Preparation of plastic fats with zero <Emphasis Type="Italic">trans</Emphasis> FA from palm oil

A series of plastic fats containing no trans FA and having varying melting or plastic ranges, suitable for use in bakery, margarines, and for cooking purposes as vanaspati, were prepared from palm oil. The process of fractionating palm oil under different conditions by dry and solvent fractionation processes produced stearins of different yields. Melting characteristics of stearin fractions varied depending on the yield and the process. The lower-yield stearins were harder and had a wider plastic range than those of higher yields. The fractions with yields of about 35% had melting profiles similar to those of commercial vanaspati. The plastic range of palm stearins was further improved by blending them with corresponding oleins and with other vegetable oils. The plasticity or solid fat content varied depending on the proportion of stearin. Blends with higher proportions of stearins were harder than those with lower proportions. the melting profiles of some blends, especially those containing 40–60% stearin of about 25% yield and 40–60% corresponding oleins or mahua or rice bran oils, were similar to those of commercial vanaspati and bakery shortenings. These formulations did not contain any trans FA, unlike those of commercial hydrogenated fats. Thus, by fractionation and blending, plastic fats with no trans acids could be prepared for different purposes to replace hydrogenated fats, and palm oil could be utilized to the maximum extent.     

Physical and chemical properties of trans-free fats produced by chemical interesterification of vegetable oil blends

Fat blends, formulated by mixing a highly saturated fat (palm stearin or fully hydrogenated soybean oil) with a native vegetable oil (soybean oil) in different ratios from 10:90 to 75:25 (wt%), were subjected to chemical interesterification reactions on laboratory scale (0.2% sodium methoxide catalyst, time=90 min, temperature=90°C). Starting and interesterified blends were investigated for triglyceride composition, solid fat content, free fatty acid content, and trans fatty acid (TFA) levels. Obtained values were compared to those of low- and high-trans commercial food fats. The interesterified blends with 30–50% of hard stock had plasticity curves in the range of commercial shortenings and stick-type margarines, while interesterified blends with 20% hard stock were suitable for use in soft tubtype margarines. Confectionery fat basestocks could be prepared from interesterified fat blends with 40% palm stearin or 25% fully hydrogenated soybean oil. TFA levels of interesterified blends were low (0.1%) compared to 1.3–12.1% in commercial food fats. Presented at the 88th AOCS Annual Meeting and Expo, May 11–14, 1997, Seattle, Washington.     

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.     

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.     

Fatty acid composition of spanish shortenings with special emphasis on <Emphasis Type="Italic">trans</Emphasis> unsaturation content as determined by fourier transform infrared spectroscopy and gas chromatography

A Fourier transform infrared spectroscopic procedure was used to analyze 34 edible fats (22 shortenings and 12 vegetable margarines) as neat fats (IR_NF) to determine their total trans fatty acid (TFA) content. The sloping baseline was corrected with a reference spectrum based on a nonprocessed olive oil. The calibration was done using seven partially hydrogenated fats with an individual TFA content previously determined by the combination of gas chromatography (GC) with argentation thin-layer chromatography. Taking into account the different absorptivities of various trans isomers, different correction factors were calculated using the calibration standards (0.83 and 1.71 for single trans bonds in both diethylene and triethylene and for trans, trans-diethylene fatty acids, respectively) and applied to calculate the total TFA of samples. Moreover, the samples were converted to their methyl esters and reanalyzed following the same procedure (IR_FAME). Differences in TFA content of fats were not found when a t-test was used to compare the results obtained by IR_NF vs. either IR_FAME or GC, suggesting that IR of neat fats could be used, thus avoiding the need to prepare sample solutions in organic solvents and to prepare fatty acid methyl esters. The mean TFA content (determined by IR_NF) of a representative group of Spanish shortenings (22 samples) that varied widely in terms of fat sources, processes, and purposes (bakery, sandwiches, ice cream, coatings, chocolate coverings) was 6.55±11.40%, although more than 54% contained <3% of TFA. Fatty acid composition of shortenings by direct GC using a 100-m polar cyanopolysiloxane capillary column indicated that the mean trans-18∶2 isomer content was 0.58%, ranging from 0.9 to 3.4%. Small amounts of trans-18∶3 isomers (<0.3%) were observed in 18 of the 22 shortenings studied; the maximal value was <2%. The mean value of the fraction saturated+TFA of shortenings was high (59.95±12.73%), including two values higher than 83%.     

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.     

Trans fatty acid composition and tocopherol content in vegetable oils produced in Mexico

The purpose of this study was to evaluate the trans fatty acid (TFA) composition and the tocopherol content in vegetable oils produced in Mexico. Sample oils were obtained from 18 different oil refining factories, which represent 72% of the total refineries in Mexico. Fatty acids and TFA isomers were determined by gas chromatography using a 100-m fused-silica capillary column (SP-2560). Tocopherol content was quantified by normal-phase high-performance liquid chromatography using an ultraviolet detector and a LiChrosorb Si60 column (25 cm). Results showed that 83% of the samples corresponded to soybean oil. Seventy-two percent of the oils analyzed showed TFA content higher than 1%. Upon comparing the tocopherol contents in some crude oils to their corresponding deodorized samples, a loss of 40–56% was found. The processing conditions should be carefully evaluated in order to reduce the loss of tocopherols and the formation of TFA during refining.     

<Emphasis Type="Italic">trans</Emphasis> Fatty Acid Content of Canadian Margarines Prior to Mandatory <Emphasis Type="Italic">trans</Emphasis> Fat Labelling

Dietary trans fatty acids (TFA) are of major concern because of their adverse effects on blood lipid levels and coronary heart disease. In Canada, margarines were significant sources of TFA during the 1980s and 1990s. However, this is expected to change with increased public awareness over their adverse health effects and the introduction of new legislature to include TFA content on the Nutritional Facts table of food labels. In this study, the TFA content of the top-selling 29 Canadian margarines, which represented 96.3% of the market share, was determined by capillary gas-liquid chromatography in order to assess the influence of regulatory development during the 3-year transition period between the announcement of new food labelling regulations in Canada that require mandatory declaration of the trans fat content in most pre-packaged foods in January 2003 and its enforcement on 12 December 2005. The 29 margarines included 15 tub margarines made from non-hydrogenated vegetable oils (NHVO-tub margarines), 11 tub margarines made from partially hydrogenated vegetable oils (PHVO-tub margarines) and three print margarines, which were also made from partially hydrogenated vegetable oils (PHVO-print margarines). The 15 NHVO tub-margarines accounted for 71% of the total margarine market share and generally contained less than 2% TFA (mean value 0.9 ± 0.3% of total fatty acids). The mean total TFA contents of PHVO-tub margarines and PHVO-print margarines, were 20.0 ± 4.5% and 39.6 ± 3.5%, and their market shares were 19.3 and 6.0%, respectively. Although during the last 10 years, increasing number of soft tub margarines that contained very little trans fats have been made available in Canada, the PHVO-tub- and -print margarines still contain high levels of trans fats similar to those margarines that were sold in the 1990s. The market share data suggest that the margarines prepared using NHVO and containing almost no TFA were preferred by Canadians over those margarines prepared using PHVO, even before the mandatory declaration of TFA content came into effect on 12 December 2005.     

Positional and geometrical isomers of linoleic acid in partially hydrogenated oils

The geometrical and positional isomers of linoleic acid of a partially hydrogenated canola oil-based spread were isolated and identified. Through partial hydrazine reduction and mass spectral studies,cis-9,trans-13 octadecadienoic acid was identified as the major isomer. Other quantitatively important isomers characterized werecis-9,trans-12;trans-9,cis-12 andcis-9,cis-15. These four were also the major isomers in margarine based on common vegetable oils. A number of minor isomers were detected and some structures identified weretrans-9,trans-12;trans-8,cis-12;trans-8,cis-13;cis-8,cis-13;trans-9,cis-15;trans-10,cis-15 andcis-9,cis-13. The proportions of the various isomers are given for some margarines in the Canadian retail market. The amounts oftrans-9,trans-12 isomer in Canadian margarines were generally below 0.5% of the total fatty acids.     

Thiyl radical-catalyzed isomerization of oils: An entry to the trans lipid library

The unsaturated fatty acyl moieties of TAG present in natural oils of borage, olive, and rice were converted to their corresponding geometrical trans isomers by thiyl radical-catalyzed isomerization. Thiyl radicals were generated from 2-mercaptoethanol under photolytic or thermal conditions. A relevant feature of this method is the absence of double-bond shifts, so that no positional trans isomers or conjugated polyenes are formed. Oils obtained after the isomerization were winterized to further increase their trans fatty acid content. Methanolysis and hydrolysis of the trans oil mixtures using an enzymatic method (lipase B from Candida antarctica) gave good conversions to the corresponding trans FAME and fatty acids, respectively. These results are relevant for the studies of lipid isomerism and trans fatty acid recognition, which is a growing concern in biochemistry and nutrition, and open new perspectives for the synthesis of glycerides and studies of their structure-activity relationships.     

Simplified method for the determination oftrans monoenes in edible fats by TLC-GLC

Several modifications of an established thin-layer chromatography-gas-liquid chromatography (TLC-GLC) procedure for quantitatingtrans unsaturated fatty acids in edible fats are presented. These refinements considerably simplify the procedure without affecting accuracy. The modifications include: i) the use of pre-coated silica sheets, dynamically impregnated with Ag⁺, which allow separated bands to be cut off with a pair of scissors; and ii) the use of stearic acid in the deliberately combined saturated andtrans monounsaturated fatty acid methyl ester bands as an (endogenous) internal standard.Trans values thereby obtained agree favorably with the results from the conventional technique.     

Thermal behavior of butterfat fractions and mixtures of tripalmitin and butterfat

The melting and crystallization behavior of blends of tripalmitin and butterfat were compared with that of butterfat fractions, which were prepared by dry fractionation and by solvent extraction. There were marked similarities in the behavior of the blends, the dry fractions and some solvent fractions. This similarity was not shared with the behavior of the hardest solvent fractions. The functionality or hard butterfat fractions seemed to derive from an enrichment in long-chain saturated triglycerides. Improved functionality could therefore be achieved equally well by blending or by fractionation. Blends of tripalmitin and butterfat could be used as model butterfat fractions, or as an alternative to butterfat fractions in some applications.     

Methyl esters from a partially hydrogenated vegetable oil is a better infrared external standard than methyl elaidate for the measurement of totaltrans content

An infrared spectrophotometric procedure, based on the fatty acid methyl ester mixture derived from a partially hydrogenated vegetable oil as the calibration standard, has been developed for accurate analysis of the totaltrans content of hydrogenated fats. This procedure produces more accurate results than the current official methods of Association of Official Analytical Chemists and American Oil Chemists’ Society, both of which use methyl elaidate as the external standard. The results obtained with this procedure were in close agreement to those determined by the combined procedure of silver-nitrate thin-layer chromatography and capillary gas-liquid chromatography. The improved results, obtained with the partially hydrogenated vegetable oil methyl esters as the calibration standard, may be attributable to its assortment oftrans isomers, which may have different absorptivities relative to methyl elaidate.     

<Emphasis Type="Italic">Trans</Emphasis> FA content in Danish margarines and shortenings

Margarines and shortenings have been major contributors to the intake by humans of the probably atherogenic trans FA (TFA). In 1999, all 73 brands of margarines and shortenings on the Danish market were analyzed by GLC on a 50-m highly polar capillary column, and the results were compared with similar investigations in 1992 and 1995. A gradual decline of TFA in Danish margarines was observed. From 1992 to 1995, a reduction of TFA from 10.4 to 3.6% took place in margarines with 20–40% linoleic acid. In 1999, TFA was practically absent in all the margarines, but it remained unchanged in shortenings, averaging about 6–7%. Long-chain TFA from hydrogenated fish oil, although present in 13 brands in 1995, were not found at all in the 1999 samples. Trans-linoleic acids or CLA were not found. The reduction in TFA content in margarines has not resulted in a systematic change over the years in the content of saturated FA, monounsaturated FA, or PUFA. Calculated from sales figures, the intake of TFA decreased from 2.2 g per capita per year in 1992, to 1.5 g in 1995, and to 0.4 g in 1999.     

Evaluation of the CP-Sil 88 and SP-2560 GC columns used in the recently approved AOCS official method Ce 1h-05: Determination of cis-, trans-, saturated, monounsaturated, and polyunsaturated fatty acids in vegetable or non-ruminant animal oils and fats by capillary GLC method

The AOCS Official Method Ce 1h-05 was recently approved at the 96th AOCS Annual Meeting (2005) by the Uniform Methods Committee as the official method for determining cis and trans FA in vegetable or non-ruminant fats and oils. A series of experiments was undertaken using a margarine (hydrogenated soybean oil) sample containing approximately 34% total trans FA (28% 18∶1 trans, 6% 18∶2 trans, and 0.2% 18∶3 trans), a low-trans oil (ca. 7% total trans FA), and a proposed system suitability mixture (12∶0, 9c−18∶1, 11c−18;1, 9c,12c,15c−18∶3, 11c−20∶1, and 21∶0) in an effort to evaluate and optimize the separation on the 100-m SP-2560 and CP-Sil 88 flexible fused-silica capillary GC columns recommended for the analysis. Different carrier gases and flow rates were used during the evaluation, which eventually lead to the final conditions to be used for AOCS Official Method Ce 1h-05.     

Formulation of zero-<Emphasis Type="Italic">trans</Emphasis> acid shortenings and margarines and other food fats with products of the oil palm

The fruit of the oil palm yields two types of oil. The flesh yields 20–22% of palm oil (C16∶0 44%, C18∶1 39%, C18∶2 10%). This represents about 90% of the total oil yield. The other 10%, obtained from the kernel, is a lauric acid oil similar to coconut oil. Palm oil is semisolid, and a large part of the annual Malaysian production of about 14 million tonnes is fractionated to give palm olein, which is widely used for industrial frying, and palm stearin, a valuable hard stock. Various grades of the latter are available. Formulae have been developed by straight blending and by interesterification of palm oil and palm kernel oil to produce shortenings and margarines using hydrogenated fats to give the consistency required. Products that include these formulations are cake shortenings, vanaspati (for the Indian subcontinent), soft and brick margarines, pastry margarines, and reduced fat spreads. Other food uses of palm products in vegetable-fat ice cream and cheese, salad oils, as a peanut butter stabilizer, and in confectioners fats are discussed briefly here.     

Enzymatic synthesis of fatty alcohol esters by alcoholysis

Lipase-catalyzed conversions of some minor oils and fats like mowrah (Madhuca latifolia), mango (Mangifera indica) kernel, and sal (Shorea robusta) fats into low, medium, and high molecular weight alcohol esters have been investigated. In solvent-free medium, alcoholysis of the above-mentioned fats with 10% (w/w) Mucor miehei lipase produced alcohol esters in good yield. The percentage molar conversions of C₄, C₈, C₁₀, C₁₂, C₁₄, C₁₆, C₁₈, and C_18:1 alcohols into corresponding alcohol esters ranged from 86.8 to 99.2, while the percentage molar conversions on the basis of oil were in the range of 108.0 to 123.5.     

A critical evaluation of thermal fractionation of butter oil

Butter was fractionated on the basis of temperature (17–29°C) without agitation using slow cooling of melted anhydrous fat in conjunction with gentle vaccum filtration to produce four solid and four liquid fractions. Each of the fractions was analyzed for fatty acid composition, triglyceride profile, and characterized by gel permeation high performance liquid chromatography and differential scanning calorimetry thermograms. Fatty acid analysis indicated that the solid fractions had slightly higher amounts of palmitic and stearic acid and lower levels of oleic acid, while the remaining analyses did not indicate any substantial compositional differences between the fractions. Although the 29°C solid fraction (∼10%) could be said to be somewhat unique, the natural variation in the normal seasonal composition of butterfat was almost equal to that obtained by fractionation. The experimental physicochemical data obtained for the fractions in this study extend and verify previous work on butteroil fractionation, and indicate that thermal fractionation has marginal merit. On the other hand, literature describing more positive thermal butteroil fractionation results obtained by the properietary Tirtiaux process (Fleurus, Belgium), indictes that it may be a more expedient avenue to explore and let market forces determine whether fractionation has a future in Canada and North America.     

Determination of trans fatty acids and fatty acid profiles in margarines marketed in spain

Two gas chromatography (GC) procedures were compared for routine analysis of trans fatty acids (TFA) of vegetable margarines, one direct with a 100-m high-polarity column and the other using argentation thin-layer chromatography and GC. There was no difference (P>0.05) in the total trans 18∶1 percentage of margarines with a medium level of TFA (∼18%) made using either of the procedures. Both methods offer good repeatability for determination of total trans 18∶1 percentage. The recoveries of total trans isomers of 18∶1 were not influenced (P>0.1) by the method used. Fatty acid composition of 12 Spanish margarines was determined by the direct GC method. The total contents of trans isomers of oleic, linoleic, and linolenic acids ranged from 0.15 to 20.21, from 0.24 to 0.99, and from 0 to 0.47%, respectively, and the mean values were 8.18, 0.49, and 0.21%. The mean values for the ratios [cis-polyunsaturated/(saturated +TFA)] and [(cis-polyunsaturated + cis-monounsaturated)/(saturated +TFA)] were 1.25±0.39 and 1.92±0.43, respectively. Taking into account the annual per capita consumption of vegetable margarine, the mean fat content of the margarines (63.5%), and the mean total TFA content (8.87%), the daily per capita consumption of TFA from vegetable margarines by Spaniards was estimated at about 0.2 g/person/d.