Effects of forage source and soybean and marine algal oil supplementation on milk fatty acid composition in ewes

The objective of the present studies was to determine effects of basal dietary forage source on the response of milk fatty acid composition to an oil supplement based (2:1, respectively, w/w) on soybean oil and marine algae biomass oil high in cis-9, cis-12 C18:2n − 3 and C22:6n − 3, respectively. In Study 1, Hampshire × Dorset ewes (48) were randomly assigned to one of four treatments and 12 pens in a completely randomized design blocked on the basis of lambing date and number of lambs suckled. Control rations (60:40 forage:concentrate, dry matter (DM) basis) based on alfalfa pellets (AP) or corn silage (CS) were fed from lambing. Beginning at 22 days postpartum, three pens of ewes fed AP and three pens of ewes fed CS were supplemented with oil (30 g/kg of ration DM) in place of corn meal. Average ewe DM intake (DMI) and average daily gain (ADG) were measured weekly. Milk yield and composition were measured at 42 days postpartum. DMI was lower (P<0.02) for CS and for oil, but milk yield was not affected by forage source or oil supplementation. Milk fat content was higher for oil (P<0.10) and milk protein content was higher for AP (P<0.04). Total CLA concentration (g/100 g fatty acids) increased (P<0.01) with CS and oil, and the response to oil was greater for AP (P<0.04). Similarly, total trans-C18:1 and C22:6ω−3 concentrations were higher for CS and oil, but the response to oil was greater for CS (P<0.06 and P<0.01, respectively). In Study 2, the experiment was repeated using alfalfa haylage (AH) instead of AP. The DMI decreased (P<0.05) with oil feeding, but was not affected by forage source. Milk yield was decreased by feeding oil with AH, but not by feeding oil with CS (P<0.03). Milk fat content tended to be increased by feeding oil with AH, but tended to be decreased by feeding oil with CS (P<0.08). Total CLA concentration was increased (P<0.01) for AH versus CS and by oil, and the response to oil supplementation was greater for AH (P<0.01). In contrast, total trans-C18:1 concentration was higher for CS versus AH, with a greater response to oil for CS (P<0.05). Feeding marine oil increased the C22:6ω−3 (P<0.01) concentration, and the response was greater for AH (P<0.04). To further characterize the response of milk fat composition to dietary oil in ewes, a third study used six pens of three ewes each assigned to either the control CS diet used for Study 2 or the same diet supplemented with 45 g/kg (DM basis) of the oil mixture. Feeding oil had no effect on DMI, milk yield or milk fat concentration, but again increased (P<0.001) total trans-C18:1 and C22:6ω−3 concentrations and numerically increased (114%) total CLA concentration. Milk fatty acid composition responses to supplemental vegetable and marine oils were affected by forage source. Milk trans-C18:1 concentration was higher when CS was fed in Studies 1 and 2, but the effect of forage species on CLA concentration differed between studies, which may reflect differences in diet PUFA content and consumption, as well as amounts of dietary starch and fiber consumed. Despite large increases in trans-C18:1 concentration, milk fat content was not decreased by feeding unsaturated oils to ewes, even at diet levels of 45 g/kg of ration DM.

Examination of the persistency of milk fatty acid composition responses to fish oil and sunflower oil in the diet of dairy cows

Based on the potential benefits of cis-9, trans-11 conjugated linoleic acid (CLA) for human health, there is a need to develop effective strategies for enhancing milk fat CLA concentrations. Levels of cis-9, trans-11 CLA in milk can be increased by supplements of fish oil (FO) and sunflower oil (SO), but there is considerable variation in the response. Part of this variance may reflect time-dependent ruminal adaptations to high levels of lipid in the diet, which lead to alterations in the formation of specific biohydrogenation intermediates. To test this hypothesis, 16 late lactation Holstein-British Friesian cows were used in a repeated measures randomized block design to examine milk fatty acid composition responses to FO and SO in the diet over a 28-d period. Cows were allocated at random to corn silage-based rations (8 per treatment) containing 0 (control) or 45 g of oil supplement/ kg of dry matter consisting (1:2; wt/wt) of FO and SO (FSO), and milk composition was determined on alternate days from d 1. Compared with the control, the FSO diet decreased mean dry matter intake (21.1 vs. 17.9 kg/d), milk fat (47.7 vs. 32.6 g/kg), and protein content (36.1 vs. 33.3 g/kg), but had no effect on milk yield (27.1 vs. 26.4 kg/d). Reductions in milk fat content relative to the FSO diet were associated with increases in milk trans-10 18: 1, trans-10, cis-12 CLA, and trans-9, cis-11 CLA concentrations (r(2) = 0.74, 0.57, and 0.80, respectively). Compared with the control, the FSO diet reduced milk 4: 0 to 18: 0 and cis 18:1 content and increased trans 18:1, trans 18:2, cis-9, trans-11 CLA, 20: 5 n-3, and 22: 6 n-3 concentrations. The FSO diet caused a rapid elevation in milk cis-9, trans-11 CLA content, reaching a maximum of 5.37 g/100 g of fatty acids on d 5, but these increases were transient, declining to 2.35 g/100 g of fatty acids by d 15. They remained relatively constant thereafter. Even though concentrations of trans-11 18: 1 followed the same pattern of temporal changes as cis-9, trans-11 CLA, the total trans 18:1 content of FSO milk was unchanged because of the concomitant increases in the concentration of other isomers (Delta(4-10) and Delta(12-15)), predominantely trans-10 18:1. In conclusion, supplementing diets with FSO enhances milk fat cis-9, trans-11 CLA content, but the high level of enrichment declines because of changes in ruminal biohydrogenation that result in trans-10 replacing trans-11 as the major 18:1 biohydrogenation intermediate formed in the rumen.

Antioxidant and anti-atherogenic activities of olive oil phenolics

The aim of the current study was to investigate the antioxidant and cellular activity of the olive oil phenolics oleuropein, tyrosol, hydroxytyrosol, and homovanillic alcohol (which is also a major metabolite of hydroxytyrosol). Well-characterized chemical and biochemical assays were used to assess the antioxidant potential of the compounds. Further experiments investigated their influence in cell culture on cytotoxic effects of hydrogen peroxide and oxidized low-density lipoprotein (LDL), nitric oxide production by activated macrophages, and secretion of chemoattractant and cell adhesion molecules by the endothelium. Inhibitory influences on in vitro platelet aggregation were also measured. The antioxidant assays indicated that homovanillic alcohol was a significantly more potent antioxidant than the other phenolics, both in chemical assays and in prolonging the lag phase of LDL oxidation. Cell culture experiments suggested that the olive oil phenolics induce a significant reduction in the secretion of intercellular adhesion molecule-1 and vascular cell adhesion molecule-1 (and a trend towards a reduced secretion of monocyte chemoattractant protein-1), and protect against cytotoxic effects of hydrogen peroxide and oxidized LDL. However, no influence on nitric oxide production or platelet aggregation was evident. The data show that olive oil phenolics have biochemical and cellular actions, which, if also apparent in vivo, could exert cardioprotective effects.

A mechanistic study of the low pressure pyrolysis of linear siloxanes

Matrix isolation IR spectroscopy has been used to study the vacuum pyrolysis of 1,1,3,3-tetramethyldisiloxane (L1), 1,1,3,3,5,5-hexamethyltrisiloxane (L2) and 3H,5H-octamethyltetrasiloxane (L3) at ca. 1000 K in a flow reactor at low pressures. The hydrocarbons CH3, CH4, C2H2, C2H4, and C2H6 were observed as prominent pyrolysis products in all three systems, and amongst the weaker features are bands arising from the methylsilanes Me2SiH2 (for L1 and L2) and Me3SiH (for L3). The fundamental of SiO was also observed very weakly. By use of quantum chemical calculations combined with earlier kinetic models, mechanisms have been proposed involving the intermediacy of silanones Me2Si = O and MeSiH = O. Model calculations on the decomposition pathways of H3SiOSiH3 and H3SiOSiH2OSiH3 show that silanone elimination is favoured over silylene extrusion.

Nitrogen management is essential to prevent tropical oil palm plantations from causing ground-level ozone pollution

More than half the world's rainforest has been lost to agriculture since the Industrial Revolution. Among the most widespread tropical crops is oil palm (Elaeis guineensis): global production now exceeds 35 million tonnes per year. In Malaysia, for example, 13% of land area is now oil palm plantation, compared with 1% in 1974. There are enormous pressures to increase palm oil production for food, domestic products, and, especially, biofuels. Greater use of palm oil for biofuel production is predicated on the assumption that palm oil is an "environmentally friendly'' fuel feedstock. Here we show, using measurements and models, that oil palm plantations in Malaysia directly emit more oxides of nitrogen and volatile organic compounds than rainforest. These compounds lead to the production of ground-level ozone (O-3), an air pollutant that damages human health, plants, and materials, reduces crop productivity, and has effects on the Earth's climate. Our measurements show that, at present, O-3 concentrations do not differ significantly over rainforest and adjacent oil palm plantation landscapes. However, our model calculations predict that if concentrations of oxides of nitrogen in Borneo are allowed to reach those currently seen over rural North America and Europe, ground-level O-3 concentrations will reach 100 parts per billion (10(9)) volume (ppbv) and exceed levels known to be harmful to human health. Our study provides an early warning of the urgent need to develop policies that manage nitrogen emissions if the detrimental effects of palm oil production on air quality and climate are to be avoided.

Pyrolysis of polymer-derived carbons in the formation of graphitizing carbons and nanoparticles of zirconia

Carbons have been prepared by the low-temperature pyrolysis, under argon, of a number of long-chain polymers. We have found that the resistivity (Omega cm(-1)) varies considerably with the temperature of pyrolysis; thus, for ammonium polyacrylate, the resistivity of that pyrolyzed at 600 degrees C is 9.7 x 10(4) Omega cm(-1) whereas that pyrolyzed at 1000 degrees C is ca. 3 Omega cm(-1). A similar situation arises for the other polymers studied (including radiolyzed cross-linked polyacrylamide). All those pyrolyzed at 600 degrees C had a resistivity of > 1 x 10(6) Omega cm(-1), whereas those pyrolyzed at 1000 degrees C had a resistivity of ca. 3-5 Omega cm(-1). A notable exception was that of unirradiated polyacrylamide, where the resistivity remained at > 1 x 10(6) Omega cm(-1) over the range of temperatures studied. The decrease of resistivity with increase of temperature of pyrolysis has been related to the formation of glassy carbon. Nanoparticles (4 nm) of tetragonal zirconia were formed when zirconium polyacrylate was pyrolyzed under similar conditions.

The cyclopropene pyrolysis story

Cyclopropene is the last of the small strained ring hydrocarbons to have its thermal decomposition subjected to intensive investigation. This critical review describes the nearly 40 year history of this investigation largely by gas kinetic methods with chromatographic analysis. These studies have revealed that cyclopropenes can decompose by a variety of mechanisms involving diradicals, vinylcarbenes and vinylidenes. Much detailed information has been obtained about the reactivity of these intermediates which has wider implications for thermal hydrocarbon pyrolysis. Theory has also played a important role. Cyclopropene itself has been shown to be an intermediate in the allene A propyne rearrangement. The story itself illustrates how the evolution of mechanistic understanding has been anything but straightforward. (68 references.).

Detection of pressed hazelnut oil in virgin olive oil by analysis of polar components: improvement and validation of the method

An improved method for the detection of pressed hazelnut oil in admixtures with virgin olive oil by analysis of polar components is described. The method. which is based on the SPE-based isolation of the polar fraction followed by RP-HPLC analysis with UV detection. is able to detect virgin olive oil adulterated with pressed hazelnut oil at levels as low as 5% with accuracy (90.0 +/- 4.2% recovery of internal standard), good reproducibility (4.7% RSD) and linearity (R-2: 0.9982 over the 5-40% adulteration range). An international ring-test of the developed method highlighted its capability as 80% of the samples were, on average, correctly identified despite the fact that no training samples were provided to the participating laboratories. However, the large variability in marker components among the pressed hazelnut oils examined prevents the use of the method for quantification of the level of adulteration. (C) 2003 Elsevier Ltd. All rights reserved.

Antioxidant and anti-atherogenic activities of olive oil phenolics

The aim of the current study was to investigate the antioxidant and cellular activity of the olive oil phenolics oleuropein, tyrosol, hydroxytyrosol, and homovanillic alcohol (which is also a major metabolite of hydroxytyrosol). Well-characterized chemical and biochemical assays were used to assess the antioxidant potential of the compounds. Further experiments investigated their influence in cell culture on cytotoxic effects of hydrogen peroxide and oxidized low-density lipoprotein (LDL), nitric oxide production by activated macrophages, and secretion of chemoattractant and cell adhesion molecules by the endothelium. Inhibitory influences on in vitro platelet aggregation were also measured. The antioxidant assays indicated that homovanillic alcohol was a significantly more potent antioxidant than the other phenolics, both in chemical assays and in prolonging the lag phase of LDL oxidation. Cell culture experiments suggested that the olive oil phenolics induce a significant reduction in the secretion of intercellular adhesion molecule-1 and vascular cell adhesion molecule-1 (and a trend towards a reduced secretion of monocyte chemoattractant protein-1), and protect against cytotoxic effects of hydrogen peroxide and oxidized LDL. However, no influence on nitric oxide production or platelet aggregation was evident. The data show that olive oil phenolics have biochemical and cellular actions, which, if also apparent in vivo, could exert cardioprotective effects.

Effect of forage type and proportion of concentrate in the diet on milk fatty acid composition in cows given sunflower oil and fish oil

Based on the potential benefits of cis-9, trans- 11 conjugated linoleic acid (CLA) for human health there is a need to develop effective strategies for enhancing milk fat CLA concentrations. In this experiment, the effect of forage type and level of concentrate in the diet on milk fatty acid composition was examined in cows given a mixture of fish oil and sunflower oil. Four late lactation Holstein-British Friesian cows were used in a 4 x 4 Latin-square experiment with a 2 x 2 factorial arrangement of treatments and 21-day experimental periods. Treatments consisted of grass (G) or maize (M) silage supplemented with low (L) or high (H) levels of concentrates (65: 35 and 35: 65; forage: concentrate ratio, on a dry matter (DM) basis, respectively) offered as a total mixed ration at a restricted level of intake (20 kg DM per day). Lipid supplements (30 g/kg DM) containing fish oil and sunflower oil (2: 3 w/w) were offered during the last 14 days of each experimental period. Treatments had no effect on total DM intake, milk yield, milk constituent output or milk fat content, but milk protein concentrations were lower (P<0.05) for G than M diets (mean 43.0 and 47.3 g/kg, respectively). Compared with grass silage, milk fat contained higher (P<0.05) amounts Of C-12: 0, C-14: 0, trans C-18:1 and long chain >= C20 (n-3) polyunsaturated fatty acids (PUFA) and lower (P<0.05) levels Of C-18:0 and trans C-18:2 when maize silage was offered. Increases in the proportion of concentrate in the diet elevated (P<0.05) C-18:2 (n-6) and long chain >= C20 (n-3) PUFA content, but reduced (P<0.05) the amount Of C-18:3 (n-3). Concentrations of trans-11 C-18:1 in milk were independent of forage type, but tended (P<0.10) to be lower for high concentrate diets (mean 7.2 and 4.0 g/100 g fatty acids, for L and H respectively). Concentrations of trans-10 C-18:1 were higher (P<0.05) in milk from maize compared with grass silage (mean 10.3 and 4.1 g/100 g fatty acids, respectively) and increased in response to high levels of concentrates in the diet (mean 4.1 and 10.3 g/100 g fatty acids, for L and H, respectively). Forage type had no effect (P>0.05) on total milk conjugated linoleic acid (CLA) (2.7 and 2.8 g/100 g fatty acids, for M and G, respectively) or cis-9, trans-11 CLA content (2.2 and 2.4 g/100 g fatty acids). Feeding high concentrate diets tended (P<0.10) to decrease total CLA (3.3 and 2.2 g/100 g fatty acids, for L and H, respectively) and cis-9, trans-11 CLA (2.9 and 1/7 g/100 g fatty acids) concentrations and increase milk trans-9, cis-11 CLA and trans-10, cis-12 CLA content. In conclusion, the basal diet is an important determinant of milk fatty acid composition when a supplement of fish oil and sunflower oil is given.

Effect of dietary fish oil on biohydrogenation of fatty acids and milk fatty acid content in cows

Mechanisms underlying milk fat conjugated linoleic acid (CLA) responses to supplements of fish oil were investigated using five lactating cows each fitted with a rumen cannula in a simple experiment consisting of two consecutive 14-day experimental periods. During the first period cows were offered 18 kg dry matter (DM) per day of a basal (B) diet formulated from grass silage and a cereal based-concentrate (0.6 : 0.4; forage : concentrate ratio, on a DM basis) followed by the same diet supplemented with 250 g fish oil per day (FO) in the second period. The flow of non-esterified fatty acids leaving the rumen was measured using the omasal sampling technique in combination with a triple indigestible marker method based on Li-Co-EDTA, Yb-acetate and Cr-mordanted straw. Fish oil decreased DM intake and milk yield, but had no effect on milk constituent content. Milk fat trans-11C(18:1), total trans-C-18:1, cis-9 trans-11 CLA, total CLA, C-18 :2 (n- 6) and total C-18:2 content were increased in response to fish oil from 1.80, 4.51, 0.39, 0. 56, 0.90 and 1.41 to 9.39, 14.39, 1.66, 1.85, 1.25 and 4.00 g/100 g total fatty acids, respectively. Increases in the cis-9, trans-11 isomer accounted for proportionately 0.89 of the CLA response to fish oil. Furthermore, fish oil decreased the flow of C-18:0 (283 and 47 g/day for B and FO, respectively) and increased that of trans-C-18:1 fatty acids entering the omasal canal (38 and 182 g/day). Omasal flows of trans-C-18:1 acids with double bonds in positions from delta-4 to -15 inclusive were enhanced, but the effects were isomer dependent and primarily associated with an increase in trans-11C(18:1) leaving the rumen (17.1 and 121.1 g/day for B and FO, respectively). Fish oil had no effect on total (4.36 and 3.50 g/day) or cis-9, trans-11 CLA (2.86 and 2.08 g/day) entering the omasal canal. Flows of cis-9, trans-11 CLA were lower than the secretion of this isomer in milk. Comparison with the transfer of the trans-9, trans-11 isomer synthesized in the rumen suggested that proportionately 0.66 and 0.97 of cis-9, trans-11 CLA was derived from endogenous conversion of trans-11 C-18:1 in the mammary gland for B and FO, respectively. It is concluded that fish oil enhances milk fat cis-9, trans-11 CLA content in response to increased supply of trans-11 C-18:1 that arises from an inhibition of trans C-18:1 reduction in the rumen.

Effects of enhanced consumption of fruit and vegetables on plasma antioxidant status and oxidative resistance of LDL in smokers supplemented with fish oil

Objective: To determine whether consumption of five portions of fruit and vegetables per day reduces the enhancement of oxidative stress induced by consumption of fish oil. Subjects: A total of 18 free-living healthy smoking volunteers, aged 18-63 y, were recruited by posters and e-mail in The University of Reading, and by leaflets in local shops. Design: A prospective study. Setting: Hugh Sinclair Unit of Human Nutrition, School of Food Biosciences, The University of Reading, Whiteknights PO Box 226, Reading RG6 6AP, UK. Intervention: All subjects consumed a daily supplement of 4 x 1 g fish oil capsules for 9 weeks. After 3 weeks, they consumed an additional five portions of fruits and vegetables per day, and then they returned to their normal diet for the last 3 weeks of the study. Fasting blood samples were taken at the ends of weeks 0, 3, 6 and 9. Results: The plasma concentrations of ascorbic acid, lutein, beta-cryptoxanthin, alpha-carotene and beta-carotene all significantly increased when fruit and vegetable intake was enhanced (P<0.05). Plasma concentrations of α-tocopherol, retinol and uric acid did not change significantly during the period of increased fruit and vegetable consumption. Plasma oxidative stability, assessed by the oxygen radical absorbance capacity (ORAC) assay, also increased from weeks 3-6 (P<0.001) but not in association with increases in measured antioxidants. Lag phase before oxidation of low-density lipoprotein (LDL) significantly decreased in the first 3 weeks of the study, reflecting the incorporation of EPA and DHA into LDL (P<0.0001). Subsequent enhanced fruit and vegetable consumption significantly reduced the susceptibility of LDL to oxidation (P<0.005). Conclusion: Fish oil reduced the oxidative stability of plasma and LDL, but the effects were partially offset by the increased consumption of fruit and vegetables.

Effects of copper on the antioxidant activity of olive polyphenols in bulk oil and oil-in-water emulsions

The antioxidant activity and interactions with copper of four olive oil phenolic compounds, namely oleuropein, hydroxytyrosol, 3,4- dihydroxyphenylethanol- elenolic acid ( 1), and 3,4- dihydroxyphenyl-ethanolelenolic acid dialdehyde ( 2), in olive oil and oil- in- water emulsions stored at 60 degrees C were studied. All four phenolic compounds significantly extended the induction time of lipid oxidation in olive oil with the order of activity being hydroxytyrosol > compound 1 > compound 2 > oleuropein > alpha- tocopherol; but in the presence of Cu( II), the stability of oil samples containing phenolic compounds decreased by at least 90%, and the antioxidant activity of hydroxytyrosol and compounds 1 and 2 became similar. In oil- in- water emulsions prepared from olive oil stripped of tocopherols, hydroxytyrosol enhanced the prooxidant effect of copper at pH 5.5 but not at pH 7.4. The stability of samples containing copper at pH 5.5 was not significantly different if oleuropein was present from that of the control. Oleuropein at pH 7.4, and compounds 1 and 2 at both pH values tested, reduced the prooxidant effect of copper. The lower stability and the higher reducing capacity of all compounds at pH 7.4 could not explain the higher stability of emulsions containing phenolic compounds at this pH value. However, mixtures containing hydroxytyrosol or oleuropein with copper showed higher 1,1-diphenyl- 2- picrylhydrazyl radical scavenging activity at pH 7.4 than at pH 5.5. Moreover, the compound 2- copper complex showed higher radical scavenging activity then the uncomplexed compound at pH 5.5. It can be concluded that the formation of a copper complex with radical scavenging activity is a key step in the antioxidant action of the olive oil phenolic compounds in an emulsion containing copper ions.

Activity and location of olive oil phenolic antioxidants in liposomes

The antioxidant activity of hydroxytyrosol, hydroxytyrosol acetate, oleuropein, 3,4-dihydroxyphenylelenolic acid (3,4-DHPEA-EA) and 3,4-dihydroxyphenyielenolic acid dialdehyde (3,4-DHPEA-EDA) towards oxidation initiated by 2,2'-azobis (2-amidinopropane) hydrochloride in a soybean phospholipid liposome system was studied. The antioxidant activity of these olive oil phenols was similar and the duration of the lag phase was almost twice that of alpha-tocopherol. Trolox(R), a water-soluble analogue of alpha-tocopherol, showed the worst antioxidant activity. However, oxidation before the end of the lag phase was inhibited less effectively by the olive oil phenols than by alpha-tocopherol and Trolox(R). Synergistic effects (11-20% increase in lag phase) were observed in the antioxidant activity of combinations of alpha-tocopherol with olive oil phenols both with and without ascorbic acid. Fluorescence anisotropy of probes and fluorescence quenching studies showed that the olive oil phenols did not penetrate into the membrane, but their effectiveness as antioxidants showed they were associated with the surface of the phospholipid bilayer. (C) 2003 Elsevier Science Ireland Ltd. All rights reserved.

Interactions of ferric ions with olive oil phenolic compounds

The ferric complexing capacity of four phenolic compounds, occurring in olives and virgin olive oil, namely, oleuropein, hydroxytyrosol, 3,4-dihydroxyphenylethanol-elenolic acid (3,4-DHPEA-EA), and 3,4-dihydroxyphenylethanol-elenolic acid dialdehyde (3,4-DHPEA-EDA), and their stability in the presence of ferric ions were studied. At pH 3.5, all compounds formed a reversible 1:1 complex with ferric ions, but hydroxytyrosol could also form complexes containing > 1 ferric ion per phenol molecule. At pH 5.5, the complexes between ferric ions and 3,4-DHPEA-EA or 3,4-DHPEA-EDA were relatively stable, indicating that the antioxidant activity of 3,4-DHPEA-EA or 3,4-DHPEA-EDA at pH 5.5 is partly due to their metal-chelating activity. At pH 7.4, a complex containing > 1 ferric ion per phenol molecule was formed with hydroxytyrosol. Oleuropein, 3,4-DHPEA-EA, and 3,4-DHPEA-EDA also formed insoluble complexes at this pH. There was no evidence for chelation of Fe(II) by hydroxytyrosol or its derivatives. At all pH values tested, hydroxytyrosol was the most stable compound in the absence of Fe(III) but the most sensitive to the presence of Fe(III).