Inhibitory effect of linoleic acid on chain elongation and desaturation of 18∶2 c,t isomers in lactating and neonatal rats

The previous studies showed that dietary 18∶2 c,t isomers could be chain-elongated and desaturated to produce unusual 20∶4 isomers. The present study was undertaken to determine the minimal amount of 18∶2n−6 required to suppress the chain elongation and desaturation of 18∶2 c,t isomers in the lactating and neonatal rats when animals were fed 15% partially hydrogenated canola oil diet containing 1.72% energy as 18∶2 c,t isomers and varying amounts of free 18∶2n−6. These diets induced marginal essential fatty acid (EFA) deficiency states (0.56% energy 18∶2n−6) to EFA adequacy (2.56% energy 18∶2n−6). After feeding for 50 d, the female animals were mated with males by overnight pairing. After conception, the lactating rats were killed, together with one pup from each dam, at term and day 26 of lactation. Two unusual 20∶4 isomers in both maternal and neonatal liver phospholipids were identified as 20∶4Δ5c,8c,11c,14t and 20∶4Δ5c,8c,11c,15t, which were derived from 18∶2Δ9c,12t, and 18∶2Δ9c,13t, respectively. The results showed that 18∶2n−6 at about 2.0% of total energy in maternal diet was required to block the production of 20∶4Δ5c,8c,11c,14t and 20∶4Δ5c,8c,11c,15t in the maternal liver, whereas 18∶2n−6 at about 2.5% of total energy in maternal diet was required to suppress production of these unusual 20∶4 isomers in the neonatal liver.     

Effect of 18∶1n−9, 20∶5n−3, and 22∶6n−3 on lipid accumulation and secretion by atlantic salmon hepatocytes

We have studied the effects of dietary FA on the accumulation and secretion of [³H]glycerolipids by salmon hepatocytes in culture. Atlantic salmon were fed diets supplemented with either 100% soybean oil (SO) or 100% fish oil (FO), and grew from an initial weight of 113±5 g to a final weight of 338 ±19 g. Hepatocytes were isolated from both dietary groups and incubated with [³H]glycerol in an FA-free medium; a medium supplemented with 0.75 mM of one of three FA—18∶1n−9, 20∶5n−3, or 22∶6n−3—or a medium supplemented with 0.75 mM of the sulfur-substituted FA analog tetradecylthioacetic acid (TTA), which cannot undergo β-oxidation. Incubations were allowed to proceed for 1,2,6, or 24 h. The rate of the secretion of radioactive glycerolipids with no FA added was 36% lower from hepatocytes isolated from fish fed the FO diet than it was from hepatocytes isolated from fish fed the SO diet. Hepatocytes incubated with 18∶1n−9 secreted more [³H]TAG than when incubated with no FA, whereas hepatocytes incubated with 20∶5n−3 or TTA secreted less labeled TAG than when incubated with no FA. This observation was independent of the feeding group. Hepatocytes incubated with 22∶6n−3 secreted the highest amounts of total [³H]glycerolipids compared with the other treatments, owing to increased secretion of phospholipids and mono- and diacylglycerols (MDG). In contrast, the same amounts of [³H]TAG were secreted from these cells as from cells incubated in an FA-free medium. The lipid-lowering effect of FO is thus independent of 22∶6n−3, showing that 20∶5n−3 is the FA that is responsible for the lipid-lowering effect. The ratio of TAG to MDG in lipids secreted from hepatocytes to which 20∶5n−3 or TTA had been added was lower than that in lipids secreted from hepatocytes incubated with 18∶1n−9 or 22∶6n−3, suggesting that the last step in TAG synthesis was inhibited. Morphometric measurements revealed that hepatocytes incubated with 20∶5n−3 accumulated significantly more cellular lipid than cells treated with 18∶1n−9, 22∶6n−3, TTA, or no treatment. The area occupied by mitochondria was also greater in these cells. The present study shows that dietary FO reduces TAG secretion from salmon hepatocytes and that 20∶5n−3 mediates this effect.     

Effects of margarine and butter consumption on distribution of trans-18∶1 fatty acid isomers and conjugated linoleic acid in major serum lipid classes in lactating women

Trans FA (TFA) have at least one trans double bond and comprise several isomers and types, including many of the CLA (e.g., c9, t11–18∶2 CLA). Some TFA may have adverse effects (e.g., cardiovascular disease), whereas some are though to have beneficial effects (e.g., anticarcinogenicity). The presence of TFA in human tissues and fluids is related to dietary intake, although this relationship is not completely understood—especially in regard to serum lipid fractions. This study was conducted as part of an investigation designed to test the influence of butter (B), “low TFA” margarine (LT), and regular margarine (RM) on milk fat content. Here we tested the secondary hypothesis that consumption of B, LT, and RM by lactating women would result in differential distribution of TFA and CLA in major serum lipid classes. Breastfeeding women (n=11) participated in this randomized Latinsquare study consisting of five periods: intervention I (5 d), washout I (7 d), intervention II (5 d), washout II (7 d), and intervention III (5 d). Extracted serum lipid was separated into cholesterol ester (CE), TAG, and phospholipid (PL) fractions and analyzed for total and isomeric TFA and CLA concentrations. Data indicate that TAG consistently contained the highest concentration of total t-18∶1. No interaction between treatment and fraction was found for any of the t-18∶1 isomers identified. Absolute concentration of each t-18∶1 isomer was greatest during the RM period, regardless of fraction. On a relative basis, concentrations of t10–18∶1 and t12–18∶1 were most responsive to treatment in the CE fraction. The concentration of c9, t11–18∶2 CLA was highest in the TAG fraction and lowest in the PL fraction, regardless of treatment. In summary, these results indicate (i) that there is a differential distribution of some isomeric TFA and CLA among human serum lipid fractions and (ii) that dietary TFA intake influences absolute and relative concentrations of some of the isomers in selected fractions.     

Biosynthesis and tissue deposition of docosahexaenoic acid (22∶6n−3) in rainbow trout (Oncorhynchus mykiss)

Rainbow trout (Oncorhynchus mykiss) weighing ca. 5 g and previously acclimated for 8 wk on a diet comprising vegetable oil (11%), fish meal (5%), and casein (48%) as the major constituents were fed a pulse of diet containing deuterated (D₅) (17,17,18,18,18)-18∶3n−3 ethyl ester. The synthesis and tissue distribution of D₅-22∶6n−3 was determined 3,7,14, 24, and 35 d after the pulse. The whole-body accumulation of D₅-22∶6n−3 was linear over the first 7 d, corresponding to a rate of 0.54±0.12 μg D₅-22∶6n−3/g fish/mg D₅-18∶3n−3 eaten/d. Maximal accretion of D₅-22∶6n−3 was 4.3±1.2 μg/g fish/mg of D₅-18∶3n−3 eaten after 14 d. The amount of D₅-22∶6n−3 peaked in liver at day 7, in brain and eyes at day 24, and plateaued after day 14 in visceral and eye socket adipose tissue and in the whole fish. The majority of D₅-22∶6n−3 was found in the carcass (remaining tissues minus the above tissues analyzed separately) at all times. On a per milligram lipid basis, liver and eyes had the highest concentration of D₅-22∶6n−3. The experimental diet also contained 21∶4n−6 ethyl ester as a marker to estimate the amount of food eaten by individual fish. From such estimates it was calculated that the great majority of the D₅-tracer was catabolized, with the combined recovery of D₅-18∶3n−3 plus D₅-22∶6n−3 being 2.6%. The recovery of 21∶4n−6 was 57.6%. The concentration of 22∶6n−3 in the fish decreased during the 13-wk period, and the amount of 22∶6n−3 synthesized from 18∶3n−3 was only about 5% of that obtained directly from the fish meal in the diet.     

Direct and improved synthesis of the tri-nickel sandwich-type polyoxoanion [Ni3Na(H2O)2(PW9O34)2]11−

The direct use of preformed B,α-Na₉PW₉O₃₄ was successful in improving the synthesis of Na₁₁[Ni₃Na(H₂O)₂(PW₉O₃₄)₂]·14H₂O. The complex was characterized by elemental analysis, IR spectroscopy, magnetic properties and cyclic voltammetry. The yield was increased to 30%, which is four times more than that obtained in the initial synthesis. The delay before the appearance of the first crystals is drastically shortened, from months to hours, and these crystals are predominantly those of the yellow compound of interest. Keys to these improvements are the use of freshly prepared B,α-Na₉PW₉O₃₄ through prolonged heating of A,β-Na₉PW₉O₃₄ and the increase of the concentrations of the reactants in a close-to-neutral pH medium. Starting the synthesis with several concentrations of preformed A,β-Na₉PW₉O₃₄ revealed the importance of the concentrations of reactants in speeding up the formation of crystals and suggested strongly that the [A-PW₉O₃₄]⁹⁻→[B-PW₉O₃₄]⁹⁻ isomerization might be the slow step in the whole process. Cyclic voltammograms as well as X-ray diffraction structure determination confirm that the synthesized compound is indeed Na₁₁[Ni₃Na(H₂O)₂(PW₉O₃₄)₂]·14H₂O. A study of the magnetic properties of Na₁₁[Ni₃Na(H₂O)₂(PW₉O₃₄)₂]·14H₂O indicates that the three nickel centres exhibit ferromagnetic exchange interactions.     

Preparation and electrical properties of (1−x)SrBi2Nb2O9−xBiFeO3 lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics, (1−x)SrBi₂Nb₂O₉−xBiFeO₃ [(1−x)SBN−xBFO] (x=0.0, 0.03, 0.05, 0.07, 0.10) were prepared by a conventional solid-state reaction method. The crystal structure, microstructure and electrical properties were systematically investigated. All compositions formed layered perovskite structure without any detectable secondary phases. Plate-like morphology of the grains which is characteristic for layer-structure Aurivillius compounds was clearly observed. The excellent electrical properties (e.g., d₃₃~19 pC/N, 2P_r~18.8 μC/cm²) and a high Curie temperature (e.g., T_c~449 °C) were simultaneously obtained in the ceramics with x=0.05. Additionally, thermal annealing studies indicated that the BFO modified SBN ceramics system possessed stable piezoelectric properties, demonstrating that the modified SBN-based ceramics are the promising candidates for high-temperature applications.     

Dietary comparison of conjugated linolenic acid (9 cis, 11 trans, 13 trans) and α-tocopherol effects on blood lipids and lipid peroxidation in alloxan-induced diabetes mellitus in rats

The present study investigated the dietary effect of conjugated linolenic acid (CLnA) on lipid profiles and lipid peroxidations in alloxan-induced diabetes mellitus in rats. Diabetic rats were fed with 20% sunflower oil (diabetic control), sunflower oil supplemented with 0.5% CLnA, sunflower oil supplemented with 0.15% α-tocopherol, and sunflower oil containing 0.25% CLnA+0.15% α-tocopherol. The results demonstrated that 0.5% CLnA, 0.15% α-tocopherol, and 0.25% CLnA+0.15% α-tocopherol each on supplementation significantly lowered total cholesterol and non-HDL-cholesterol in comparison with the diabetic control group. The TAG level was significantly lowered in both the 0.15% α-tocopherol and 0.25% CLnA+0.15% α-tocopherol groups. LDL lipid peroxidation and erythrocyte membrane lipid peroxidation were reduced significantly in each of the experimental groups vs. the control group. The CLnA+α-tocopherol diet induced a greater reduction in membrane lipid and liver lipid peroxidation than the α-tocopherol diet alone. In conclusion, dietary CLnA exerts antioxidant activity as evidenced by reduced lipid peroxidation in chemically induced diabetes mellitus.     

1-O-alkyl-2-(ω-oxo)acyl-sn-glycerols from shark oil and human milk fat are potential precursors of PAF mimics and GHB

This study examines the feasibility that peroxidation and lipolysis of 1-O-alkyl-2,3-diacyl-sn-glycerols (DAGE) found in shark liver oil and human milk fat constitutes a potential source of dietary precursors of platelet activating factor (PAF) mimics and of gamma-hydroxybutyrate (GHB). Purified DAGE were converted into 1-O-alkyl-2-acyl-sn-glycerols by pancreatic lipase, without isomerization, and transformed into 1-O-alkyl-2-oxoacyl-sn-glycerols by mild autooxidation. The various core aldehydes without derivatization, as well as the corresponding dinitrophenylhydrazones, were characterized by chromatographic retention time and diagnostic ions by online electrospray mass spectrometry. Core aldehydes of oxidized shark liver oil yielded 23 molecular species of 1-O-alkyl-sn-glycerols with short-chain sn-2 oxoacyl groups, ranging from 4 to 13 carbons, some unsaturated. Autooxidation of human milk fat yielded 1-O-octadecyl-2-(9-oxo)nonanoyl-sn-glycerol, as the major core aldehyde. Because diradylglycerols with short fatty chains are absorbed in the intestine and react with cytidine diphosphate-choline in the enterocytes, it is concluded that formation of such PAF mimics as 1-O-alkyl-2-(ω-oxo)acyl-sn-glycerophosphocholine from unsaturated dietary DAGE is a realistic possibility. Likewise, a C₄ core alcohol produced by aldol-keto reduction of a C₄ core aldehyde constitutes a dietary precursor of the neuromodulator and recreational drug GHB, which has not been previously pointed out.     

Preparation and dielectric properties of ceramics in the SrBi2(Ta1−xNbx)2O9 solid solution system

Ceramics in the SrBi₂(Ta_1−xNb_x)₂O₉ solid solution system were prepared by a solid state reaction process, and the dielectric characteristics were determined together with the microstructures. An increased dielectric constant and improved temperature coefficient of permittivity were achieved in this solid solution system, while the dielectric loss remained at the same level as that of SrBi₂Ta₂O₉.     

A boron cluster with a pair of carboxylic acid groups on adjacent borons: Synthesis and structure of 7,12-(COOH)2-CB11H10−

The dicarboxylic acid, 7,12-(COOH)₂-CB₁₁H₁₀⁻, was prepared and characterized by NMR, IR, MS, and single-crystal X-ray diffraction. Titration studies reveal that 7,12-(COOH)₂-CB₁₁H₁₀⁻ has a pK_a of > 6.35, indicating that this is a significantly weaker acid than typical organic carboxylic acids. This compound is the first example of a CB₁₁⁻ cluster with a B-COOH group to be characterized by X-ray diffraction and the only X-ray structure of a boron cluster that contains an adjacent pair of these groups.     

Influences of dietary n−3 long-chain PUFA on body concentrations of 20∶5n−3, 22∶5n−3, and 22∶6n−3 in the larvae of a marine teleost fish from Australian waters,the striped trumpeter (<Emphasis Type="Italic">Latris lineata</Emphasis>)

We determined the effect of dietary long-chain (≥C₂₀) PUFA (LC-PUFA), 20∶5n−3 and 22∶6n−3, on larval striped trumpeter (Latris lineata) biochemistry through early development and during live feeding with rotifers (Brachionus plicatilis). Rotifers were enriched using seven experimental emulsions formulated with increasing concentrations of n−3 LC-PUFA, mainly 20∶5n−3 and 22∶6n−3. Enriched rotifer n−3 LC-PUFA concentrations ranged from 10–30 mg/g dry matter. Enriched rotifers were fed to striped trumpeter larvae from 5 to 18 d post-hatch (dph) in a short-term experiment to minimize gross deficiency symptoms such as poor survival that could confound results. No relationships were observed between larval growth or survival with dietary n−3 LC-PUFA at 18 dph. The larval FA profiles generally reflected those of the rotifer diet, and significant positive regressions were observed between most dietary and larval FA at 10, 14, and 18 dph. The major exception observed was an inverse relationship between dietary and larval 22∶5n−3. The presence of 22∶5n−3 in elevated amounts when dietary 22∶5n−3. The presence of 22∶5n−3 in elevated amounts when dietary 22∶6n−3 was depressed suggests that elongation of 20∶5n−3 may be occurring in an attempt to raise body concentrations of 22∶6n−3. We hypothesize that accumulation of 22∶5n−3 might be an early indicator of 22∶6n−3 deficiency in larval fish that precedes a reduction in growth or survival. A possible role of 22∶5n−3 as a biochemical surrogate for 22∶6n−3 is discussed.     

1-(3-biaryloxy-2-oxopropyl)indole-5-carboxylic acids and related compounds as dual inhibitors of human cytosolic phospholipase A2α and fatty acid amide hydrolase

Cytosolic phospholipase A2α (cPLA2α) and fatty acid amide hydrolase (FAAH) are enzymes that have emerged as attractive targets for the development of analgesic and anti-inflammatory drugs. We recently reported that 1-[3-(4-octylphenoxy)-2-oxopropyl]indole-5-carboxylic acid (5) is a dual inhibitor of cPLA2α and FAAH. Structure-activity relationship studies revealed that substituents at the indole 3- and 5-positions and replacement of the indole scaffold of this compound by other heterocycles strongly influences the inhibitory potency against cPLA2α and FAAH, respectively. Herein we report the effect of variation of the 4-octyl residue of 5 and an exchange of its carboxylic acid moiety by some bioisosteric functional groups. Several of the compounds assayed were favorably active against both enzymes, and could therefore represent agents with improved analgesic and anti-inflammatory qualities in comparison with selective cPLA2 α and FAAH inhibitors.     

Reduction potentials of H3+xPMo12–xVxO40 and H6+xP2Mo18−xVxO62 heteropolyacid (HPA) catalysts and their catalytic activity for the vapor-phase oxidative dehydrogenation of isobutyric acid

Vanadium-containing H_6+xP₂Mo_18−xV_xO₆₂ (x = 0, 1, 2, and 3) Wells-Dawson heteropolyacid (HPA) catalysts were prepared for use in the oxidative dehydrogenation of isobutyric acid (IBA) to methacrylic acid (MAA). Vanadium-containing H_3+xPMo_12−xV_xO₄₀ (x = 0, 1, 2, and 3) Keggin HPA catalysts were also investigated for the purpose of comparison. The reduction potentials of H_3+xPMo_12−xV_xO₄₀ and H_6+xP₂Mo_18−xV_xO₆₂ catalysts were determined by temperature-programmed reduction (TPR) measurements. The reduction potentials of H_3+xPMo_12−xV_xO₄₀ and H_6+xP₂Mo_18−xV_xO₆₂ catalysts showed volcano-shaped curves and exhibited the same trend with respect to vanadium substitution. The conversions of IBA over H_3+xPMo_12−xV_xO₄₀ and H_6+xP₂Mo_18−xV_xO₆₂ catalysts also showed volcano-shaped curves and exhibited the same trend with respect to vanadium substitution. However, the H_6+xP₂Mo_18−xV_xO₆₂ catalysts showed a higher reduction potential and a higher conversion of IBA than the H_3+xPMo_12−xV_xO₄₀ catalysts at the same level of vanadium substitution. A correlation between reduction potential and catalytic activity of the HPA catalysts clearly demonstrated that the conversion of IBA increased monotonically with increasing reduction potential of the HPA catalysts, across both families of vanadium-containing HPA catalysts examined in this work.     

Phase transitions and electrical characterizations of (K0.5Na0.5)2x(Sr0.6Ba0.4)5−xNb10O30 (KNSBN) ceramics with ‘unfilled’ and ‘filled’ tetragonal tungsten–bronze (TTB) crystal structure

Alkali-doped strontium barium niobate (K_0.5Na_0.5)_2x(Sr_0.6Ba_0.4)_5?xNb₁₀O₃₀ (KNSBN) ceramics has been prepared by a conventional solid-state reaction method. The alkali-dopant concentration x has been varied from 0.24 to 1.15 so that the crystal structure was transformed from ‘unfilled’ to ‘filled’ tetragonal tungsten–bronze (TTB) structure. Apart from the change in the structural properties, the effects of the alkali-dopants on the phase transition as well as ferroelectric, piezoelectric and pyroelectric properties have also been investigated. Phase transitions have been studied in the temperature range of ?200 °C to 350 °C. The origins of these phase transitions are discussed. The addition of the alkali-dopants enhances the ferroelectric, piezoelectric and pyroelectric properties of the KNSBN ceramics. Alkali-doping also favors abnormal grain growth and thus results in a porous microstructure, which might contribute to the enhancement of the pyroelectric performance.     

Highly Selective and Efficient Membrane Transport of Copper as Cu(SCN)2− 4 Ion Using K+-Dicyclohexyl-18-crown-6 as Carrier

Abstract

Potassium-Dicyclohexyl-18-Crown-6 Complex Was Used As A Highly Efficient Carrier For The Uphill Transport Of Copper As Cu(SCN)^2? ₄ Complex Ion Through A Chloroform Bulk Liquid Membrane. By Using Histidine As A Metal Ion Acceptor In The Receiving Phase At The Optimum Ph Of 7.4, The Amount Of Copper Transported Across The Liquid Membrane After 2 Hours Was 90.2 ± 1.0%. The Selectivity And Efficiency Of Copper Transport From Aqueous Solutions Containing Equimolar Mixtures Of Ag⁺, Cd²⁺, Zn²⁺, Ni²⁺, Fe²⁺, Co²⁺, Pb²⁺, Mn²⁺, Fe³⁺, Bi³⁺, And Cr³⁺ Ions Were Investigated. In The Presence Of Pyrophosphate As A Suitable Masking Agent In The Source Phase, The Interfering Effects Of Co²⁺, Zn²⁺, Pb²⁺, And Cd²⁺ Ions Were Completely Eliminated.     

Sandwich type organic-inorganic hybrid of 3d–4f heterometallic containing germanotungstates [{Cu2(1,10-phen)2(μ-CH3COO)2}Ln(α-GeW11O39)2]11 −: Syntheses,crystal structures,magnetic and photoluminescence properties

Alkali salts of organic-inorganic hybrid 3d-4f heterometallic containing derivatives of sandwich type germanotungstates: [{Cu₂(1,10-phen)₂(μ-CH₃COO)₂}Ln(α-GeW₁₁O₃₉)₂]^11 − [Ln = Pr^III (1a), Nd^III (2a), Sm^III (3a), Eu^III (4a), Gd^III (5a); 1,10-phen = 1.10-phenanthroline] have been prepared in the aqueous potassium acetate buffer (pH 4.7) solution. All these compounds were synthesized following by one pot reaction procedure under mild reaction conditions. All compounds were isolated as mixed alkali sodium/potassium salts from the solution and used for further structural characterization by single crystal XRD, powder-XRD, FT-IR, liquid UV/vis, solid state photoluminescence spectroscopy and thermo-gravimetric analysis. FT-IR spectra and powder-XRD pattern suggest that all compounds (1a–5a) are isomorphous. Further single crystal XRD analysis shows that all these compounds exhibit sandwich-type [Ln(α-GeW₁₁O₃₉)₂]^13 − structural feature in the polyoxoanions as the fundamental building block units, and the copper complexes coordinated with 1,10-phen and acetate ligands are coordinated to the terminal oxygen of the polyanion. The compounds 1a, 3a and 4a show good photoluminescence properties at room temperature. The compound 5a shows weak ferromagnetic behavior.     

Bond characteristics,sintering behavior and microwave dielectric properties of Ce2[Zr1−x(Ca1/3Sb2/3)x]3(MoO4)9 ceramics

Ce₂[Zr_1?x(Ca_1/3Sb_2/3)_x]₃(MoO₄)₉ (CZ_1?x(CS)_xM) (x = 0.02–0.10) ceramics were prepared by the conventional solid-state reaction method. The correlations between the chemical bond parameters and microwave dielectric properties were calculated and analyzed by using the Phillips–Van Vechten–Levine (P–V–L) theory. Phase composition and microstructures were evaluated by scanning electron microscopy and X-ray diffraction patterns. Lattice parameters were obtained by Rietveld refinements based on XRD data. Excellent properties for Ce₂[Zr_0.96(Ca_1/3Sb_2/3)_0.04]₃(MoO₄)₉ ceramic sintered at 775 °C: ε_r = 10.68, Q×f = 85,336 GHz and τ_f = ?7.58 ppm/°C were achieved.     

A highly nuclear vanadium-containing tungstobismutate: synthesis and crystal structure of K11H[(BiW9O33)3Bi6(OH)3(H2O)3V4O10]·25 H2O

A novel and large heteropolyanion [(BiW₉O₃₃)₃Bi₆(OH)₃(H₂O)₃V₄O₁₀]¹²⁻ has been synthesized by reaction of sodium metavanadate with Na₉[BiW₉O₃₃]·16H₂O in acetate buffer solutions (at pH 4.8). The present anion has a trilobal structure in which three α-B {BiW₉O₃₃} units are connected to each other by an unique core [Bi₆(OH)₃(H₂O)₃V₄O₁₀]¹⁵⁺. A central bismutate/vanadate-mixed core comprises three sets of two types of the BiO₆ pentagonal pyramid, the edge-sharing VO₅ square-pyramidal triad, and a VO₄ tetrahedron.