Composition and structure of some consumer-available edible fats

Samples of polyunsaturated margarines, table margarines, hard cube polyunsaturated vegetable oil, hard cube vegetable oil, animal fat, and blends of vegetable oil and animal fat were analyzed for fatty acid composition, percentage ofcis,cis-methylene interrupted polyunsaturated fatty acids, percentage isolatedtrans-unsaturation, and percentage conjugated diene. Gas liquid chromatography was used to separate and measure the geometric isomers of the octadecaenoic and octadecadienoic acids. Selected samples were analyzed for the content of positional isomers in theircis monoene andtrans monoene fractions, and for the percentage of fatty acid esterified in the 2-position of their triglycerides.     

Fatty acid composition of danish margarines and shortenings,with special emphasis ontrans fatty acids

Trans fatty acids from hydrogenated vegetable and marine oils could be as hypercholesterolemic and atherogenic as saturated fatty acids. Hence, it is important to know the fatty acid composition in major food contributors, e.g., margarines and shortenings. In 1992 margarines were examined, and in 1995 brands covering the entire Danish market were examined. Significant amounts oftrans-18∶1 were found only in hard margarines (mean: 4.2±2.8%) and shortenings (mean: 6.8 ±3.1%), whereas the semisoft and soft margarines contained substantially lesstrans-18∶1 in 1995 than in 1992. Where marine oils had been used to a larger degree the meantrans-monoenoic content was about 15%, of which close to 50% was made up of long-chain (C₂₀ and C₂₂)trans fatty acids. A note-worthy decrease in the content oftrans-18∶1 had occurred for the semisoft margarines, from 9.8±6.1% in 1992 to 1.2±2.2% in 1995. Calculated from sales figures, the supply oftrans-18∶1 plus saturated fatty acids from margarines had decreased over this three-year period by 1.4 g/day, which has been replaced bycis monounsaturated and polyunsaturated fatty acids.     

Fatty acid composition and contents of trans monounsaturated fatty acids in frying fats, and in margarines and shortenings marketed in Denmark

This study examined trans monounsaturated fatty acid contents in all margarines and shortenings marketed in Denmark, and in frying fats used by the fast-food restaurants Burger King and McDonald’s. Trans C_18:1 content was 4.1±3.8% (g per 100 g fatty acids) in hard margarines, significantly higher than the content in soft margarines of 0.4±0.8%. Shortenings had an even higher content of trans C_18:1, 6.7±2.3%, than the hard margarines. Margarines and shortenings with high contents of long-chain fatty acids had about 20% total trans monoenoic of which close to 50% were made up of trans long-chain fatty acids. Both fast-food frying fats contained large amounts of trans C_18:1, 21.9±2.9% in Burger King and 16.6±0.4% in McDonald’s. In Denmark the per capita supply of trans C_18:1 from margarines and shortenings and frying fats has decreased steadily during recent years. The supply of trans C_18:1 from margarines and shortenings in the Danish diet is now 1.1 g per day.     

cis-trans isomerization of unsaturated fatty acids withp-toluenesulfinic acid

Elaidination of unsaturated fatty acids usingp-toluenesulfinic acid yielded 77–80% totaltrans unsaturation in the products. Results from reactions with monoene, diene, and triene isomers indicated that only geometric isomerization takes place. Each double bond isomerized randomly and independently in the polyunsaturated fatty acids. Reactions proceeded quickly, and the method proved convenient and reliable.     

Fatty acid composition and contents of trans monounsaturated fatty acids in frying fats, and in margarines and shortenings marketed in Denmark

This study examined trans monounsaturated fatty acid contents in all margarines and shortenings marketed in Denmark, and in frying fats used by the fast-food restaurants Burger King and McDonald’s. Trans C_18:1 content was 4.1±3.8% (g per 100 g fatty acids) in hard margarines, significantly higher than the content in soft margarines of 0.4±0.8%. Shortenings had an even higher content of trans C_18:1, 6.7±2.3%, than the hard margarines. Margarines and shortenings with high contents of long-chain fatty acids had about 20% total trans monoenoic of which close to 50% were made up of trans long-chain fatty acids. Both fast-food frying fats contained large amounts of trans C_18:1, 21.9±2.9% in Burger King and 16.6±0.4% in McDonald’s. In Denmark the per capita supply of trans C_18:1 from margarines and shortenings and frying fats has decreased steadily during recent years. The supply of trans C_18:1 from margarines and shortenings in the Danish diet is now 1.1 g per day.     

Trans fatty acids in Canadian margarines: Recent trends

The fatty acid composition and the trans fatty acid content of the top-selling 109 Canadian margarines were determined by a combined capillary gas-liquid chromatography/infrared spectroscopy method. The 109 brands accounted for 68% of the margarine brands sold in Canada and represented 74% of the market share. The mean level of total trans content in tub margarines (n=79) was 18.8% (g/100 g fatty acids) and ranged from 0.9 to 46.4%. The most frequent occurrence of trans in tub margarines was in the 15–20% range; 48 of the 79 tub brands were in this range but seven brands contained more than 40% trans. The trans content of hard margarines (n=30) ranged from 16.3 to 43.7% and the mean value was 34.3%. In 20 of the 109 brands, the levels of trans,trans isomers of linoleic acid exceeded the maximum level of 1% recommended for Canadian margarines. The levels of cis,trans/trans,cis isomers of linoleic acid were also high; 78 brands contained more than 1% and in 16 brands, the levels were in the 6–7% range. Linoleic acid content in the 109 brands ranged from 1.0 to 45.2% and averaged 18.3%. In 33 samples, linoleic acid was below the level of 5% recommended by an ad hoc committee of Health Canada. Moreover, in these, the total trans content exceeded 30%, and trans polyunsaturated fatty acid level was greater than 5%. There were eight margarines prepared from nonhydrogenated fat and their total trans content was below 2.5%. From the trans content and market share of each of the margarine brands, the average intake of trans fatty acids from margarine was estimated as 0.96 g/person/d. The intake of trans fatty acids in Canada from various sources was previously estimated by us as 8.4 g/person/d. Thus it is suggested that only 11% of the dietary trans fatty acids are supplied by margarines and the majority of trans fatty acids in the Canadian diet is derived from hidden fats in fast foods and bakery products.     

Lipid composition of selected vegetable oils

This paper gives analytical data on the composition of 14 selected consumer-available liquid vegetable oils, including soybean, soybean-cottonseed blends, corn, safflower, peanut, olive and apricot kernel oils. Label information identified six samples as specially processed or refined and three samples as cold pressed with no preservative added; the labels of the remaining five samples did not mention processing. Data are given for fatty acid composition,trans content, location of the double bonds in the unsaturated fatty acids, percent conjugation, tocopherol content, fatty acid composition of the 2-poisition of the triglycerides, polyunsaturated to saturated fatty acid (P/S) ratio, and the ratio of α-tocopherol to polyunsaturated fatty acids (α-T/P). The ranges of values found were: conjugated unsaturation, 0.18–1.09%; α-tocopherol, 0.01–0.60 mg/gm; total tocopherol 0.14–1.52 mg/gm; P/S, 0.5–8.7; and α-TP, 0.03–2.26. The compositions of the fatty acids on the 2-position and on the 1,3-position of the triglycerides were compared with those calculated by the Evans’ hypothesis and found to agree well for all but olive and apricot kernel oils. Mention of a trademark or proprietary product does not constitute a guarantee or warranty of the product by the U.S. Department of Agriculture, and does not imply its approval to the exclusion of other products that may also be suitable. Deceased     

Determination of fatty acids and some undesirable fatty acid isomers in selected Turkish margarines

The fatty acid composition and total trans fatty acid content in 10 margarines produced in Turkey were determined by capillary gas chromatography and Fourier transform‐infrared spectroscopy (FT‐IR) spectroscopy. The fatty acid composition ranged as follows: saturated fatty acids, C16:0 (palmitic) 11.3 to 31.8% and C18:0 (stearic) 5.7 to 8.7%, monounsaturated fatty acids, C18:1 (oleic) 21.8 to 35.7% and C18:1 trans isomers 0.4 to 27.4%, polyunsaturated fatty acid, C18:2 linoleic acid 5.2 to 40.2%. Some positional isomers of C18:1 as cis‐11‐octadecenoic acid varied from 0.7 to 4.6% and cis‐13 trace to 2.4%. The total trans fatty acid contents were between 0.9 and 32.0% when measured with capillary gas chromatography and between 0 and 30.2% with FT‐IR spectroscopy. Some of the margarines analyzed contained trace amount of trans fatty acids which could not be detected by FT‐IR spectroscopy.     

Conversion of polyunsaturates in vegetable oils tocis-monounsaturates by homogeneous hydrogenation catalyzed with chromium carbonyls

Chromium carbonyl complex catalysts were used to selectively hydrogenate polyunsaturates in vegetable oils into products retaining 90% to 95%cis configuration and their liquid properties. The product from soybean oil contained 42–69% monoene, 10–40% diene and 0–4% triene. The product from safflower oil contained 73–82% monoene and 8–17% diene. About 45–55% of the double bonds in monoenes from hydrogenated soybean oil remained in the C₉ position, and the rest was distributed between C₁₀, C₁₁, and C₁₂. Preliminary oxidative and flavor stability evaluations showed that these hydrogenated soybean oils compared favorably with a commercial sample of hydrogenated-winterized soybean oil. Liquid fatty acids prepared by saponification of hydrogenated soybean and safflower oils (IV 90–100) had analyses about the same as those of commercial oleic acid. Presented before the Division of Agricultural and Food Chemistry, 156th American Chemical Society National Meeting, Atlantic City, N.J., September 1968.     

Sperm oil replacements from selectively hydrogenated soybean and linseed esters: Special lubricants

Soybean and linseed oils were selectively hydroenated with copper-on-silica gel catalyst. The linolenate content of the oils was reduced to diene and monoene with no appreciable increase in saturates. Hydrogenated soybean oils contained 68–76% monoene, 11–18% diene, 0% conjugated diene and triene, 1–6% conjugatable diene, 0–0.3% conjugatable triene, and 23–40% isolatedtrans double bonds. Hydrogenated linseed oils contained 44–54% monoene, 35–45% diene, 0% conjugated diene and triene, 0–7% conjugatable diene, 0–02% conjugatable triene, and 44–59% isoaltedtrans double bonds. Esters of fatty acids, derived from these selectively hydrogenated oils, were prepared with trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, ethylene glycol, C₁₈ saturated cyclic alcohols, primary C₁₂–C₁₈ saturated (nC₁₂, nC₁₄, nC₁₆, nC₁₈) alcohol, and primary C₁₆–C₁₈ saturated (nC₁₆, nC₁₈) alcohol blends. Measurements of viscosities and of smoke, flash, and fire points indicate that these esters are possible replacements for sperm oil. Certain of them, after sulfurization, also have potential as extreme pressure lubricant additives. Presented at the AOCS meeting in Philadelphia, September 1974.     

Trans-18:1 acids in french tub margarines and shortenings: Recent trends

The fatty acid composition of twelve French tub margarines and three industrial shortenings was established with particular attention to theirtrans-18:1 acid content. Four of the twelve margarines (including two major brands, with 60% of market share) were devoid oftrans isomers, one contained less than 2%trans-18:1 acids, whereas the seven others had a mean content of 13.5 ± 3.6%trans isomers. Four years ago, no margarines with 0%trans-18:1 acids could be found. It is deduced that the recent Dutch and American studies on possible effects oftrans acids on human health (serum cholesterol, heart disease risks) may have had some influence on French margarine manufacturers. Presently, an average French tub margarine contains only 3.8% oftrans-18:1 acids instead of 13% four years ago. To protect brand names, some manufacturers have replaced partially hydrogenated oils with tropical fats or fully hydrogenated oils. On the other hand, two of the three shortenings had high levels oftrans-18:1 acids: 53.5 and 62.5%. This last value, obtained for a sample of hydrogenated arachis oil, seems to be one of the highest values ever reported for edible hydrogenated oils. In this sample,trans-18:1 plus saturated acids accounted for 85% of total fatty acids. This would indicate that shortening producers and users are not yet aware of recent dietary recommendations, probably because these products are not easily identifiable by consumers in food items, in contrast to margarines.     

Composition,physical and textural characteristics of soft (tub) margarines

Soft (tub) margarines were analyzed for fatty acid,trans and polyunsaturated fatty acid (PUFA) content. Soybean and sunflower-palm kernel-palm margarines contained high levels ofcis-cis methylene interrupted (CCMI)-PUFA. Canola and canola-palm products contained the lowest amounts of saturated fatty acids. Polymorphic forms of the crystals were as follows: soybean beta prime, canola beta, canola-palm and a sunflower-palm kernel-palm—a mixture of beta and beta prime. Dropping points of the fats ranged from 27.3 to 34.2°C. Softening points of the products were higher especially for margarines that existed in the beta form. Texture was determined by cone penetrometer, constant speed compression and penetration. Soybean margarines were generally most resistant to deformation. The solid fat content (SFC) of the “whole” margarines as determined by the Bruker Minispec was found to be slightly lower than that of the separated fat (AOCS-method) at 10°C. Correlation of values within the textural methods was significant (P<.01), but not between the texture and SFC of the product which means that the nature of the crystal network also plays a role in texture.     

Incorporation oftrans long-chain n−3 polyunsaturated fatty acids in rat brain structures and retina

During heat treatment, polyunsaturated fatty acids and specifically 18∶3n−3 can undergo geometrical isomerization. In rat tissues, 18∶3 Δ9c, 12c, 15t, one of thetrans isomers of linolenic acid, can be desaturated and elongated to givetrans isomers of eicosapentaenoic and docosahexaenoic acids. The present study was undertaken to determine whether such compounds are incorporated into brain structures that are rich in n−3 long-chain polyunsaturated fatty acids. Two fractions enriched intrans isomers of α-linolenic acid were prepared and fed to female adult rats during gestation and lactation. The pups were killed at weaning. Synaptosomes, brain microvessees and retina were shown to contain the highest levels (about 0.5% of total fatty acids) of thetrans isomer of docosahexaenoic acid (22∶6 Δ4c, 7c, 10c, 13c, 16c, 19t). This compound was also observed in myelin and sciatic nerve, but to a lesser extent (0.1% of total fatty acids). However, the ratios of 22∶6trans to 22∶6cis were similar in all the tissues studied. When the diet was deficient in α-linolenic acid, the incorporation oftrans isomers was apparently doubled. However, comparison of the ratios oftrans 18∶3n−3 tocis 18∶3n−3 in the diet revealed that thecis n−3 fatty acids were more easily desaturated and elongated to 22∶6n−3 than the correspondingtrans n−3 fatty acids. An increase in 22∶5n−6 was thus observed, as has previously been described in n−3 fatty acid deficiency. These results encourage further studies to determine whether or not incorporations of suchtrans isomers into tissues may have physiological implications. Presented in part at the 32nd International Conference on the Biochemistry of Lipids, 1991, Granada, Spain. Delta nomenclature (Δ) is used fortrans polyunsaturated fatty acids to specify the position and geometry of ethylenic bonds. Polyunsaturated fatty acids containingtrans double bonds are abbreviated giving the locations of thetrans double bonds only; e.g., 20∶5 Δ17t 20∶5 Δ5c,8c,11c,14c,17t; 22∶5 Δ19t, 22∶5 Δ7c,10c,13c,16c,19t; 22∶6 Δ19t 22∶6 Δ4c,7c,10c,13c,16c,19t.     

Desaturation of positional and geometric isomers of monoenoic fatty acids by microsomal preparations from rat liver

A range ofcis- andtrans-monoenoic fatty acids was tested as substrates for desaturation in microsomal preparations from rat liver.Trans-monoenoic acids were generally desaturated in the Δ9 position to the same extent as stearic acid. Acids with Δ7-trans- and Δ11-trans-olefinic unsaturation produced Δ7-trans,9-cis- and Δ9-cis,11-trans-conjugated dienoic acids, respectively, but the Δ8-trans- and Δ10-trans-monoenoic acids did not give Δ8,9- or Δ9,10-allenes. Of thecis-monoenoic acids examined, only those with double bonds at or beyond the Δ14 position gave any measurable Δ9 desaturation. When Δ9 desaturation of long chain saturated acids was inhibited by adding sterculic acid, these saturated acids were desaturated at the Δ5 and Δ6 positions. Many of the monoenoic acids tested were also desaturated at the Δ5 and/or Δ6 positions, although the percentage conversions were always low. Δ9-cis,11-trans-, Δ9-cis,12-trans- and Δ9-cis,13-trans-dienoic acids, produced in situ by Δ9 desaturation of the corresponding monoenoic acids, were extensively desaturated in the Δ6 position. These results are discussed in terms of: (a) the various models proposed to explain the substrate specificities of the desaturases, and (b) the metabolism of unnatural fatty acids ingested from dietary sources.     

Tocopherols and tocotrienols in Finnish foods: Oils and fats

The tocopherols and tocotrienols of vegetable oils, cod liver oil, margarines, butter and Voimariini dairy spread were analyzed by HPLC. The total tocopherol content varied from 4 (coconut oil) to 242 mg/100 g (wheat germ oil). α-tocopherol equivalents varied from 2 (coconut oil) to 225 mg/100 g (wheat germ oil). Semisoft and soft margarines had an average total tocopherol of 53 and 61 mg, and an average α-tocopherol equivalent of 17 and 27 mg/100 g, respectively. Hard margarines averaged 29 mg total tocopherol and 9 mg α-tocopherol equivalent/100 g. The average tocopherol content of butter and Voimariini was 2 and 15 mg/100 g, respectively, and the average α-tocopherol equivalent 2 and 6 mg/100 g.     

Studies on monoene fatty acid isomers in hydrogenated fish oils

An analytical study of the geometrical and positional isomerisation of the monoenoic acids of partially hydrogenated fish oil is presented. The results showed that the monoene fatty acids of chain lengths 16, 18, 20 and 22 consisted of 75% in thetrans-form and 25% in thecis-form. The double bonds were distributed symmetrically over the chain length, with well defined maxima in position Δ-9 for the fatty acids of chain length 16 and 18, and in position Δ-11 for the fatty acids of chain length 20 and 22.Trans- andcis-isomers showed the same positional distribution. Geometric as well as positional isomerization seemed to have reached an equilibrium state in the sample investigated. Presented at the ISF-AOCS World Congress, Chicago, October 1970.     

Serum cholesterol predictive equations with special emphasis on trans and saturated fatty acids. an analysis from designed controlled studies

The effects of dietary trans fatty acids on serum total and low density lipoprotein (LDL) cholesterol have been evaluated by incorporating trans fatty acids into predictive equations and comparing their effects with the effects of the individual saturated fatty acids 12∶0, 14∶0, and 16∶0. Trans fatty acids from partially hydrogenated soybean oil (TRANS V) and fish oil (TRANS F) were included in previously published equations by constrained regression analysis, allowing slight adjustments of existing coefficients. Prior knowledge about the signs and ordering of the regression coefficients was explicitly incorporated into the regression modeling by adding lower and upper bounds to the coefficients. The amounts of oleic acid (18∶1) and polyunsaturated fatty acids (18∶2, 18∶3) were not sufficiently varied in the studies, and the respective regression coefficients were therefore set equal to those found by Yu et al. [Yu, S., Derr, J., Etherton, T.D., and Kris-Etherton, P.M. (1995) Plasma Cholesterol-Predictive Equations Demonstrate That Stearic Acid Is Neutral and Monounsaturated Fatty Acids Are Hypocholesterolemic, Am. J. Clin. Nutr. 61, 1129–1139]. Stearic acid (18∶0), considered to be neutral, was not included in the equations. The regression analyses were based on results from four controlled dietary studies with a total of 95 participants and including 10 diets differing in fatty acid composition and with 30–38% of energy (E%) as fat. The analyses resulted in the following equations, where the change in cholesterol is expressed in mmol/L and the change in intake of fatty acids is expressed in E%: Δ Total cholesterol=0.01 Δ(12∶0)+0.12 Δ(14∶0)+0.057 Δ(16∶0)+0.039 Δ(TRANS F)+0.031 Δ(TRANS V)−0.0044 Δ(18∶1)−0.017 Δ(18∶2, 18∶3) and ΔLDL cholesterol =0.01 Δ(12∶0)+0.071 Δ(14∶0)+0.047 Δ(16∶0)+0.043 Δ(TRANS F)+0.025 Δ(TRANS V)−0.0044 Δ(18∶1)−0.017 Δ(18∶2, 18∶3). The regression analyses confirm previous findings that 14∶0 is the most hypercholesterolemic fatty acid and indicate that trans fatty acids are less hypercholesterolemic than the saturated fatty acids 14∶0 and 16∶0. TRANS F may be slightly more hypercholesterolemic than TRANS V or there may be other hypercholesterolemic fatty acids in partially hydrogenated fish oil than those included in the equations. The test set used for validation consisted of 22 data points from seven recently published dietary studies. The equation for total cholesterol showed good prediction ability with a correlation coefficient of 0.981 between observed and predicted values. The equation has been used by the Norwegian food industry in reformulating margarines into more healthful products with reduced content of cholesterol-raising fatty acids. These authors have contributed equally to this work.     

Contribution oftrans-18∶1 acids from dairy fat to european diets

Twelve commercial samples of French butter, purchased in October–November, and 12 other samples, purchased in May–June, were analyzed with particular attention to theirtrans-octadecenoic acid contents. The isomeric fatty acids were quantitated by a combination of gas-liquid chromatography (GLC) of total fatty acids as isopropyl esters on a polar capillary column (CPSil 88) and of silver nitrate-impregnated thin-layer chromatography followed by GLC of the pooled saturated (used as internal standards) andtrans-octadecenoic acid fractions. Autumn butters contained 3.22±0.44%trans-octadecenoic acids (relative to total fatty acids), whereas those collected during the spring contained 4.28±0.47% (P<0.01). Minimum and maximum values for the two sets of butters were 2.46 (autumn) and 5.10% (spring), respectively. The annual mean value for thetrans-octadecenoic acid content in all butter samples was 3.8% of total fatty acids (ca. 2% for thetrans-11 18∶1 acid). This value allows calculation of the daily individual intake oftrans-octadecenoic acids from dairy products by populations of member states of the European Economic Community (EEC). It varies from 0.57 g (Portugal) to 1.66 g (Denmark). The mean value for the twelve countries of the EEC is 1.16 g/person/d, which is close to data published for the United States. In France, the consumption oftrans octadecenoic acids from dairy fat is higher than that from margarines (ca. 1.5 vs. 1.1 g/person/d).     

Trans fatty acid isomers in Canadian human milk

The fatty acid composition, totaltrans content (i.e., sum of all the fatty acids which may have one or moretrans double bonds) and geometric and positional isomer distribution of unsaturated fatty acids of 198 human milk samples collected in 1992 from nine provinces of Canada were determined using a combination of capillary gas-liquid chromatography and silver nitrate thin-layer chromatography. The mean totaltrans fatty acid content was 7.19±3.03% of the total milk fatty acids and ranged from 0.10 to 17.15%. Twenty-five of the 198 samples contained more than 10% totaltrans fatty acids, and thirteen samples contained less than 4%. Totaltrans isomers of linoleic acid were 0.89% of the total milk fatty acids with 18∶2Δ9c, 13t being the most prevalent isomer, followed by 18∶2Δ9c, 12t and 18∶2Δ9t, 12c. Using the totaltrans values in human milk determined in the present study, the intake of totaltrans fatty acids from various dietary sources by Canadian lactating women was estimated to be 10.6±3.7 g/person/d, and in some individuals, the intake could be as high as 20.3 g/d. The 18∶1trans isomer distribution differed from that of cow's milk fat but was remarkably similar to that in partially hydrogenated soybean and canola oils, suggesting that partially hydrogenated vegetable oils are the major source of thesetrans fatty acids.     

Fatty acid composition andtrans isomer content of hardened olive oil

Cooking fats and margarines prepared from olive oil were analyzed gas chromatographically for fatty acid composition andtrans isomer content. Argentation thin layer chromatography and mass spectrometry were used to assist in identifications of minor components. Olive oil margarines and cooking fats contained 70–76% monoenoic acids, of which 30–37% was in thetrans configuration, and 5% dienoic acids. Twenty percent of the dienes were in the form oftrans-trans andcis-trans octadecadienoic acid.