1996-09-01

    In hydrophilic aquifer material, gasoline, immiscible solvents, and similar nonaqueous phase liquids (NAPL) form a separate nonwetting phase. If such a nonwetting liquid is spilled onto soil, it will percolate into the soil and migrate downward and laterally under the influence of gravity and capillary forces. As the nonwetting liquid drains from a portion of soil, some of this liquid is retained by capillary forces. Although current models predict that the retained nonwetting liquid is immobile a growing body of evidence indicates that it may be displaced by percolating water. A theory is developed to describe the geometry of nonwetting or nonaqueous phase liquids in moist unsaturated media. This theory predicts that liquids with positive values of the classical two-dimensional spreading coefficient form pendular rings. Liquids with negative values form pendular rings in regions of high-water tension or in regions of relatively high concentration of the nonwetting fluid, but they form insular lenses in regions of low-water tension or regions of low concentration of the nonwetting fluid. A three-dimensional spreading coefficient was developed to predict this behavior. Infiltrating water can cause transitions by breaking the pendular rings of nonwetting liquids in the unsaturated zone, and forming larger blobs as these rings coalesce. These blobs may drain downward due to gravity. These conditions may contribute to the mobility of nonwetting liquids due to percolation of water through the unsaturated zone.

  6. Carbon dioxide retention and carbon exchange on unsaturated Quaternary sediments

    USGS Publications Warehouse

    Striegl, R.G.; Armstrong, D.E.

    1990-01-01

    Retention of CO2 on three air-dried and partly water-saturated glacial and eolian sediments was measured at 20??C for a range in, PCO2 that commonly occurs in unsaturated zones. Ratios of the relative losses of CO2 and 14CO2 from a surrogate atmosphere overlying the sediments were 1:1 for the dry condition. For the wet condition, those relative losses were generally {precedes above single-line equals sign} 1:2, indicating bicarbonateion formation and C-isotope exchange. Mass losses of CO2 per surface area of sediment were similar for dry and wet conditions; however, CO2 losses for the wet condition were 8 to 17 times greater than losses predicted by calcite equilibria. Occurrence of this comparatively large reservoir of immobile, exchangeable C in unsaturated zones can cause alteration of the C-isotope composition of soil CO2 and of dissolved inorganic C in interstitial water, and needs to be considered when modeling 14CO2 movement in the unsaturated zone or when interpreting radiocarbon ages of infiltrating water. ?? 1990.

  7. The unsaturated hydraulic characteristics of the Bandelier Tuff

    SciTech Connect

    Rogers, D.B.; Gallaher, B.M.

    1995-09-01

    This report summarizes the physical and, unsaturated hydraulic properties of the Bandelier Tuff determined from laboratory measurements made on core samples collected at Los Alamos National Laboratory. We fit new van Genuchten-type moisture retention curves to this data, which was categorized according to member of the Bandelier Tuff and subunit of the Tshirege Member. Reasonable consistency was observed for hydraulic properties and retention curves within lithologic units, while distinct differences were observed for those properties between units. With the moisture retention data, we constructed vertical profiles of in situ matric suction and hydraulic head. These profiles give an indication of the likely direction of liquid water movement within the unsaturated zone and allow comparison of core-scale and field-scale estimates of water flow and solute transport parameters. Our core-derived transport velocities are much smaller than values estimated from tritium, Cl, and NO{sub 3} contamination found recently in boreholes. The contaminant tracer-derived transport velocities from Los Alamos Canyon are greater than corederived values found for the Otowi Member, and for Mortandad Canyon, greater than core-derived values for that borehole. The significant difference found for Mortandad Canyon suggests that fracture or other fast-path transport may be important there. The relatively small difference between observed and predicted velocities at Los Alamos Canyon may mean that vadose zone transport there occurs by unsaturated matrix flow.

  8. Unsaturated Zone Flow Changes After Wildfire: A Virtual Experiment Perspective

    NASA Astrophysics Data System (ADS)

    Ebel, B. A.

    2013-12-01

    Wildfire is a frequent disturbance event in the Western U.S. and other regions worldwide. It is well known that wildfire impacts the hydrologic cycle, yet the accompanying changes in unsaturated zone flow are poorly understood. This effort uses unsaturated zone flow simulation for well characterized experimental plots covering north- and south-facing slope aspects for plots both affected and unaffected by wildfire to improve understanding. Comparisons to observed soil-water content and matric potential data establish 'foundation simulations' that lay the groundwork for virtual experiments testing hypotheses developed from interpretation of field and laboratory data. The virtual experiments with the numerical model then extend understanding beyond what could be gleaned from data alone. Unsaturated zone flow is simulated with Hydrus-1D and the field site for this work is within the area affected by the 2010 Fourmile Canyon Fire near Boulder, CO USA. Preliminary work shows that loss of transpiration because of vegetation combustion/mortality caused soils to be wetter at depths greater than 5 cm on both north- and south-facing slopes. Loss of interception by the tree canopy also contributes to wetter subsurface conditions on north-facing slopes. On south-facing slopes, at depths less than 3 cm, the soil was drier after wildfire because of decreases in soil-water retention, confirming hypotheses from field and laboratory measurements.

  9. One-dimensional consolidation in unsaturated soils under cyclic loading

    NASA Astrophysics Data System (ADS)

    Lo, Wei-Cheng; Sposito, Garrison; Lee, Jhe-Wei; Chu, Hsiuhua

    2016-05-01

    The one-dimensional consolidation model of poroelasticity of Lo et al. (2014) for an unsaturated soil under constant loading is generalized to include an arbitrary time-dependent loading. A closed-form solution for the pore water and air pressures along with the total settlement is derived by employing a Fourier series representation in the spatial domain and a Laplace transformation in the time domain. This solution is illustrated for the important example of a fully-permeable soil cylinder with an undrained initial condition acted upon by a periodic stress. Our results indicate that, in terms of a dimensionless time scale, the transient solution decays to zero most slowly in a water-saturated soil, whereas for an unsaturated soil, the time for the transient solution to die out is inversely proportional to the initial water saturation. The generalization presented here shows that the diffusion time scale for pore water in an unsaturated soil is orders of magnitude greater than that in a water-saturated soil, mainly because of the much smaller hydraulic conductivity of the former.

  10. Evaluation of unsaturated zone air permeability through pneumatic tests

    USGS Publications Warehouse

    Baehr, Arthur L.; Hult, Marc F.

    1991-01-01

    Predicting the steady state distribution of air pressure in the unsaturated zone resulting from a pneumatic test provides a method for determining air-phase permeability. This technique is analogous to the inverse problem of well hydraulics; however, air flow is more complicated than ground water flow because of air compressibility, the Klinkenberg effect, variations in air density and viscosity that result from temperature fluctuations in the unsaturated zone and the possibility of inducing water movement during the pneumatic test. An analysis of these complicating factors reveals that, when induced water movement can be neglected, a linear version of the airflow equation can provide an appropriate approximation for the purpose of determining air-phase permeability. Two analytical solutions for steady state, two-dimensional, axisymmetric airflow to a single well partially screened in the unsaturated zone are developed. One solution applies where there is a stratum of relatively low air permeability, separating the stratum in which the well is completed, from the atmosphere. The other solution applies where there is no separating stratum between the domain and atmosphere. In both situations the water table forms the lower horizontal boundary. Applications of both solutions to determine air permeability from data collected during pneumatic tests are presented.

  11. Percolation induced heat transfer in deep unsaturated zones

    USGS Publications Warehouse

    Lu, N.; LeCain, G.D.

    2003-01-01

    Subsurface temperature data from a borehole located in a desert wash were measured and used to delineate the conductive and advective heat transfer regimes, and to estimate the percolation quantity associated with the 1997-1998 El Ni??no precipitation. In an arid environment, conductive heat transfer dominates the variation of shallow subsurface temperature most of the time, except during sporadic precipitation periods. The subsurface time-varying temperature due to conductive heat transfer is highly correlated with the surface atmospheric temperature variation, whereas temperature variation due to advective heat transfer is strongly correlated with precipitation events. The advective heat transfer associated with precipitation and infiltration is the focus of this paper. Disruptions of the subsurface conductive temperature regime, associated with the 1997-1998 El Ni??no precipitation, were detected and used to quantify the percolation quantity. Modeling synthesis using a one-dimensional coupled heat and unsaturated flow model indicated that a percolation per unit area of 0.7 to 1.3 m height of water in two weeks during February 1998 was responsible for the observed temperature deviations down to a depth of 35.2 m. The reported study demonstrated quantitatively, for the first time, that the near surface temperature variation due to advective heat transfer can be significant at a depth greater than 10 m in unsaturated soils and can be used to infer the percolation amount in thick unsaturated soils.

  12. Excluding the di-unsaturated alkenone in the UK37 index strengthens temperature correlation for the common lacustrine and brackish-water haptophytes

    NASA Astrophysics Data System (ADS)

    Zheng, Yinsui; Huang, Yongsong; Andersen, Robert A.; Amaral-Zettler, Linda A.

    2016-02-01

    Alkenone unsaturation indices, represented by either UK37 or UK‧37, are important tools for paleoclimate studies. The UK37 index is a reflection of the average number of double bonds from di-, tri-, tetra-unsaturated alkenones, but UK‧37 excludes the C37:4 in the calculation. Extensive studies indicate UK‧37 provides better regressions against in situ Sea Surface Temperatures (SST) than UK37 and is the most widely used SST proxy. However, recent studies have shown that including C37:4 alkenones for lacustrine or brackish water haptophytes such as Ruttnera (Chrysotila) lamellosa and Isochrysis galbana improves temperature correlations although there are still significant deviations at the extreme high and low temperatures. In this study, we use new culture-based calibration experiments alongside published culture data and in situ water column or surface sediment data, to demonstrate that a further improved temperature calibration for alkenones is, in fact, achieved when the di-unsaturated alkenone is excluded from the computation of the unsaturation index. We propose new indices, termed UK″ [UK″37 = C37:3/(C37:3 + C37:4) or UK″38 = C38:3/(C38:3 + C38:4)], for lacustrine, brackish and estuarine waters. Our observation suggests that di-unsaturated alkenones play a less important role than tri- and tetra-unsaturated alkenones in regulating cell functions to temperature variations in lacustrine and brackish waters. We suggest using UK″ indices for paleotemperature reconstructions in the lacustrine and estuarine settings.

  13. Linear unsaturating magnetoresistance in disordered systems

    NASA Astrophysics Data System (ADS)

    Lai, Ying Tong; Lara, Silvia; Love, Cameron; Ramakrishnan, Navneeth; Adam, Shaffique

    Theoretical works have shown that disordered systems exhibit classical magnetoresistance (MR). In this talk, we examine a variety of experimental systems that observe linear MR at high magnetic fields, including silver chalcogenides, graphene, graphite and Weyl semimetals. We show that a careful analysis of the magnitude of the MR, as well as the field strength at which the MR changes from quadratic to linear, reveal important properties of the system, such as the ratio of the root-mean-square fluctuations in the carrier density and the average carrier density. By looking at other properties such as the zero-field mobility, we show that this carrier density inhomogeneity is consistent with what is known about the microscopic impurities in these experiments. The application of this disorder-induced MR to a variety of different experimental scenarios underline the universality of these theoretical models. This work is supported by the Singapore National Research Foundation (NRF-NRFF2012-01) and the Singapore Ministry of Education and Yale-NUS College through Grant Number R-607-265-01312.

  14. Production of Lipase and Oxygenated Fatty Acids from Vegetable Oils

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Vegetable oils such as soybean oil and corn oil are cheap raw materials. Various value-added oxygenated fatty acids have been produced from unsaturated fatty acids such as oleic and linoleic acid by biotransformation. Lipase from the non-pathogenic yeast Candida cylindracea is another important va...

  15. Encapsulation of ployunsaturated fatty acid esters with solid lipid particles

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Polyunsaturated fatty acids (PUFA) such as a-linolenic acid (ALA) and docosahexaenoic acid (DHA) are known to improve cardiovascular and nervous system health. These compounds are increasingly used in food and animal feed formulations. However, the high degree of unsaturation in these structures can...

  16. Cis and trans unsaturated phosphatidylcholine bilayers: A molecular dynamics simulation study.

    PubMed

    Kulig, Waldemar; Pasenkiewicz-Gierula, Marta; Róg, T

    2016-02-01

    Trans unsaturated lipids are uncommon in nature. In the human diet, they occur as natural products of ruminal bacteria or from industrial food processing like hydrogenation of vegetable oils. Consumption of trans unsaturated lipids has been shown to have a negative influence on human health; in particular, the risk of cardiovascular disease is higher when the amount of trans unsaturated lipids in the diet is elevated. In this study, we first performed quantum mechanical calculations to specifically and accurately parameterize cis and trans mono-unsaturated lipids and subsequently validated the newly derived parameter set. Then, we carried out molecular dynamics (MD) simulations of lipid bilayers composed of cis or trans unsaturated lipids with and without cholesterol. Our results show that trans mono-unsaturated chains are more flexible than cis mono-unsaturated chains due to lower barriers for rotation around the single bonds next to the trans double bond than those next to the cis double bond. In effect, interactions between cholesterol and trans unsaturated chains are stronger than cis unsaturated chains, which results in a higher ordering effect of cholesterol in trans unsaturated bilayers. PMID:26187855

  17. Saturated and Unsaturated Dietary Fats Differentially Modulate Ethanol-Induced Changes in Gut Microbiome and Metabolome in a Mouse Model of Alcoholic Liver Disease.

    PubMed

    Kirpich, Irina A; Petrosino, Joseph; Ajami, Nadim; Feng, Wenke; Wang, Yuhua; Liu, Yanlong; Beier, Juliane I; Barve, Shirish S; Yin, Xinmin; Wei, Xiaoli; Zhang, Xiang; McClain, Craig J

    2016-04-01

    Alcoholic liver disease (ALD) ranks among major causes of morbidity and mortality. Diet and crosstalk between the gut and liver are important determinants of ALD. We evaluated the effects of different types of dietary fat and ethanol on the gut microbiota composition and metabolic activity and the effect of these changes on liver injury in ALD. Compared with ethanol and a saturated fat diet (medium chain triglycerides enriched), an unsaturated fat diet (corn oil enriched) exacerbated ethanol-induced endotoxemia, liver steatosis, and injury. Major alterations in gut microbiota, including a reduction in Bacteroidetes and an increase in Proteobacteria and Actinobacteria, were seen in animals fed an unsaturated fat diet and ethanol but not a saturated fat diet and ethanol. Compared with a saturated fat diet and ethanol, an unsaturated fat diet and ethanol caused major fecal metabolomic changes. Moreover, a decrease in certain fecal amino acids was noted in both alcohol-fed groups. These data support an important role of dietary lipids in ALD pathogenesis and provide insight into mechanisms of ALD development. A diet enriched in unsaturated fats enhanced alcohol-induced liver injury and caused major fecal metagenomic and metabolomic changes that may play an etiologic role in observed liver injury. Dietary lipids can potentially serve as inexpensive interventions for the prevention and treatment of ALD. PMID:27012191

  18. Optimal Production of 7,10-dihydroxy-8(E)-hexadecenoic Acid from Palmitoleic Acid by Pseudomonas aeruginosa PR3

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The hydroxylation of unsaturated fatty acids by bacterial strains is one type of value-adding bioconversion process. This process generates new hydroxy fatty acids (HFA) carrying special properties such as higher viscosity and reactivity compared with normal fatty acids. Among microbial strains te...

  19. Morita-Baylis-Hillman Reaction of α,β-Unsaturated Ketones with Allylic Acetates by the Combination of Transition-Metal Catalysis and Organomediation.

    PubMed

    Li, Ya-Qiong; Wang, Hai-Jun; Huang, Zhi-Zhen

    2016-06-01

    An intermolecular Morita-Baylis-Hillman (MBH) reaction of α,β-unsaturated ketones with allylic acetates under the catalysis of 10 mol % of tetrakis(triphenylphosphine)palladium(0) and mediation of tributylphosphine has been developed in the presence of acetic acid, affording the desired α-coupling products. The MBH reaction has the advantages of good tolerance to many functional groups, excellent regioselectivity and E-stereoselectivity, and moderate to good yields. PMID:27186906

  20. Chiral NHC Ligands Bearing a Pyridine Moiety in Copper-Catalyzed 1,2-Addition of Dialkylzinc Reagents to β-Aryl-α,β-unsaturated N-Tosylaldimines.

    PubMed

    Soeta, Takahiro; Ishizaka, Tomohiro; Ukaji, Yutaka

    2016-04-01

    Asymmetric 1,2-addition of dialkylzinc reagents to α,β-unsaturated N-tosylaldimines was catalyzed by copper salt in the presence of chiral imidazolium salts having a pyridine ring, which were derived from amino acid, to afford the corresponding chiral allylic amines with up to 91% ee in reasonably high yields. The chiral N-heterocyclic carbene (NHC) ligand played an important role in controlling chemoselectivity. PMID:26967950

  1. RNA binding by the novel helical domain of the influenza virus NS1 protein requires its dimer structure and a small number of specific basic amino acids.

    PubMed Central

    Wang, W; Riedel, K; Lynch, P; Chien, C Y; Montelione, G T; Krug, R M

    1999-01-01

    The RNA-binding/dimerization domain of the NS1 protein of influenza A virus (73 amino acids in length) exhibits a novel dimeric six-helical fold. It is not known how this domain binds to its specific RNA targets, one of which is double-stranded RNA. To elucidate the mode of RNA binding, we introduced single alanine replacements into the NS1 RNA-binding domain at specific positions in the three-dimensional structure. Our results indicate that the dimer structure is essential for RNA binding, because any alanine replacement that causes disruption of the dimer also leads to the loss of RNA-binding activity. Surprisingly, the arginine side chain at position 38, which is in the second helix of each monomer, is the only amino-acid side chain that is absolutely required only for RNA binding and not for dimerization, indicating that this side chain probably interacts directly with the RNA target. This interaction is primarily electrostatic, because replacement of this arginine with lysine had no effect on RNA binding. A second basic amino acid, the lysine at position 41, which is also in helix 2, makes a strong contribution to the affinity of binding. We conclude that helix 2 and helix 2', which are antiparallel and next to each other in the dimer conformation, constitute the interaction face between the NS1 RNA-binding domain and its RNA targets, and that the arginine side chain at position 38 and possibly the lysine side chain at position 41 in each of these antiparallel helices contact the phosphate backbone of the RNA target. PMID:10024172

  2. Fatty acid composition of brown adipose tissue in genetically heat-tolerant FOK rats

    NASA Astrophysics Data System (ADS)

    Ohno, T.; Furuyama, F.; Kuroshima, A.

    The phospholipid fatty acid composition of brown adipose tissue (BAT) was examined in inbred heat-tolerant FOK rats and compared with that in conventional Wistar rats not previously exposed to heat. The FOK rats showed higher unsaturation states, as indicated by higher levels of polyunsaturated fatty acids and a higher unsaturation index and polyunsaturated fatty acids/saturated fatty acids ratio. This higher level of unsaturation was characterized by the higher amount of polyunsaturated fatty acids such as linoleic acid, arachidonic acid and docosahexaenoic acid. It may be concluded that the increased docosahexaenoic acid level in BAT phospholipids brings about the hyperplasia of BAT, causing an enhancement of its in vivo thermogernic activity as well as the systemic non-shivering thermogenesis observed in heat-tolerant FOK rats.

  3. Herbicide Transport and Transformations in the Unsaturated Zone of Three Small Agricultural Basins with Corn and Soybean Row Crops

    NASA Astrophysics Data System (ADS)

    Hancock, T. C.; Vogel, J. R.; Sandstrom, M. W.; Capel, P. D.; Bayless, R. E.; Webb, R. M.

    2006-05-01

    In the United States, herbicides are among the most significant nonpoint-source pollutants and were applied to 95% of all fields in corn production and 97% of all fields in soybean production in 2003 and 2004. The United States Geological Survey (USGS) has conducted a study on select herbicides in the unsaturated zone under corn and soybean fields in three predominantly agricultural basins: Morgan Creek (Maryland), Leary Weber Ditch within Sugar Creek (Indiana), and Maple Creek (Nebraska). In 2004, the Morgan Creek and Leary Weber Ditch fields were in soybeans and the Maple Creek fields were in corn. The Maple Creek fields were irrigated, whereas those in Morgan Creek and Leary Weber Ditch were not. Similarities and differences in agricultural management practices, climatic conditions, and natural features, such as soil types and geology, were evaluated as part of the study. In general, the amounts of herbicides entering the unsaturated zone from rain in these basins were minor (1%) compared to amounts commonly applied to the land surface during agricultural practices. Few herbicides were detected on solid core samples from the unsaturated zones of these basins. An exception was found at a Morgan Creek site in an upland recharge area with sandier soils. Here, atrazine concentrations were highest in the near surface solids and decreased with depth. In the unsaturated-zone porewater of the Morgan Creek Basin, parent triazine and acetanilide herbicides were detected and only at the site in the upland recharge area at relatively low concentrations at depths greater than 4 meters, probably because these compounds had not been applied for several years. At the Morgan Creek and Leary Weber Ditch sites, acetanilide metabolites were frequently detected in the unsaturated-zone porewater. In general, the fraction of metolachlor ethane sulfonic acid (ESA) relative to the total mass of parent and metabolites increased with depth overall and at several individual sampling

  4. Development of an enzyme-linked immunosorbent assay to determine the numbers of chemolithotrophic bacteria at acid-mine-drainage sites. Technical report (Final)

    SciTech Connect

    Blake, R.C.; Revis, N.W.; Holdsworth, G.

    1990-09-01

    Thiobacillus ferrooxidans is a prominent member of a group of chemo-lithotrophic bacteria that bear principal responsibility for the formation of acid mine drainage. A prototype enzyme-linked immunosorbent assay (ELISA) for enumerating and qualifying T. ferrooxidans was assembled and characterized. The immunoassay protocol consisted of sequential incubations of the sample with (i) the primary antibody, (ii) the enzyme-labeled secondary antibody, and (iii) a chromogenic substrate specific for the enzyme lable. The necessary reagents comprised primary polyclonal rabbit antibodies directed against T. ferrooxidans ATCC 23270, alkaline phosphatase-copled goat anti-rabbit polyclonal antibodies, and phenolphrhalein monophosphate. The ELISA developed herein correctly identified whether iron-oxidizing bacteria were present in each of 4 samples supplied and analyzed by an independent laboratory. Sufficient preliminary data was obtained to warrant further research and development activities.

  5. Number Guessing

    ERIC Educational Resources Information Center

    Sezin, Fatin

    2009-01-01

    It is instructive and interesting to find hidden numbers by using different positional numeration systems. Most of the present guessing techniques use the binary system expressed as less-than, greater-than or present-absent type information. This article describes how, by employing four cards having integers 1-64 written in different colours, one…

  6. Numbers, Please!

    ERIC Educational Resources Information Center

    Thelin, John R.

    2013-01-01

    What topic would you choose if you had the luxury of writing forever? In this article, John Thelin provides his response: He would opt to write about the history of higher education in a way that relies on quantitative data. "Numbers, please!" is his research request in taking on a longitudinal study of colleges and universities over…

  7. Numbers Sense

    ERIC Educational Resources Information Center

    Kathotia, Vinay

    2009-01-01

    This article reports on work undertaken by schools as part of Qualifications and Curriculum Authority's (QCA's) "Engaging mathematics for all learners" project. The goal was to use in the classroom, materials and approaches from a Royal Institution (Ri) Year 10 master-class, "Number Sense", which was inspired by examples from Michael Blastland and…

  8. Unsaturated platinum-rhenium cluster complexes. Synthesis, structures and reactivity.

    PubMed

    Adams, Richard D; Captain, Burjor; Smith, Mark D; Beddie, Chad; Hall, Michael B

    2007-05-01

    Two new compounds PtRe3(CO)12(PBut3)(micro-H)3, 9, and PtRe2(CO)9(PBut3)(micro-H)2, 10, were obtained from the reaction of Pt(PBut3)2 with Re3(CO)12(micro-H3), 8, at room temperature. Compound 9 contains a butterfly cluster of four metals formed by the insertion of the platinum atom from a Pt(PBut3) group into one of the hydride-bridged metal-metal bonds of 8. The three hydrido ligands are bridging ligands across each of three new Pt-Re bonds. Compound 10 contains a triangular PtRe2 cluster with two hydrido ligands; one bridges a Pt-Re bond, and the other bridges the Re-Re bond. The new compound Pt2Re2(CO)7(PBut3)2(micro-H)2, 11, was obtained from the reaction of 8 with Pt(PBut3)2 in hexane at reflux. Compound 11 was also obtained from 10 by reaction with an additional quantity of Pt(PBut3)2. Compound 11 contains a tetrahedral cluster of four metal atoms with two dynamically active hydrido ligands. A CO ligand on one of the two platinum atoms also exchanges between the two platinum atoms rapidly on the NMR time scale. Compound 11 is electronically unsaturated and was found to add hydrogen at room temperature to form the tetrahydrido cluster complex, Pt2Re2(CO)7(PBut3)2(micro-H)4, 12. Compound 12 has a structure similar to 11 but contains one triply bridging hydrido ligand, two edge bridging hydrido ligands, and one terminal hydrido ligand on one of the two platinum atoms. A kinetic isotope effect D/H of 1.5(1) was determined for the addition of H2 to 11. Hydrogen can be eliminated from 12 by heating to 97 degrees C or by the application of UV-vis irradiation at room temperature. Compound 12 adds CO at room temperature to yield the complex Pt2Re2(CO)8(PBut3)2(micro-H)4, 13, which contains a planar cluster of four metal atoms with a Pt-Pt bond and four edge bridging hydrido ligands. Compounds 11 and 12 react with Pt(PBut3)2 to yield the known five metal cluster complexes Pt3Re2(CO)6(PBut3)3(micro-H)2, 14, and Pt3Re2(CO)6(PBut3)3(micro-H)4, 15, respectively. Density

  9. Unsaturated Zone and Saturated Zone Transport Properties (U0100)

    SciTech Connect

    J. Conca

    2000-12-20

    This Analysis/Model Report (AMR) summarizes transport properties for the lower unsaturated zone hydrogeologic units and the saturated zone at Yucca Mountain and provides a summary of data from the Busted Butte Unsaturated Zone Transport Test (UZTT). The purpose of this report is to summarize the sorption and transport knowledge relevant to flow and transport in the units below Yucca Mountain and to provide backup documentation for the sorption parameters decided upon for each rock type. Because of the complexity of processes such as sorption, and because of the lack of direct data for many conditions that may be relevant for Yucca Mountain, data from systems outside of Yucca Mountain are also included. The data reported in this AMR will be used in Total System Performance Assessment (TSPA) calculations and as general scientific support for various Process Model Reports (PMRs) requiring knowledge of the transport properties of different materials. This report provides, but is not limited to, sorption coefficients and other relevant thermodynamic and transport properties for the radioisotopes of concern, especially neptunium (Np), plutonium (Pu), Uranium (U), technetium (Tc), iodine (I), and selenium (Se). The unsaturated-zone (UZ) transport properties in the vitric Calico Hills (CHv) are discussed, as are colloidal transport data based on the Busted Butte UZTT, the saturated tuff, and alluvium. These values were determined through expert elicitation, direct measurements, and data analysis. The transport parameters include information on interactions of the fractures and matrix. In addition, core matrix permeability data from the Busted Butte UZTT are summarized by both percent alteration and dispersion.

  10. Flow and transport through unsaturated fractured rock: An overview

    NASA Astrophysics Data System (ADS)

    Evans, Daniel D.; Rasmussen, Todd C.; Nicholson, Thomas J.

    Groundwater flow and contaminant transport through the unsaturated zone continue to receive attention as former nuclear weapons development sites are being characterized for determining decommissioning options, and geologic sites are being considered for deep disposal of nuclear and hazardous waste. The ability to make decisions with regard to cleanup, site suitability, and anticipated performance of disposal or storage facilities is dependent upon the characterization and modeling of unsaturated flow and transport features, events, and processes. Hazardous materials may be mobilized by infiltrating water and move downward to affect groundwater resources. These contaminants may also move upward or laterally by capillary movement or as vapor to the accessible environment. Substantial experience exists with respect to near-surface partially saturated porous media, traditionally the domain of the soil scientists and geotechnical engineers, but does not exist for fractured rock in either near-surface or deep, complex, unsaturated systems that are now being characterized and modeled. The ability to represent these complex systems composed of both a matrix and a fracture component is being tested through a variety of field experiments and comparisons to natural analogues. The present focus is on evaluating conceptual flow and transportmodels and quantifying the spatial and temporal parameters for these models using laboratory and field methods, and environmental tracer analyses. Modeling of these dynamic and transient systems has followed two paths, porous equivalency and discrete fracture models. In general, characterization methods and modelingare in the confirmation stage with the greatest lack of knowledge being the interaction between fracture and matrix properties for flow and transport.

  11. Coupled hydromechanical and electromagnetic disturbances in unsaturated porous materials

    PubMed Central

    Revil, A; Mahardika, H

    2013-01-01

    A theory of cross-coupled flow equations in unsaturated soils is necessary to predict (1) electroosmotic flow with application to electroremediation and agriculture, (2) the electroseismic and the seismoelectric effects to develop new geophysical methods to characterize the vadose zone, and (3) the streaming current, which can be used to investigate remotely ground water flow in unsaturated conditions in the capillary water regime. To develop such a theory, the cross-coupled generalized Darcy and Ohm constitutive equations of transport are extended to unsaturated conditions. This model accounts for inertial effects and for the polarization of porous materials. Rather than using the zeta potential, like in conventional theories for the saturated case, the key parameter used here is the quasi-static volumetric charge density of the pore space, which can be directly computed from the quasi-static permeability. The apparent permeability entering Darcy's law is also frequency dependent with a critical relaxation time that is, in turn, dependent on saturation. A decrease of saturation increases the associated relaxation frequency. The final form of the equations couples the Maxwell equations and a simplified form of two-fluid phases Biot theory accounting for water saturation. A generalized expression of the Richard equation is derived, accounting for the effect of the vibration of the skeleton during the passage of seismic waves and the electrical field. A new expression is obtained for the effective stress tensor. The model is tested against experimental data regarding the saturation and frequency dependence of the streaming potential coupling coefficient. The model is also adapted for two-phase flow conditions and a numerical application is shown for water flooding of a nonaqueous phase liquid (NAPL, oil) contaminated aquifer. Seismoelectric conversions are mostly taking place at the NAPL (oil)/water encroachment front and can be therefore used to remotely track the

  12. Injection of Nuclear Rocket Engine Exhaust into Deep Unsaturated Zones

    NASA Astrophysics Data System (ADS)

    Cooper, C. A.; Decker, D.

    2008-05-01

    Nuclear rocket engine technology is being considered as a means of interplanetary vehicle propulsion for a manned mission to Mars. To achieve this, a test and development facility must be constructed to safely run nuclear engines. The testing of nuclear engines in the 1950's and 1960's was accomplished by exhausting the engine gases into the atmosphere, a practice that is no longer acceptable. Injection into deep unsaturated zones of radioactive exhaust gases and water vapor associated with the testing of nuclear rocket engines is being considered as a way of sequestering radionuclides from the environment. Numerical simulations were conducted to determine the ability of an unsaturated zone with the hydraulic properties of Frenchman Flat alluvium at the Nevada Test Site to contain gas-phase radionuclides. Gas and water vapor were injected for two hours at rates of 14.5 kg s-1 and 15 kg s-1, respectively, in an interval between 100 and 430 m below the land surface into alluvium with an intrinsic permeability of 10-11 m2 and porosity of 0.35. The results show that during a test of an engine, radionuclides with at least greater than 10-year half-lives may reach the land surface within several years after injection. Radionuclide transport is primarily controlled by the upward pressure gradient from the point of injection to the lower (atmospheric) pressure boundary condition at the land surface. Radionuclides with half-lives on the order of days should undergo enough decay prior to reaching the land surface. A cooling water vapor injected into the unsaturated zone simultaneously with the exhaust gas will condense within several meters of the injection point and drain downward toward the water table. However, the nearly horizontal hydraulic groundwater gradient present in several of the basins at NTS should limit lateral migration of radionuclides away from the vicinity of injection.

  13. Modeling field scale unsaturated flow and transport processes

    SciTech Connect

    Gelhar, L.W.; Celia, M.A.; McLaughlin, D.

    1994-08-01

    The scales of concern in subsurface transport of contaminants from low-level radioactive waste disposal facilities are in the range of 1 to 1,000 m. Natural geologic materials generally show very substantial spatial variability in hydraulic properties over this range of scales. Such heterogeneity can significantly influence the migration of contaminants. It is also envisioned that complex earth structures will be constructed to isolate the waste and minimize infiltration of water into the facility. The flow of water and gases through such facilities must also be a concern. A stochastic theory describing unsaturated flow and contamination transport in naturally heterogeneous soils has been enhanced by adopting a more realistic characterization of soil variability. The enhanced theory is used to predict field-scale effective properties and variances of tension and moisture content. Applications illustrate the important effects of small-scale heterogeneity on large-scale anisotropy and hysteresis and demonstrate the feasibility of simulating two-dimensional flow systems at time and space scales of interest in radioactive waste disposal investigations. Numerical algorithms for predicting field scale unsaturated flow and contaminant transport have been improved by requiring them to respect fundamental physical principles such as mass conservation. These algorithms are able to provide realistic simulations of systems with very dry initial conditions and high degrees of heterogeneity. Numerical simulation of the movement of water and air in unsaturated soils has demonstrated the importance of air pathways for contaminant transport. The stochastic flow and transport theory has been used to develop a systematic approach to performance assessment and site characterization. Hypothesis-testing techniques have been used to determine whether model predictions are consistent with observed data.

  14. Parametric study of unsaturated drainage layers in a capillary barrier

    SciTech Connect

    Morris, C.E.; Stormont, J.C.

    1999-12-01

    Unsaturated drainage layers (UDLs) have been demonstrated to greatly increase the lateral diversion capacity of capillary barriers. The inclusion of a UDL allows native soils suitable for vegetation growth to be used as the finer soil as lateral drainage properties of the layer no longer need to be considered. A comprehensive numerical study was conducted to investigate the influence of the interface slope and the UDL material on the system's ability to laterally divert downward moving moisture. A capillary barrier system with and without a UDL was simulated for 10 years using daily varying climatic data for three locations in the US. Three different sands were simulated as the UDL and were modeled at slopes of 5, 10, and 20%. The numerical results confirm that the inclusion of an unsaturated drainage layer at the fine/coarse interface of a capillary barrier can provide significant improvements in the performance of the cover system by laterally draining water. This improvement in performance may allow the system to be successfully implemented in climates wetter than previously were thought suitable. The diversion length (the distance water is diverted laterally with no downward flow through the fine/coarse interface) of a capillary barrier with a UDL was found to be proportional to the slope of the fine/coarse interface. In addition, a relationship between lateral diversion lengths in a capillary barrier and the UDL material was developed and found to be dependent on the unsaturated flow characteristics of the UDL. These relationships allow the performance of a variety capillary barrier UDL designs to be calculated knowing the behavior of one system for a given location.

  15. Coupled hydromechanical and electromagnetic disturbances in unsaturated porous materials.

    PubMed

    Revil, A; Mahardika, H

    2013-02-01

    A theory of cross-coupled flow equations in unsaturated soils is necessary to predict (1) electroosmotic flow with application to electroremediation and agriculture, (2) the electroseismic and the seismoelectric effects to develop new geophysical methods to characterize the vadose zone, and (3) the streaming current, which can be used to investigate remotely ground water flow in unsaturated conditions in the capillary water regime. To develop such a theory, the cross-coupled generalized Darcy and Ohm constitutive equations of transport are extended to unsaturated conditions. This model accounts for inertial effects and for the polarization of porous materials. Rather than using the zeta potential, like in conventional theories for the saturated case, the key parameter used here is the quasi-static volumetric charge density of the pore space, which can be directly computed from the quasi-static permeability. The apparent permeability entering Darcy's law is also frequency dependent with a critical relaxation time that is, in turn, dependent on saturation. A decrease of saturation increases the associated relaxation frequency. The final form of the equations couples the Maxwell equations and a simplified form of two-fluid phases Biot theory accounting for water saturation. A generalized expression of the Richard equation is derived, accounting for the effect of the vibration of the skeleton during the passage of seismic waves and the electrical field. A new expression is obtained for the effective stress tensor. The model is tested against experimental data regarding the saturation and frequency dependence of the streaming potential coupling coefficient. The model is also adapted for two-phase flow conditions and a numerical application is shown for water flooding of a nonaqueous phase liquid (NAPL, oil) contaminated aquifer. Seismoelectric conversions are mostly taking place at the NAPL (oil)/water encroachment front and can be therefore used to remotely track the

  16. Conformational Change in the Active Site of Streptococcal Unsaturated Glucuronyl Hydrolase Through Site-Directed Mutagenesis at Asp-115.

    PubMed

    Nakamichi, Yusuke; Oiki, Sayoko; Mikami, Bunzo; Murata, Kousaku; Hashimoto, Wataru

    2016-08-01

    Bacterial unsaturated glucuronyl hydrolase (UGL) degrades unsaturated disaccharides generated from mammalian extracellular matrices, glycosaminoglycans, by polysaccharide lyases. Two Asp residues, Asp-115 and Asp-175 of Streptococcus agalactiae UGL (SagUGL), are completely conserved in other bacterial UGLs, one of which (Asp-175 of SagUGL) acts as a general acid and base catalyst. The other Asp (Asp-115 of SagUGL) also affects the enzyme activity, although its role in the enzyme reaction has not been well understood. Here, we show substitution of Asp-115 in SagUGL with Asn caused a conformational change in the active site. Tertiary structures of SagUGL mutants D115N and D115N/K370S with negligible enzyme activity were determined at 2.00 and 1.79 Å resolution, respectively, by X-ray crystallography. The side chain of Asn-115 is drastically shifted in both mutants owing to the interaction with several residues, including Asp-175, by formation of hydrogen bonds. This interaction between Asn-115 and Asp-175 probably prevents the mutants from triggering the enzyme reaction using Asp-175 as an acid catalyst. PMID:27402448

  17. Methods of refining and producing isomerized fatty acid esters and fatty acids from natural oil feedstocks

    DOEpatents

    Snead, Thomas E.; Cohen, Steven A.; Gildon, Demond L.; Beltran, Leslie V.; Kunz, Linda A.; Pals, Tessa M.; Quinn, Jordan R; Behrends, Jr., Raymond T.; Bernhardt, Randal J.

    2016-07-05

    Methods are provided for refining natural oil feedstocks and producing isomerized esters and acids. The methods comprise providing a C4-C18 unsaturated fatty ester or acid, and isomerizing the fatty acid ester or acid in the presence of heat or an isomerization catalyst to form an isomerized fatty ester or acid. In some embodiments, the methods comprise forming a dibasic ester or dibasic acid prior to the isomerizing step. In certain embodiments, the methods further comprise hydrolyzing the dibasic ester to form a dibasic acid. In certain embodiments, the olefin is formed by reacting the feedstock in the presence of a metathesis catalyst under conditions sufficient to form a metathesized product comprising olefins and esters, separating the olefins from the esters in the metathesized product, and transesterifying the esters in the presence of an alcohol to form a transesterified product having unsaturated esters.

  18. Liquid flow and distribution in unsaturated porous media

    NASA Technical Reports Server (NTRS)

    Alexander, J. Iwan

    2004-01-01

    Flow and transport in permeable or porous media and microchannels occurs in a variety of situations in micro- and reduced-gravity environments, many of them associated with environmental control and life support systems. While the role of gravity is limited, due to the typically small size scales associated permeable media, gravity, at the very least, affects the overall disposition of fluid in a macroscopic system. This presentation will discuss examples where the absence of gravity affects flow and phase distribution in selected examples of unsaturated flow and transport of heat and mass in porous media and microchannels that are pertinent to spacecraft systems.

  19. Evaluation of α,β-Unsaturated Ketones as Antileishmanial Agents

    PubMed Central

    Vasquez, Miguel A.; Iniguez, Eva; Das, Umashankar; Beverley, Stephen M.; Herrera, Linda J.; Dimmock, Jonathan R.

    2015-01-01

    In this study, we assessed the antileishmanial activity of 126 α,β-unsaturated ketones. The compounds NC901, NC884, and NC2459 showed high leishmanicidal activity for both the extracellular (50% effective concentration [EC50], 456 nM, 1,122 nM, and 20 nM, respectively) and intracellular (EC50, 1,870 nM, 937 nM, and 625 nM, respectively) forms of Leishmania major propagated in macrophages, with little or no toxicity to mammalian cells. Bioluminescent imaging of parasite replication showed that all three compounds reduced the parasite burden in the murine model, with no apparent toxicity. PMID:25801571

  20. Performance of the Fluidized Bed Steam Reforming product under hydraulically unsaturated conditions.

    PubMed

    Neeway, James J; Qafoku, Nikolla P; Williams, Benjamin D; Rod, Kenton; Bowden, Mark E; Brown, Christopher F; Pierce, Eric M

    2014-05-01

    Several candidates for supplemental low-activity waste (LAW) immobilization at the Hanford site in Washington State, USA are being considered. One waste sequestering technology considered is Fluidized Bed Steam Reforming (FBSR). The granular product resulting from the FBSR process is composed primarily of an insoluble sodium aluminosilicate matrix with the dominant phases being feldspathoid minerals with a 1:1:1 molar ratio of Na, Al and Si. To demonstrate the durability of the product, which can be disposed of at the unsaturated Integrated Disposal Facility (IDF) at Hanford, a series of tests has been performed using the Pressurized Unsaturated Flow (PUF) system, which allows for the accelerated weathering of the solid materials. The system maintains hydraulically unsaturated conditions, thus mimicking the open-flow and transport properties that will be present at the IDF. Two materials were tested using the system: 1) the FBSR granular product and 2) the FBSR granular product encapsulated in a geopolymer to form a monolith. Results of the experiments show a trend of relatively constant effluent concentration of Na, Si, Al, and Cs as a function of time from both materials. The elements I and Re show a steady release throughout the yearlong test from the granular material but their concentrations seem to be increasing at one year from the monolith material. This result suggests that these two elements may be present in the sodalite cage structure rather than in the predominant nepheline phase because their release occurs at a different rate compared to nepheline phase. Also, these elements to not seem to reprecipitate when released from the starting material. Calculated one-year release rates for Si are on the order of 10(-6) g/(m(2) d) for the granular material and 10(-5) g/(m(2) d) for the monolith material while Re release is seen to be two orders of magnitude higher than Si release rates. SEM imaging and XRD analysis show how the alteration of the two

  1. Performance of the Fluidized Bed Steam Reforming product under hydraulically unsaturated conditions

    SciTech Connect

    Neeway, James J; Rod, Kenton A.; Bowden, Mark E; Pierce, Eric M; Qafoku, Nikolla; Williams, Benjamin D; Brown, Christopher F

    2014-01-01

    Several candidates for supplemental low-activity waste (LAW) immobilization at the Hanford site in Washington State, USA are being considered. One waste sequestering technology considered is Fluidized Bed Steam Reforming (FBSR). The granular product resulting from the FBSR process is composed primarily of an insoluble sodium aluminosilicate matrix with the dominant phases being feldspathoid minerals with a 1:1:1 molar ratio of Na, Al and Si. To demonstrate the durability of the product, which can be disposed of at the unsaturated Integrated Disposal Facility (IDF) at Hanford, a series of tests has been performed using the Pressurized Unsaturated Flow (PUF) system, which allows for the accelerated weathering of the solid materials. The system maintains hydraulically unsaturated conditions, thus mimicking the open-flow and transport properties that will be present at the IDF. Two materials were tested using the system: 1) the FBSR granular product and 2) the FBSR granular product encapsulated in a geopolymer to form a monolith. Results of the experiments show a trend of relatively constant effluent concentration of Na, Si, Al, and Cs as a function of time from both materials. The elements I and Re show a steady release throughout the yearlong test from the granular material but their concentrations seem to be increasing at one year from the monolith material. This result suggests that these two elements may be present in the sodalite cage structure rather than in the predominant nepheline phase because their release occurs at a different rate compared to nepheline phase. Also, these elements to not seem to reprecipitate when released from the starting material. Calculated one-year release rates for Si are on the order of 10 6 g/(m2 d) for the granular material and 10 5 g/(m2 d) for the monolith material while Re release is seen to be two orders of magnitude higher than Si release rates. SEM imaging and XRD analysis show how the alteration of the two materials is

  2. Effect of the fluorination degree of hydrophobic chains on the monolayer behavior of unsaturated diacylphosphatidylcholines bearing partially fluorinated 9-octadecynoyl (stearoloyl) groups at the air-water interface.

    PubMed

    Baba, Teruhiko; Takai, Katsuki; Takagi, Toshiyuki; Kanamori, Toshiyuki

    2014-11-01

    The effect of the fluorination degree of hydrophobic chains on the monolayer behavior of unsaturated diacylphosphatidylcholines (PCs) was examined by employing a series of PCs bearing partially fluorinated 9-octadecynoyl (stearoloyl) groups (DFnStPCs, n: the number of fluorinated carbon atoms in a stearoloyl group; n=1, 2, 4, 8), including their hydrophobic parts--partially fluorinated stearolic acids (FnStAs)--at the air-water interface. π-A isotherm measurements and Brewster angle microscope observations revealed: (i) all DFnStPCs including FnStAs form monolayers of liquid character at 25 °C; (ii) they form more expanded monolayers than their non-fluorinated counterparts, distearoloyl-PC (DStPC) and stearolic acid, while the monolayer stability increases with n; (iii) compared with DStPC and DF8StPC, DFnStPCs (n=1, 2, 4) in the low-π region tend to show a weakening in their self-aggregation property and an increase in the work required for monolayer compression; (iv) although DF8StPC forms the most expanded monolayer, the behavior of DF8StPC resembles that of DStPC rather than that of DFnStPCs (n=1, 2, 4). The monolayer behavior of DFnStPCs (n=1, 2, 4) is explained by postulating a flatly-lying conformation of hydrophobic chains, in which three polar parts (ester group, triple bond, CF2-CH2 linkage) in chains are immersed in the subphase at large areas. DStPC and DF8StPC lacking a CF2-CH2 linkage, however, do not likely adopt such a conformation. PMID:25264284

  3. Computational study of the acid dissociation of esters and lactones. A case study of diketene.

    PubMed

    Gómez-Bombarelli, Rafael; González-Pérez, Marina; Pérez-Prior, María Teresa; Calle, Emilio; Casado, Julio

    2009-07-17

    A computational study of the aqueous pK(a) of some saturated and unsaturated cyclic and linear esters and ketones was carried out at the DFT-B3LYP 6-31++G(2df,2pd), CBS-Q, and G2 levels, with the integral equation formalism polarizable continuum model for solvation, using a proton exchange mechanism. The influence of unsaturation, position of the double bond, and cyclization were studied. The computational results show that (a) in all cases studied except that of diketene (4-methylene-2-oxetanone), the alpha-beta unsaturated isomer is 20-30 kJ mol(-1) lower in energy that the beta-gamma unsaturated one; (b) alpha-beta unsaturation lowers the pK(a) of an ester approximately 6 units, whereas beta-gamma unsaturation lowers it by approximately 10 units, and cyclization lowers the pK(a) by approximately 3 units. In order to check the predictive power of the methodology, the acid dissociation constant of diketene in water was measured via kinetic study of its base-catalyzed hydrolysis. The pK(a) value obtained (15.2 +/- 0.3) is in keeping with the expected value for a beta-gamma unsaturated beta-lactone. This low value also suggests that deprotonated diketene does not interconvert to a more stable, less acidic alpha-beta unsaturated isomer, which is also consistent with computational results. PMID:19459649

  4. Relative turnover numbers of maize endosperm and potato tuber ADP-glucose pyrophosphorylases in the absence and presence of 3-phosphoglyceric acid.

    PubMed

    Burger, Brian T; Cross, Joanna M; Shaw, Janine R; Caren, Joel R; Greene, Thomas W; Okita, Thomas W; Hannah, L Curtis

    2003-07-01

    Adenosine diphosphate glucose pyrophosphorylase (AGPase; EC 2.7.7.27) synthesizes the starch precursor, ADP-glucose. It is a rate-limiting enzyme in starch biosynthesis and its activation by 3-phosphoglyceric acid (3PGA) and/or inhibition by inorganic phosphate (Pi) are believed to be physiologically important. Leaf, tuber and cereal embryo AGPases are highly sensitive to these effectors, whereas endosperm AGPases are much less responsive. Two hypotheses can explain the 3PGA activation differences. Compared to leaf AGPases, endosperm AGPases (i) lack the marked ability to be activated by 3PGA or (ii) they are less dependent on 3PGA for activity. The absence of purified preparations has heretofore negated answering this question. To resolve this issue, heterotetrameric maize ( Zea mays L.) endosperm and potato ( Solanum tuberosum L.) tuber AGPases expressed in Escherichia coli were isolated and the relative amounts of enzyme protein were measured by reaction to antibodies against a motif resident in both small subunits. Resulting reaction rates of both AGPases are comparable in the presence but not in the absence of 3PGA when expressed on an active-protein basis. We also placed the potato tuber UpReg1 mutation into the maize AGPase. This mutation greatly enhances 3PGA sensitivity of the potato AGPase but it has little effect on the maize AGPase. Thirdly, lysines known to bind 3PGA in potato tuber AGPase, but missing from the maize endosperm AGPase, were introduced into the maize enzyme. These had minimal effect on maize endosperm activity. In conclusion, the maize endosperm AGPase is not nearly as dependent on 3PGA for activity as is the potato tuber AGPase. PMID:14520572

  5. 3D printing of new biobased unsaturated polyesters by microstereo-thermallithography.

    PubMed

    Gonçalves, Filipa A M M; Costa, Cátia S M F; Fabela, Inês G P; Farinha, Dina; Faneca, Henrique; Simões, Pedro N; Serra, Arménio C; Bártolo, Paulo J; Coelho, Jorge F J

    2014-09-01

    New micro three-dimensional (3D) scaffolds using biobased unsaturated polyesters (UPs) were prepared by microstereo-thermal-lithography (μSTLG). This advanced processing technique offers indubitable advantages over traditional printing methods. The accuracy and roughness of the 3D structures were evaluated by scanning electron microscopy and infinite focus microscopy, revealing a suitable roughness for cell attachment. UPs were synthesized by bulk polycondensation between biobased aliphatic diacids (succinic, adipic and sebacic acid) and two different glycols (propylene glycol and diethylene glycol) using fumaric acid as the source of double bonds. The chemical structures of the new oligomers were confirmed by proton nuclear magnetic resonance spectra, attenuated total reflectance Fourier transform infrared spectroscopy and matrix assisted laser desorption/ionization-time of flight mass spectrometry. The thermal and mechanical properties of the UPs were evaluated to determine the influence of the diacid/glycol ratio and the type of diacid in the polyester's properties. In addition an extensive thermal characterization of the polyesters is reported. The data presented in this work opens the possibility for the use of biobased polyesters in additive manufacturing technologies as a route to prepare biodegradable tailor made scaffolds that have potential applications in a tissue engineering area. PMID:25190707

  6. Unsaturated Glycoceramides as Molecular Carriers for Mucosal Drug Delivery of GLP-1

    PubMed Central

    te Welscher, Yvonne M.; Chinnapen, Daniel J.-F.; Kaoutzani, Lydia; Mrsny, Randall J.; Lencer, Wayne I.

    2014-01-01

    Summary The incretin hormone Glucagon-like peptide 1 (GLP-1) requires delivery by injection for the treatment of Type 2 diabetes mellitus. Here, we test if the properties of glycosphingolipid trafficking in epithelial cells can be applied to convert GLP-1 into a molecule suitable for mucosal absorption. GLP-1 was coupled to the extracellular oligosaccharide domain of GM1 species containing ceramides with different fatty acids and with minimal loss of incretin bioactivity. When applied to apical surfaces of polarized epithelial cells in monolayer culture, only GLP-1 coupled to GM1-ceramides with short-or cis-unsaturated fatty acids trafficked efficiently across the cell to the basolateral membrane by transcytosis. In vivo studies showed mucosal absorption after nasal administration. The results substantiate our recently reported dependence on ceramide structure for trafficking the GM1 across polarized epithelial cells and support the idea that specific glycosphingolipids can be harnessed as molecular vehicles for mucosal delivery of therapeutic peptides. PMID:24370893

  7. Quasi-steady centrifuge method for unsaturated hydraulic properties

    USGS Publications Warehouse

    Caputo, M.C.; Nimmo, J.R.

    2005-01-01

    [1] We have developed the quasi-steady centrifuge (QSC) method as a variation of the steady state centrifuge method that can be implemented simply and inexpensively with greater versatility in terms of sample size and other features. It achieves these advantages by somewhat relaxing the criterion for steadiness of flow through the sample. This compromise entails an increase in measurement uncertainty but to a degree that is tolerable in most applications. We have tested this new approach with an easily constructed apparatus to establish a quasi-steady flow of water in unsaturated porous rock samples spinning in a centrifuge, obtaining measurements of unsaturated hydraulic conductivity and water retention that agree with results of other methods. The QSC method is adaptable to essentially any centrifuge suitable for hydrogeologic applications, over a wide range of sizes and operating speeds. The simplified apparatus and greater adaptability of this method expands the potential for exploring situations that are common in nature but have been the subject of few laboratory investigations. Copyright 2005 by the American Geophysical Union.

  8. Pore scale imaging of transport in unsaturated flows

    NASA Astrophysics Data System (ADS)

    Jimenez-Martinez, J.; De Anna, P.; Turuban, R.; Tabuteau, H.; Le Borgne, T.; Meheust, Y.

    2013-12-01

    The unsaturated zone plays a key role in the transfer of chemical elements from the surface to the subsurface. Predicting the transport of chemical species through unsaturated porous media poses several challenges. The spatial distribution of wetting (water) and non-wetting (air) clusters focuses the water flow onto narrow and complex flow paths. The resulting velocity distribution is wider than that of saturated flow, and is controlled by the saturation degree. As saturation decreases, very low velocity zones in regions of trapped fluid coexist with connected fluid clusters with relatively high velocities. As a consequence, the dispersion of solute elements strongly depends on the saturation degree. We use a novel experimental setup to study the dependence on saturation of the longitudinal dispersion coefficient. The two-dimensional (2d) horizontal medium consists of cylindrical grains and is built using soft lithography. The joint injection of the two phases (wetting and non-wetting) provides a controlled homogeneous saturation in the medium. The simultaneous precise measurement of the flow field, the spatial distribution of wetting and non-wetting phases, and the 2d tracer concentration field, as well as breakthrough curves at different locations, are used to investigate the relationship between the flow field complexity and dispersion properties. The experimental results show a non-Fickian transport behavior, characterized by heavy tailed breakthrough curves and a longitudinal plume variance that does not scale linearly with time. We document and discuss the dependence of these transport properties on the saturation degree.

  9. Colloid suspension stability and transport through unsaturated porous media

    SciTech Connect

    McGraw, M.A.; Kaplan, D.I.

    1997-04-01

    Contaminant transport is traditionally modeled in a two-phase system: a mobile aqueous phase and an immobile solid phase. Over the last 15 years, there has been an increasing awareness of a third, mobile solid phase. This mobile solid phase, or mobile colloids, are organic or inorganic submicron-sized particles that move with groundwater flow. When colloids are present, the net effect on radionuclide transport is that radionuclides can move faster through the system. It is not known whether mobile colloids exist in the subsurface environment of the Hanford Site. Furthermore, it is not known if mobile colloids would likely exist in a plume emanating from a Low Level Waste (LLW) disposal site. No attempt was made in this study to ascertain whether colloids would form. Instead, experiments and calculations were conducted to evaluate the likelihood that colloids, if formed, would remain in suspension and move through saturated and unsaturated sediments. The objectives of this study were to evaluate three aspects of colloid-facilitated transport of radionuclides as they specifically relate to the LLW Performance Assessment. These objectives were: (1) determine if the chemical conditions likely to exist in the near and far field of the proposed disposal site are prone to induce flocculation (settling of colloids from suspension) or dispersion of naturally occurring Hanford colloids, (2) identify the important mechanisms likely involved in the removal of colloids from a Hanford sediment, and (3) determine if colloids can move through unsaturated porous media.

  10. Rheological behaviour of nanocellulose reinforced unsaturated polyester nanocomposites.

    PubMed

    Chirayil, Cintil Jose; Mathew, Lovely; Hassan, P A; Mozetic, Miran; Thomas, Sabu

    2014-08-01

    Nanocellulose (NC) reinforced unsaturated polyester (UPR) composites were prepared by mechanical mixing process. Effect of isora nanocellulose on the properties of polyester composites has been studied in detail. Rheological properties of unsaturated polyester resin suspensions containing various amounts (0.5, 1 and 3wt%) of nanocellulose were investigated by oscillatory rheometer with parallel plate geometry. Analysis of curing revealed that the time required for gelation in NC filled UPR is lower than neat resin, which describe the catalytic action of NC on cure reaction. NC reinforced polyester suspensions showed shear thinning behaviour initially and at higher shear rates they showed Newtonian behaviour. Tensile and impact properties showed superior behaviour revealing improved interfacial bonding between nanofiller and the polymer matrix. With respect to the neat polyester the percentage increase in tensile strength of 0.5wt% NC reinforced composite is 57%. Optical and atomic force microscopic studies confirmed that the dispersion state of NC within the polyester matrix was adequate. Maximum glass transition temperature is obtained for 0.5wt% NC reinforced composite, which showed an increase of 10°C than neat resin. PMID:24877644

  11. Review of Upscaling Methods for Describing Unsaturated Flow

    SciTech Connect

    BD Wood

    2000-09-26

    The representation of small-scale features can be a challenge when attempting to model unsaturated flow in large domains. Upscaling methods offer the possibility of reducing the amount of resolution required to adequately simulate such a problem. In this report, the various upscaling techniques that are discussed in the literature are reviewed. The following upscaling methods have been identified from the literature: (1) stochastic methods, (2) renormalization methods, and (3) volume averaging and homogenization methods; in addition, a final technique, full resolution numerical modeling, is also discussed. Each of these techniques has its advantages and disadvantages. The trade-off is a reduction in accuracy in favor of a method that is easier to employ. For practical applications, the most reasonable approach appears to be one in which any of the upscaling methods identified above maybe suitable for upscaling in regions where the variations in the parameter fields are small. For regions where the subsurface structure is more complex, only the homogenization and volume averaging methods are probably suitable. With the continual increases in computational capacity, fill-resolution numerical modeling may in many instances provide a tractable means of solving the flow problem in unsaturated systems.

  12. Physical Morphology and Surface Properties of Unsaturated Pseudomonas putida Biofilms

    PubMed Central

    Auerbach, Ilene D.; Sorensen, Cody; Hansma, Helen G.; Holden, Patricia A.

    2000-01-01

    Unsaturated biofilms of Pseudomonas putida, i.e., biofilms grown in humid air, were analyzed by atomic force microscopy to determine surface morphology, roughness, and adhesion forces in the outer and basal cell layers of fresh and desiccated biofilms. Desiccated biofilms were equilibrated with a 75.5% relative humidity atmosphere, which is far below the relative humidity of 98 to 99% at which these biofilms were cultured. In sharp contrast to the effects of drying on biofilms grown in fluid, we observed that drying caused little change in morphology, roughness, or adhesion forces in these unsaturated biofilms. Surface roughness for moist and dry biofilms increased approximately linearly with increasing scan sizes. This indicated that the divides between bacteria contributed more to overall roughness than did extracellular polymeric substances (EPS) on individual bacteria. The EPS formed higher-order structures we termed mesostructures. These mesostructures are much larger than the discrete polymers of glycolipids and proteins that have been previously characterized on the outer surface of these gram-negative bacteria. PMID:10850998

  13. In vivo measurement of plasma cholesterol and fatty acid synthesis with deuterated water: determination of the average number of deuterium atoms incorporated.

    PubMed

    Diraison, F; Pachiaudi, C; Beylot, M

    1996-07-01

    Fractional lipid synthesis can be measured using the incorporation of deuterium from deuterated water. The calculations require knowledge of the maximum incorporation number (N) of deuterium atoms in the molecules synthesized. For both tissue palmitate and cholesterol, N values have been found to be higher during in vivo versus in vitro experiments. We determined the N values to be used for measuring the fractional synthesis of plasma cholesterol and of palmitate triglycerides (TG). Rats were given drinking water enriched (7% to 10%) with deuterated water, and N was determined from the mass isotopomer distributions of plasma cholesterol and plasma TG palmitate and the deuterium enrichment of plasma water. We found N to be 21 for palmitate and 27 for cholesterol. These values agree with those reported for tissue palmitate and cholesterol in vivo, and are higher than values found in vitro. We also found large deuterium enrichments in plasma glucose and in liver lactate and pyruvate. We suggest that, compared with in vitro studies, in vivo metabolism of these compounds leads to an additional pathway of incorporation of deuterium into lipids through deuterium-labeled acetyl coenzyme A (CoA). This could explain why N values are higher in vivo than in vitro. PMID:8692014

  14. Reaction mechanism studies of unsaturated molecules using photofragment translational spectroscopy

    SciTech Connect

    Longfellow, C.A. |

    1996-05-01

    A number of molecules have been studied using the technique of photofragment translational spectroscopy. In Chapter One a brief introduction to the experimental technique is given. In Chapter Two the infrared multiphoton dissociation (IRMPD) of acetic acid is discussed. Carbon dioxide and methane were observed for the first time as products from dissociation under collisionless conditions. Chapter Three relates an IRMPD experiment of hexafluoropropene. The predominant channel produces CFCF{sub 3} or C{sub 2}F{sub 4} and CF{sub 2}, with the heavier species undergoing further dissociation to two CF{sub 2} fragments. In Chapter Four the ultraviolet (UV) dissociation of hexafluoropropene is investigated. Chapter Five explores the IRMPD of octafluoro-1-butene and octafluoro-2-butene.

  15. Liquid-phase catalytic hydrogenation of unsaturated compounds: A new view on the causes of the zero order of the reaction

    SciTech Connect

    Paseka, I. )

    1990-02-01

    The hydrogenation of maleic acid has been studied as a model hydrogenation of unsaturated double-bond compounds in aqueous and alcoholic 1 M H{sub 2}SO{sub 4} solutions. The curves of hydrogenation uptake time and catalyst potential time show that as the reaction proceeds the degree of surface coverage by the organic substance decreases with the logarithm of its bulk concentration. The kinetic equation derived for the reaction indicates that the decrease in the surface coverage is offset by a change in the catalyst potential or in the chemical potential of adsorbed hydrogen, resulting in a constant hydrogenation rate and zero-order reaction with respect to the unsaturated compound.

  16. Vinasse application to sugar cane fields. Effect on the unsaturated zone and groundwater at Valle del Cauca (Colombia).

    PubMed

    Ortegón, Gloria Páez; Arboleda, Fernando Muñoz; Candela, Lucila; Tamoh, Karim; Valdes-Abellan, Javier

    2016-01-01

    Extensive application of vinasse, a subproduct from sugar cane plantations for bioethanol production, is currently taking place as a source of nutrients that forms part of agricultural management in different agroclimatic regions. Liquid vinasse composition is characterised by high variability of organic compounds and major ions, acid pH (4.7), high TDS concentration (117,416-599,400mgL(-1)) and elevated EC (14,350-64,099μScm(-1)). A large-scale sugar cane field application is taking place in Valle del Cauca (Colombia), where monitoring of soil, unsaturated zone and the aquifer underneath has been made since 2006 to evaluate possible impacts on three experimental plots. For this assessment, monitoring wells and piezometers were installed to determine groundwater flow and water samples were collected for chemical analysis. In the unsaturated zone, tensiometers were installed at different depths to determine flow patterns, while suction lysimeters were used for water sample chemical determinations. The findings show that in the sandy loam plot (Hacienda Real), the unsaturated zone is characterised by low water retention, showing a high transport capacity, while the other two plots of silty composition presented temporal saturation due to La Niña event (2010-2011). The strong La Niña effect on aquifer recharge which would dilute the infiltrated water during the monitoring period and, on the other hand dissolution of possible precipitated salts bringing them back into solution may occur. A slight increase in the concentration of major ions was observed in groundwater (~5% of TDS), which can be attributed to a combination of factors: vinasse dilution produced by water input and hydrochemical processes along with nutrient removal produced by sugar cane uptake. This fact may make the aquifer vulnerable to contamination. PMID:26372944

  17. THE RETC CODE FOR QUANTIFYING THE HYDRAULIC FUNCTIONS OF UNSATURATED SOILS

    EPA Science Inventory

    This report describes the RETC computer code for analyzing the soil water retention and hydraulic conductivity functions of unsaturated soils. These hydraulic properties are key parameters in any quantitative description of water flow into and through the unsaturated zone of soil...

  18. Odd-chain polyunsaturated fatty acids in thraustochytrids.

    PubMed

    Chang, Kim Jye Lee; Mansour, Maged P; Dunstan, Graeme A; Blackburn, Susan I; Koutoulis, Anthony; Nichols, Peter D

    2011-08-01

    A series of unusual odd-chain fatty acids (OC-FA) were identified in two thraustochytrid strains, TC 01 and TC 04, isolated from waters off the south east coast of Tasmania, Australia. FA compositions were determined by capillary GC and GC-MS, with confirmation of polyunsaturated fatty acids (PUFA) structure performed by analysis of 4,4-dimethyloxazoline derivatives. PUFA constituted 68-74% of the total FA, with the essential PUFA; eicosapentaenoic acid (20:5ω3, EPA), arachidonic acid (20:4ω6, AA) and docosahexaenoic acid (22:6ω3, DHA), accounting for 42-44% of the total FA. High proportions of the saturated OC-FA 15:0 (7.1% in TC 01) and 17:0 (6.2% in TC 04) were detected. The OC-FA 17:1ω8 was present at 2.8% in TC 01. Of particular interest, the C₂₁ PUFA 21:5ω5 and 21:4ω7 were detected at 3.5% and 4.1%, respectively, in TC 04. A proposed biosynthesis pathway for these OC-PUFA is presented. It is possible that the unsaturated OC-PUFA found previously in a number of marine animals were derived from dietary thraustochytrids and they could be useful biomarkers in environmental and food web studies. PMID:21546043

  19. An Analytical Model for Solute Transport in Unsaturated Flowthrough a Single Fracture and Porous Rock Matrix

    SciTech Connect

    Houseworth, J.E.

    2004-09-16

    Exact analytical solutions are presented for solute transport in an unsaturated fracture and porous rock matrix. The problem includes advective transport in the fracture and rock matrix as well as advective and diffusive fracture-matrix exchange. Linear sorption in the fracture and matrix and radioactive decay are also treated. The solution is for steady, uniform transport velocities within the fracture and matrix, but allows for independent specification of each of the velocities. The problem is first solved in terms of the solute concentrations that result from an instantaneous point source. Superposition integrals are then used to derive the solute mass flux at a fixed downstream position from an instantaneous point source and for the solute concentrations that result from a continuous point source. Solutions are derived for cases with the solute source in the fracture and the solute source in the matrix. The analytical solutions are closed-form and are expressed in terms of algebraic functions, exponentials, and error functions. Comparisons between the analytical solutions and numerical simulations, as well as sensitivity studies, are presented. Increased sensitivity to cross-flow and solute source location is found for increasing Peclet number. The numerical solutions are found to compare well with the analytical solutions at lower Peclet numbers ,but show greater deviation at higher Peclet numbers.

  20. Changes in ester-linked phospholipid fatty acid profiles of subsurface bacteria during starvation and desiccation in a porous medium

    SciTech Connect

    Kieft, T.L.; Ringelberg, D.B.; White, D.C.

    1994-09-01

    Ester-linked phospholipid fatty acid (PLFA) profiles of a Pseudomonas aureofaciens strain and an Arthrobacter protophormiae strain, each isolated from a subsurface sediment, were quantified in a starvation experiment in a silica sand porous medium under moist and dry conditions. Washed cells were added to sand microcosms and maintained under saturated conditions or subjected to desiccation by slow drying over a period of 16 days. In a third treatment, cells were added to saturated microcosms along with organic nutrients and maintained under saturated conditions. The numbers of culturable cells of both bacterial strains declined to below detection level within 16 days in both the moist and dried nutrient-deprived conditions, while direct counts and total PLFAs remained relatively constant. Both strains of bacteria maintained culturability in the nutrient-amended microcosms. The dried P. aureofaciens cells showed increased ratios of saturated to unsaturated fatty acids, increased ratios of trans- to cis-monoenoic fatty acids, and increased ratios of cyclopropyl fatty acids to their monoenoic precursors. P. aureofaciens starved under moist conditions showed few changes in PLFA profiles during the 16-day incubation, whereas cells incubated in the presence of nutrients showed decreases in the ratios of both saturated fatty acids to unsaturated fatty acids and cyclopropyl fatty acids to their monoenoic precursors. The PLFA profiles of A. protophormiae changed very little in response to either nutrient deprivation or desiccation. Diglyceride fatty acids, proposedindicators of dead or lysed cells, remained relatively constant throughout the experiment. The results of this laboratory experiment can be useful for interpreting PLFA profiles of subsurface communities of microorganisms for the purpose of determining their physiological status. 43 refs., 8 figs.