The fatty acid composition of lipids from muscle and adipose tissues of pigs fed various oil mixtures differing in their ratio between oleic acid and linoleic acid

High concentrations of polyunsaturated fatty acids (PUFA) in meat have detrimental effects on its technical properties. The present study was carried out to investigate whether PUFA levels in pork can be reduced by increasing the concentrations of oleic acid in pig diets. To this end a bifactorial experiment was carried out with 48 female growing finishing pigs. Six different diets were used with two different concentrations of linoleic acid (12 vs. 24 g/kg) and three different concentrations of oleic acid (12 vs. 18 vs. 24 g/kg). The experiment started at a body weight (BW) of 58 kg and continued until 115 kg BW. The fatty acid composition of total lipids of backfat, perirenal fat and musculus (m.) longissimus dorsi was analysed. Concentrations of linoleic acid and total PUFA in backfat and perirenal fat were affected only by the dietary linoleic acid content but not at all by the dietary oleic acid content. Increasing the dietary concentration of oleic acid raised the level of oleic acid in those tissues at the expense of saturated fatty acids, suggesting competition between monounsaturated fatty acids and saturated fatty acids for incorporation into triglycerides. At the low dietary linoleic acid concentration, the percentages of linoleic acid and total PUFA in total lipids of m. longissimus dorsi were also unaffected by the dietary oleic acid content. In contrast, at the high dietary linoleic acid concentration, percentages of linoleic acid and total PUFA of the m. longissimus dorsi were reduced by increasing the dietary concentration of oleic acid, suggesting that oleic acid and linoleic acid compete for incorporation into muscle lipids. Thus, at high dietary linoleic acid levels the fatty acid composition of the m. longissimus dorsi was favourably affected by high dietary oleic acid concentrations; in backfat and perirenal fat, however, no beneficial effect of high dietary oleic acid levels was seen.     

A comparative study of fatty acid profiles in ruminant and non‐ruminant milk

This is a comprehensive study of fatty acid (FA) profiles in milk from bovine, caprine, ovine, asine, and equine species. Milks from these species are universally common as constituents in a variety of different food and dairy products. We have obtained structural information on FAs, and discussed their correlation to health effects. The extracted fat from all species were derivatized to FA methyl esters for analysis by GC‐MS. Large differences in the lipid content and FA composition between ruminants and non‐ruminants were observed. Ovine milk showed the highest lipid content of all the animals tested, both ruminants and non‐ruminants. Among the ruminants, bovine milk was richer in saturated FAs (69.7%) than ovine‐ and caprine milk (57.5 and 59.9%, respectively). Ovine milk contained the highest amounts of monounsaturated FAs (39.1%) and also odd‐ and branched‐chain FAs (5.5%). Milk from the monogastric animals, mares and donkeys, were highest in polyunsaturated FAs with a content of 19.3 and 14.2%, respectively. The assumed health negative trans FAs were analyzed to be highest in the ruminant milk (0.7–1.0%). Milk from these species contained also the highest amount of the health beneficial CLA (0.4–0.7%). Practical applications: This is a comprehensive study of milk from five species analyzed under identical conditions. The different fatty acids and their derivatives are increasingly important components because of the contradictory reports on positive and negative effects on human health. New information on the composition of milk from different species is of great importance. The results may give valuable information to producers and nutritional advisors on the consumption of milk and milk products.     

Characterization of the glycerolipid composition of a high‐palmitoleic acid sunflower mutant

The glycerolipid composition of a high‐palmitoleic acid sunflower (Helianthus annuus L.) mutant accumulating up to 20% of n‐7 fatty acids was studied. This line produces oil with a complex triacylglycerol (TAG) composition, containing species that have not been previously identified in sunflower. In this regard, palmitoleic acid was esterified in an unexpected way in the three positions of the TAG molecules. The polar glycerolipid composition of the mutant was also studied, in order to identify and quantify the changes in membrane lipids imposed by the sunflower enzymatic machinery during the accumulation of the unusual n‐7 fatty acids. The high‐palmitoleic mutant accumulated important quantities of n‐7 fatty acids in the polar lipid fraction, especially in the phosphatidylcholine lipid class. However, the total polar lipid content of these lines was not affected. On the other hand, the mutations responsible for the n‐7 lipid accumulation induced an important decrease in the oil yield of the new mutant.     

Detecting the modest signals of omega‐3 fatty acids' antidepressant effects by homogenizing depressed patient groups

Major depressive disorder (MDD) is predicted to become the top leading cause of disability worldwide by 2020, with a high lifetime prevalence rate of up to one‐tenth or possibly even one‐fifth [1]. The current psychopharmacologic interventions have had fairly limited success and the development of novel antidepressant medications has had mixed results with several unfortunate failures due to limited efficacy and adverse side effects. With such challenges of prevailing pharmacotherapies towards MDD, a new therapeutic strategy in treatment with omega‐3 polyunsaturated fatty acids (omega‐3 or n‐3 PUFAs) supplementation has shown promising outcomes in lowering the risk of depression.     

Effect of chlorine dioxide treatment on lipid oxidation and fatty acid composition in salmon and red grouper fillets

Chlorine dioxide (CIO₂) has been explored as a potential substitute for aqueous chlorine to clean seafood products. In an attempt to understand the interaction of CIO₂ with organic compounds, duplicate fillets of Atlantic salmon (Salmo salar) and red grouper (Epinephelus morio) were treated for 5 min with freshly prepared aqueous CIO₂ at 20, 40, 100, and 200 ppm total available CIO₂ in 3.5% brine. Thiobarbituric acid (TBA) values and fatty acid composition were determined. CIO₂-treated salmon and red grouper showed a dose-related increase in TBA; the 100 and 200 ppm groups had significantly (P<0.05) greater TBA values than controls and the 20 ppm group. Treated red grouper and salmon did not differ in percentage monounsaturated and polyunsaturated fatty acids compared to controls, although differences occurred with some individual fatty acids. Thus, CIO₂ treatment did not greatly affect fatty acid composition of treated fillets.     

The effect of fatty acid composition of rapeseed oil on plasma lipids and oxidative stability of low‐density lipoproteins in cholesterol‐fed hamsters

We studied the effect of four rapeseed oils with different fatty acid profiles on parameters implicated in the pathogenesis of atherosclerosis in humans in a model experiment with hamsters. The hamsters were divided into seven groups and fed a semi‐synthetic, cholesterol‐enriched diet (5 g/kg diet) containing 15% of the fat in question for a period of six weeks. The following rapeseed oils were used: (1) conventional rapeseed oil (6% saturated fatty acids [SFA], 64% monounsaturated fatty acids [MUFA], 18% linoleic acid [LA], 9% α‐linolenic acid [ALA]), (2) linoleic acid‐rich rapeseed oil (6% SFA, 61% MUFA, 28% LA, 2% ALA), (3) oleic acid‐rich rapeseed oil (6% SFA, 74% MUFA, 11% LA, 5% ALA), (4) myristic acid‐rich rapeseed oil (11% myristic acid, 35% SFA, 44% MUFA, 14% LA, 5% ALA). Sunflower oil, olive oil and lard were used as control fats. The concentrations of the lipids in the plasma, in the lipoprotein fractions and in the liver, the fatty acid composition of various tissues, the tocopherol status and the susceptibility of low‐density lipoproteins (LDL) to in vitro‐oxidation were determined. The concentrations of total cholesterol found in the plasma and in the LDL fraction and the ratios of LDL to HDL were similar after feeding the four different types of rapeseed oil, sunflower oil and olive oil. Lard produced the highest concentrations of cholesterol in plasma and the LDL fraction and the highest ratio of LDL to HDL. Feeding conventional, oleic acid‐ and myristic acid‐rich rapeseed oils resulted in markedly lower ratios of arachidonic to eicosapentaenoic acid in the lipids of the liver and the erythrocytes. This is considered beneficial for the formation of eicosanoids. The lag‐time before the onset of peroxidation of the LDL lipids, induced by copper ions, was not statistically significant between the seven hamster groups suggesting that the susceptibility of LDL to lipid peroxidation was similar after feeding all types of fat. Considering all parameters obtained in the used hamster model it is obvious that all four rapeseed oils are at least as favourable as olive oil or sunflower oil.     

Production of structured triacylglycerols in an immobilised lipase packed‐bed reactor: batch mode operation

Structured triacylglycerols with caprylic acid at the sn‐1 and sn‐3 positions of the glycerol backbone and eicosapentaenoic acid (EPA) at the position sn‐2 were synthesised by acidolysis of a commercially available EPA‐rich oil (EPAX4510, Pronova Biocare) and caprylic acid catalysed by the 1,3‐specific immobilised lipase Lipozyme IM. The reaction was carried out in an immobilised lipase packed‐bed reactor by recirculating the reaction mixture through the bed. The exchange equilibrium constants between caprylic acid and the native fatty acids of EPAX4510 were determined. The n‐3 polyunsaturated fatty acids (PUFAs), EPA and docosohexaenoic acid (DHA), were the most easily displaced by the caprylic acid. The exchange equilibrium constants were 3.68 and 3.06 for EPA and DHA, respectively. The influence of the flow rate of the reaction mixture through the packed‐bed and the substrate concentration in the reaction rate were studied. For flow rates between 74 and 196 cm³ h^?1 (bed of 6.6 mm internal diameter and 0.46 porosity) and triacylglycerol concentrations between 0.036 and 0.108 M , the data fitted well to an empirical kinetic model which allowed representative values of the apparent kinetic constant to be obtained. Hence, the average reaction rates and kinetic constants of exchange of caprylic acid and native fatty acids of EPAX4510 could be calculated. In the conditions indicated, the parameter (lipase mass × time/triacylglycerol mass, m_Lt/V[TG]₀) constituted the intensive variable of the process for use in predicting the composition of structured triacylglycerols at different reaction times. At equilibrium, the structured triacylglycerol produced had the following composition: caprylic acid 59.5%, EPA 9.6%, DHA 2.2% and oleic acid 11.8%. Copyright © 2004 Society of Chemical Industry     

Evidence of Strict Stereospecificity in the Structure of sn‐1,2‐Diacyl‐3‐Acetyl‐Glycerols from Euonymus maximowiczianus Seeds Using Nuclear Magnetic Resonance Spectroscopy

Asymmetric, optically active sn‐1,2‐diacyl‐3‐acetyl‐glycerols (AcDAG) have been known to scientists for several decades. However, to date, the problem of their structure has not been definitely resolved, which has led to a vast diversity of terms used for their designation in the literature. Using two‐dimensional nuclear magnetic resonance, we have investigated AcDAG from the mature seeds of Euonymus maximowiczianus, from which we have been able to both identify a correlation of the methyl group in acetic acid residue with protons at the carbon atom at sn‐3 position in the glycerol residue of the AcDAG molecule and, for the first time, demonstrate that this correlation is observed exclusively with one carbon atom at the α‐position, but not with two as would have been expected in case of a racemic mixture. Moreover, results of our analysis of AcDAG isolated from the seeds of E. maximowiczianus directly confirm that diacylglycerol‐3‐acetyl‐transferase is responsible for their biosynthesis, which reveals a strict specificity not only to acetyl‐CoA as one of the substrates but also to the sn‐3‐position of the glycerol residue in sn‐1,2‐diacylglycerol during their biosynthesis.     

Characterization of the effects of β‐carotene on the thermal oxidation of triacylglycerols using HPLC‐ESI‐MS

RP HPLC method coupled to ESI‐MS was used for the analysis and characterization of the oxidation of model triacylglycerols (TAGs) in presence of β‐carotene. β‐Carotene was added to the TAGs and oxidized in the Rancimat at 110°C. The samples were separated isocratically using a mixture of isopropanol with methanol and a Phenomenex C18 column. β‐Carotene degradation was measured using high performance TLC. We found that β‐carotene plays an important role during the thermal degradation of high oleic acid model TAGs. Half of the β‐carotene was degraded before 3 h of thermal treatment. β‐Carotene significantly increases the peroxide value of the TAGs after the third hour, suggesting a pro‐oxidant action. However, different TAGs show different activity toward thermal treatment and β‐carotene. The LLL was found to be less stable, OLL and OLO were stable till 10 and 12 h respectively, while POO, OOO, and OSO were the stable TAGs till 14 h. In TAGs, replacing linoleic acid by oleic acid, the stability of the corresponding TAG was found to increase by 2 h. A new class of oxidized TAGs was reported for the first time, together with previously reported species. The proposed mechanism of formation and identification of the newly identified species have been explained. Among the oxidized species of TAGs, mono‐hydroperoxides, bis‐hydroperoxides, epoxy‐epidioxides, and epoxides were the major compounds identified.     

Identification of n‐6 Monounsaturated Fatty Acids in Acer Seed Oils

Seed oils from Acer species are a potential source of the nutraceutical fatty acids, nervonic acid (cis‐15‐tetracosenoic acid, NA), and γ‐linolenic acid (cis‐6,9,12‐octadecatrienoic acid, GLA). To further characterize the genus, seed fatty acid content and composition were determined for 20 species of Acer. Fatty acid content ranged from 8.2% for Acer macrophyllum to over 36% for A. mono and A. negundo. The presence of very‐long‐chain fatty acids (VLCFA), with chain length of 20‐carbons or greater, and GLA were characteristic features of the seed oils. In all species, erucic acid (cis‐13‐docosenoic acid, EA) was the predominant VLCFA with the highest level of NA being only 8.6% in A. olivianum. Regioselective lipase digestion demonstrated that VLCFA are largely absent from the sn‐2 position of seed triacylglycerol, whereas GLA is primarily located at this position. Five Acer species contained low levels (<2%) of cis‐12‐octadecenoic acid and cis‐14‐eicosenoic acid, uncommon n‐6 fatty acids not previously reported from Acer.     

Transition‐metal trifluoromethane‐sulphonates‐recyclable catalysts for the synthesis of branched fatty derivatives by Diels‐Alder reactions at unsaturated fatty esters

Diels‐Alder reactions of conjugated linoleic acid ethyl ester (1) with different quinones and with a variety of α/βunsaturated aldehydes and ketones are described in this paper. Using Sc(OTf)₃ or Cu(OTf)₂ as catalysts the reactions can be carried out at 25—40 °C with good yields. For the first time in oleochemistry it is possible to prepare Diels‐Alder cycloadditions with catalyst concentrations of 10 mol‐% instead of stoichiometric amounts of Lewis acids. Furthermore, the reaction time was partly shortened drastically. The catalyst Sc(OTf)₃ can be removed by a simple extraction of the organic layer with water. After evaporation of the aqueous phase to dryness the catalyst can be reused without loss of yield.     

Stereospecific analyses of seed triacylglycerols from high-erucic acid brassicaceae: Detection of erucic acid at thesn-2 position inBrassica oleracea L. Genotypes

Stereospecific analyses of triacylglycerols from selected high-erucic acid breeding lines or cultivars ofBrassica napus L. andB. oleracea L. have been performed. Initial lipase screening revealed that while allB. napus lines contained little or no erucic acid at thesn-2 position, several of theB. oleracea lines had significant proportions of erucic acid at this position. Detailed stereospecific analyses were performed on the triacylglycerols from these lines by using a Grignard-based deacylation, conversion of thesn-1,sn-2 andsn-3 monoacylglycerols to their di-dinitrophenyl urethane (DNPU) derivatives, resolution of the di-DNPU-monoacylglycerols (MAGs) by high-performance liquid chromatography on a chiral column, transmethylation of eachsn-di-DNPU MAG fraction and analysis of the resulting fatty acid methyl esters by gas chromatography. The findings unequivocally demonstrate for the first time that, within the Brassicaceae, there existsB. oleracea germplasm containing seed oils with substantial erucic acid (30–35 mol%) at thesn-2 position. This has important implications for biotechnology and breeding efforts designed to increase the levels of erucic acid in rapeseed beyond 66 mol% to supply strategic industrial feedstocks. In the first instance, the germplasm will be of direct use in retrieving a gene encoding aBrassica lyso-phosphatidic acid acyltransferase with an affinity for erucoyl-CoA. In a breeding program, the germplasm offers promise for the introduction of this trait intoB. napus by interspecific hybridization and embryo rescue.     

Effects of frying on the trans‐fatty acid formation in soybean oils

To evaluate the effects of repeated deep‐frying on the trans‐fatty acid (TFA) formation in soybean oils, simultaneous frying experiments were carried out. French fries were prepared using three different types of soybean oil (pressed soybean oil, PSBO; first‐grade solvent extracted soybean oil, FG‐SESBO; and third‐grade solvent extracted soybean oil, TG‐SESBO). French fries were fried intermittently at 180–185°C for a total frying time of 32 h and at an interval time of 30 min. It was found that the initial amount of total TFAs was 0.29 g/100 g, 0.31 g/100 g, and 0.90 g/100 g in PSBO, TG‐SESBO, and FG‐SESBO, respectively. Before the frying started, the C18:1,t‐9, trans‐linoleic acid (TLA), trans‐linolenic acid (TLNA), and total TFA content of the PSBO and TG‐SESBO were significantly lower than in the FG‐SESBO (p<0.05). However, in the frying oil samples, the final concentration of total TFA in the PSBO, TG‐SESBO, and FG‐SESBO were 1.79 ± 0.17 g/100 g, 1.12 ± 0.10 g/100 g, and 1.70 ± 0.07 g/100 g, which was 6.17‐, 3.61‐, and 1.89‐fold higher that in fresh oil, respectively. The highest increasing slopes of C18:1,t‐9, TLA, TLNA, and total TFA were observed in the PSBO. Practical applications : A high intake of TFAs has been shown to lead to an increased risk of coronary heart disease. Plant oils, particularly soybean oil, have been widely used in the food industry in China. Frying is one of the most common methods to cook food. The formation of TFAs during frying has been shown to be closely related to the temperature and duration of the frying process. However, the effects of frying on the formation of TFAs in different soybean oils have not been well studied. In the present study, we demonstrated that increasing the number of frying cycles can cause an intensive increase in the concentration of TFAs in different types of soybean oil, but especially in PSBO.     

Effect of fatty acid positional distribution and triacylglycerol composition on lipid by-products formation during heat treatment: II. Trans isomers

This study examined the effect of the fatty acid positional distribution and of the triacylglycerol (TG) composition on heat-induced trans isomerization of linoleic and linolenic acids. For this, we synthesized diacid TG molecules that were acylated only with linoleic acid (L) or with linolenic acid (Ln) along with palmitic acid (P). The fatty acid of interest was positioned either in the central position (PLP and PLnP, respectively) or in one of the two outer positions (PPL and PPLn, respectively). Monoacid TG, i.e., trilinolein and trilinolenin, were also synthesized and mixed with tripalmitin in a 1:2 ratio. This model TG was also compared to another TG model, which consisted of a canola oil and its randomized counterpart whose fatty acid positional distribution and TG composition were determined by means of high-performance liquid chromatography. After heating, the content of trans isomers was determined by gas-liquid chromatography with a polar capillary column. In model TG, polyunsaturated fatty acids in monoacid TG (LLL and LnLnLn) exhibited the highest degree of isomerization, compared to diacid TG, and this effect was greatest at 220°C. At this temperature, an effect of the TG structure was observed only with linolenic acid. In that situation, 18:3n-3 acylated in the central position of the TG molecule (PLnP) displayed the highest sensitivity to trans geometrical isomerization. Although to a lesser extent, the same trends as for the pure TG model were observed with the canola oil model with regard to the influence of the fatty acid positional distribution and TG molecular species.     

Estimating the content of free fatty acids in high‐oleic sunflower seeds by near‐infrared spectroscopy

The content of free fatty acids (FFA) in vegetable oils represents an important quality factor in oil crops. The objective of the investigation was to develop a near‐infrared (NIR) calibration for estimating the FFA content in high‐oleic sunflower seeds. A sample set of different varieties from the harvest of 2004 as well as of 2005 from two locations in Germany was used; additionally seeds from 2003 were stored under unsuitable conditions to obtain samples utilised for calibration with an extended FFA range. A direct titration method for FFA determination was developed and adjusted to the official AOCS method. The modified method is sufficiently reliable, much faster than the AOCS method and therefore suitable for use in the calibration of NIR spectrometers. The developed NIR spectroscopy (NIRS) calibration was calculated with a modified partial least square algorithm, standard normal variate and detrend scatter correction and the 2^nd derivative of the spectra of ground sunflower seeds. The standard error of prediction of the validated calibration was 0.20, and the multiple coefficient of determination (RSQ_val) reached 0.94. The obtained results demonstrated clearly the efficiency and how cost effective the NIRS method is for the estimation of FFA content in sunflower seeds.     

Effect of fatty acid positional distribution and triacylglycerol composition on lipid by-products formation during heat treatment: II. Trans isomers

This study examined the effect of the fatty acid positional distribution and of the triacylglycerol (TG) composition on heat-induced trans isomerization of linoleic and linolenic acids. For this, we synthesized diacid TG molecules that were acylated only with linoleic acid (L) or with linolenic acid (Ln) along with palmitic acid (P). The fatty acid of interest was positioned either in the central position (PLP and PLnP, respectively) or in one of the two outer positions (PPL and PPLn, respectively). Monoacid TG, i.e., trilinolein and trilinolenin, were also synthesized and mixed with tripalmitin in a 1:2 ratio. This model TG was also compared to another TG model, which consisted of a canola oil and its randomized counterpart whose fatty acid positional distribution and TG composition were determined by means of high-performance liquid chromatography. After heating, the content of trans isomers was determined by gas-liquid chromatography with a polar capillary column. In model TG, polyunsaturated fatty acids in monoacid TG (LLL and LnLnLn) exhibited the highest degree of isomerization, compared to diacid TG, and this effect was greatest at 220°C. At this temperature, an effect of the TG structure was observed only with linolenic acid. In that situation, 18:3n-3 acylated in the central position of the TG molecule (PLnP) displayed the highest sensitivity to trans geometrical isomerization. Although to a lesser extent, the same trends as for the pure TG model were observed with the canola oil model with regard to the influence of the fatty acid positional distribution and TG molecular species.