Effect of interesterification on the structure and physical properties of high-stearic acid soybean oils

Triglyceride structures of genetically modified soybean oils high in stearic acid were determined by high-pressure liquid chromatography, and their physical properties were assessed by dilatometry and dropping point. In their natural state, these oils lack sufficient solids at 10–33°C to qualify as margarine oils. However, after random interesterification, soybean oil containing 17% stearic acid shows a solid fat index (SFI) profile and dropping point closely matching those of a liquid margarine oil. Other oils, with stearic acid contents in the range of 20–33%, showed appreciable SFI values at 10°C but lacked sufficient solids at 21.1–33.3°C. After random interesterification, these oils also exhibited SFI profiles suitable for soft tub margarine, and their drop points increased from 18–19°C to 36–38°C.     

Margarine and margarine oil,formulation and control

The formulation and control of margarine and margarine oils is based primarily on an understanding of the relationships between specific physical measurements and the compositions of the oils blends and their components, and secondarily, on an appreciation of processing effects, Desirable solids-to-liquid ratios are achieved by blending and hydrogenation control. Oils are chosen for their peculiar crystal habit resulting from conditions of processing both as oils, for components, and as a finished margarine product. This presentation identifies the underlying principles directly responsible for (a) proper formulation and control to achieve desirable finished product characteristics, (b) for choosing proper testing methods and (c) for developing adequate in-process controls.     

Lipid composition of selected margarines

Results of analytical studies on the composition of 10 selected margarines representative of consumeravailable hard and soft types are presented. Paired hard and soft products from the same manufacturer were chosen where possible. All of the margarines were compared on the basis of total fatty acid composition, polyunsaturated to saturated fatty acid ratios, totaltrans and thetrans content of the monoene and diene fractions, location of the double bond in the monoene isomers, per cent conjugation, distribution of the fatty acids at the 2 position of the triglycerides, tocopherol content, and the ratios of α-tocopherol to polyunsaturated fatty acids. As expected the soft margarines contained more polyunsaturated fatty acids than their companion hard types, but all soft margarines did not contain more polyunsaturated fatty acids than all of the hard margarines. The one margarine containing safflower oil had the highest polyunsaturated to saturated ratio. Eight of the ten margarines contained more than 15%trans monoene and nine contained less than 5%trans diene. Positional isomers in the monoene fraction were Δ6 toΔ12 with thecis Δ9 isomer predominating. All of the margarines contained less than 1.9% conjugation. The percentage oftrans monoene at the 2 position was greater for some margarines than that in the total fatty acid. This was attributed to the preferential placement of polyunsaturated fatty acids at the 2 position in the original vegetable oils. The forms of tocopherol found were characteristic of the original vegetable oils. Ratios of α-tocopherol to PUFA varied from 0.1 to 0.5 mg/g. Determination of the relationship of the amount of tocopherol content to either source or hardness is not possible on the basis of our data.     

Physicochemical,Textural and Viscoelastic Properties of Palm Diacylglycerol Bakery Margarine During Storage

Physicochemical, textural and viscoelastic properties of palm diacylglycerol (PDG) bakery margarines (DOS720, DOS721 and DOS711) and commercial margarine (CM) throughout a 3-month storage period were evaluated and compared. All the margarines had significant (P < 0.05) increments in slip melting point (SMP), solid fat content (SFC) and hardness during storage with CM having the highest overall increment followed by margarines DOS711, DOS 721 and DOS720. The smaller increments are mainly due to the ability of PDG to delay polymorphic transformation from β′ to β form. In terms of viscoelastic properties, all margarines had a higher degree of firmness which may probably be due to rearrangement of the fat crystals into a three-dimensional scaffolding network upon storage. In terms of melting behavior, storage has no effects on all margarines with the exception of margarine DOS711. The melting behavior of margarine DOS711 displayed a probability of oil exudation during storage. As for polymorphic transformation, CM had the earliest polymorphic transformation with only β crystals after 8 weeks of storage. PDG bakery margarines managed to retard the transformation to more than 10 weeks of storage for DOS711 and 12 weeks of storage for DOS720 and DOS721.     

Evaluation of Transesterified Hardened and Liquid Soybean Oils as Raw Materials for Margarine Oils

Margarine oils have been prepared by transesterification of blends of hardened and liquid soybean oils or by blending of transesterified hardened oils with liquid soybean oil. The dilatometric characteristics of those oils and their nutritional values (as characterized by the L/S ratio of linoleic acid to total saturated acids) have been compared with the same parameters of margarine oils from local and foreign table margarines. It was concluded that margarine oils of suitable melting characteristics and of an average nutritional value (L/S ratio of about 0.70) can be prepared from blends of soybean oils alone, using transesterification process.     

Effect of scraped-surface tube cooler temperatures on the physical properties of palm oil margarine

The effects of scraped-surface tube cooler temperatures on the isothermal solid fat content (SFC) of palm oil margarine during processing and on margarine consistency (yield value, g/cm²), SFC, and polymorphic changes in storage were studied. SFC was measured in the mixing tank after leaving the tube cooler and the pin worker. The SFC at the tube cooler exit was proportional to the amount of cooling; a higher SFC was produced by more extreme cooling treatment. The SFC of all margarines were reduced in the pin worker, and the reduction was related to the initial SFC profile of palm oil. Margarine samples were stored at 28°C for 28 d and tested daily. Margarine processed at 25°C in the tube cooler had the highest consistency and the least change in SFC, but by the second week crystals had transformed into the β form. Uniform product consistency and SFC were observed in margarines processed at 20 and 15°C. These margarines retained the β′ crystal form for 3 and 4 wk, respectively. The best palm oil margarine was obtained with a tube cooler temperature of 15°C and a residence time of 1.8 min.     

Provitamin a activity and stability of β-carotene in margarine

Summary Samples of synthetic β-carotene have been assayed for vitamin A activity by the rat-curative, growth method against vitamin A acetate and compared with natural carotene. The U.S.P. XIV diet was modified by the addition of vitamin B₁₂ and α-tocopherol, which have been reported to enhance carotene utilization. Doses of vitamin A and carotene were given in cottonseed oil and in margarine; but, contrary to the report of Deuelet al. (13), no significant increase was observed in the utilization of carotene fed in margarine. The samples tested include crystalline all-trans β-carotene, micropulverized all-trans β-carotene in an oil suspension, and a series of 10 commercial margarines fortified with vitamin A. and carotene in a ratio of about 2 I.U. of vitamin A to 1 I.U. of carotene. In terms of vitamin A activity in the rat bioassay, the average potency of β-carotene in three separate bioassays of crystalline carotene was found to be 1,730,000 I.U. per gram with a standard error of ±3.5%. Thus in these assays 1 I.U. of vitamin A activity was found to be equivalent to 0.58 mcg. of all-trans β-carotene, a value in essential agreement with 0.6 mcg., the presently accepted International Standard. For margarine samples containing vitamin A and β-carotene, the average vitamin A activity in 2 bioassays was found to be very close to that calculated from the colorimetric assays, using the factor for β-carotene, 0.6 mcg.=1 I.U. The fact that other workers have reported higher provitamin A activity for β-carotene in the rat bioassay indicates the dependence of the results on the particular conditions of the bioassay. The stability of vitamin A and β-carotene in commercially prepared margarines stored at 40°F. and 75°F. was studied by accepted colorimetric procedures. Average retention values of 94% or better were obtained in margarines stored two months when the vitamin activity was supplied either from β-carotene or from vitamin A.     

Determination of FA composition and total trans FA of Turkish margarines by capillary GLC

In this research, FA composition and total trans FA contents of 16 different brands of margarine (8 hard-type and 8 soft-type) sold in Turkey were determined by capillary GLC method. According to the results, the contents of saturated FA, monounsaturated FA, and PUFA were within the ranges of 23.9–32.3, 44.0–61.9, and 14.2–24.1%, respectively, in hard-type margarines, and 27.0–39.9, 21.0–40.9, and 32.0–53.7%, respectively, in soft-type margarines. Hard-type margarines contained total trans FA concentrations of 20.1–34.3%, whereas soft-type margarines contained less than 8.9% total trans FA. C_18∶1 trans acid content was within the range of 18.5–29.8% in hard-type margarines, and it was significantly higher than the range in soft margarines (0.7–8.1%). C_18∶1 trans acid was the major trans FA in all margarines, and C_18∶3 trans acid concentrations were less than 0.2%.     

Changing trends in consumer margarines

Margarine has changed dramatically from 100 years ago when it was first made as a butter substitute. It is now a high technology product with many mutations and variations. There are ten different types of margarine produced today. There are regular, whipped, and polyunsaturated margarines in both stick and soft forms. There are diet margarines, liquid margarines, and new 60% vegetable oil spreads. These margarines are made from a variety of oils including soybean, cottonseed, palm, corn, safflower, and sunflower oils. These tailor-made products cater to the needs of many different segments of the population. This marketing strategy has helped to create increasing consumer demand over the years. Presented at the AOCS Meeting, New York, May 1977.     

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.     

Margarine and margarine oils: Finished product quality

Finished margarine quality is presented in terms of the margarine manufacturer’s needs as expressed by in-house quality control and oil blend specifications. The philosophy of adequate performance testing is discussed as are the needs for in-process controls. Without adequate and effective in-process controls, specification testing practices result in only after-the-fact information and defeat the real purpose of specifications, which is to insure quality production and not merely to assess whether or not it has been attained. Although margarine manufacturers have found effective means of applying these controls to their own production, they have been lax in applying them to their raw material receipts, an emphasis that is at least of equal importance to finished product quality. One of seven papers presented in the symposium “Fats and Oils in the Food Industry,” Atlantic City, October 1971.     

<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.     

Determination of seventeen elements in edible oils and margarine by instrumental neutron activation analysis

Instrumental neutron activation analysis was used to determine the concentration of As, Ba, Ce, Co, Cr, Cs, Eu, Fe, Hg, K, Na, Rb, Sb, Sc, Se, Sr and Zn in almond, sunflower, peanut, sesame, linseed, soy, corn and olive oils, as well as in three margarine brands. The concentration of As, Ba, Ce, Cs, Eu, Hg, Rb, Se and Sr were below the system detection limit under the experiment conditions. Chromium was detected only in one of the margarine samples (171 μg/g); Sb only in corn oil (18 ng/g) and Sc only in linseed oil (19 ng/g). Cobalt, Fe, K, Na and Zn were detected in all oil and margarine samples investigated. The concentration ranges for Co, Fe, K, Na and Zn in oils were: 0.016–0.053; 4.45–19.1; 5.93–47.2; 2.44–12.9 and 0.48–1.54 μg/g, respectively. For margarine, the concentration ranges for Co, Fe, K, Na and Zn were 0.09–0.012; 4.53–10.6; 58.3–1140; 13.2–9870 and 0.38–0.47 μg/g, respectively. The elemental contents of the analyzed samples are within the ranges reported in the literature for edible oils and fats.     

The development and application of novel vegetable oils tailor‐made for specific human dietary needs

Conventional edible oils, such as sunflower, safflower, soya bean, rapeseed (canola) oils, were modified to obtain high‐oleic, low‐linoleic or even low‐linolenic oils. The aim was to develop salad, cooking and frying oils, that are very stable against lipid peroxidation. They are also suitable for margarine blends, as additives to cheeses and sausages, or even as feed components. Oils containing higher amounts of medium‐chain length or long‐chain polyunsaturated fish oil fatty acids are suitable as special dietetic oils or as nutraceuticals. High‐stearic oils are designed as trans‐fatty acid‐free substitutes for hydrogenated oils. New tailor‐made (designer) oils are thus a new series of vegetable oils suitable for edible purposes, where conventional oils are not suitable.     

Phylloquinone (vitamin K1) and dihydrophylloquinone content of fats and oils

Assessment of vitamin K (VK) dietary intakes has been limited by the incompleteness of VK food composition data for the U.S. food supply, particularly for VK-rich oils. The phylloquinone (VK-1) and 2′,3′-dihydrophylloquinone (dK) concentrations of margarines and spreads (n=43), butter (n=4), shortening (n=4), vegetable oils (n=6), and salad dressings (n=24) were determined by RP-HPLC with fluorescence detection. Each sample represented a composite of units or packages obtained from 12 or 24 outlets, which were geographically representative of the U.S. food supply. Butter, which is derived from animal fat sources, had less VK-1 compared to vegetable oil sources. The VK-1 and dK of the margarines and spreads increased with fat content and the degree of hydrogenation, respectively. In some margarines or spreads and in all shortenings, the dK concentrations were higher than the corresponding VK-1 concentrations. As the fat content of salad dressings increased, the VK-1 concentrations also increased. Fat-free foods had <1 μg/100 g of either form of the vitamin. No dK was detected in the salad dressings or oils tested. Some margarines, spreads, and salad dressings may be significant sources of vitamin K in the U.S. food supply.     

Determination of the solid-liquid ratio of fats by wide-line nuclear magnetic resonance

The Newport Quantity Analyzer is suitable for the determination of the solid-liquid ratio in fats provided an accurate and rapidly reacting temperature control for the sample between the magnets is used. Hydrogen content and relaxation times determine the NMR signals. The hydrogen content can be calculated from the iodine value and the saponification value. In order to obtain a reliable “liquidline ” for a given sample, the NMR read out is measured at 60 C (completely molten state) and this value is multiplied by fixed factors for each temperature. With the Newport instrument, these conversion factors are still slightly dependent on the hydrogen content. Determinations of the solids content of various margarine blends, shortenings and hydrogenated oils were made. The relation between dilatometry and NMR results is temperature dependent. The correlations were especially good at low temperature, but poor at > 30 C. One of 10 papers to be published from the Symposium “Wide Line Nuclear Magnetic Resonance” presented at the AOCS Meeting, Minneapolis, October 1969.     

A review of rapeseed oil uses for edible purposes

Food technological aspects on the use of rape-seed oil and otherCruciferae seed oils as salad oils, in margarine, shortenings and some other foods are briefly reviewed. It is concluded that these oils in hydrogenated or nonhydrogenated form may compete favorably with other vegetable oils and animal fats. One of nine papers published from the Symposium, “Cruciferous Oilseeds,” ISF-AOCS World Congress, Chicago, September 1970.     

Content of trans-fatty acids in edible margarines

Fatty acid composition, including trans-isomers, was determined for four types of imported margarines consumed by the Bulgarian population. The results were compared with data obtained from a Bulgarian edible margarine produced under German license. Fatty acid composition and trans-isomer content were determined by gas chromatography of fatty acid methyl esters on a packed and capillary column, respectively. The total contents of trans-isomers of oleic and linoleic acid were within the ranges of 1.9–8.0% and 0.4–1.4%, respectively. The Bulgarian margarine contained similar quantities of trans-isomers.     

Elaboration of enriched margarine with lentisk oil and honey: Formulation,characterization, and monitoring of oxidative stability

This study focused on the use of lentisk oil and honey as natural sources to formulate margarine with ameliorated quality and oxidative stability. For this, five margarines were formulated with honey and different concentrations of lentisk oil. Analyses were performed on oil and honey used, and then physicochemical characterization and several oxidative stability tests were applied to assess margarine quality. The results showed a significant richness of lentisk oil and honey in total phenolics and total flavonoids and expressed good antioxidant activities. As well as the evaluation of oxidative stability of enriched margarines during 3 months of storage demonstrated that margarine added with 2% lentisk oil (M1) had the best resistance properties and longer Rancimat induction time (22.26 h), better than the control and margarines added with 5% (M2), 10% (M3), and 15% (M4) lentisk oil. Globally, margarines prepared with high concentrations of lentisk oil (M2–M4) were not different from the control, whereas only M1 was permitted to ameliorate the stability of margarine with a slight influence on physicochemical parameters. The elaboration of margarine supplemented with 2% lentisk oil improves the properties of the product, which could then be applied to margarine manufacturing.     

Fatty Acid Profile Including <Emphasis Type="Italic">Trans</Emphasis> Fatty Acid Content of Margarines Marketed in Mexico

In this study, the fatty acid profile of 42 margarines marketed in Mexico was identified and quantified including the total trans fatty acids (TFA). The ratio of the sum of cholesterol-lowering fatty acids CLFA (cis-oleic, linoleic and α-linolenic fatty acids) to the sum of cholesterol-raising fatty acids CRFA (C12:0, C14:0, C16:0, TFA) and the ω6/ω3 ratio were calculated to evaluate the nutritional quality of the margarine samples. The results showed that the high content of C12:0, C14:0 and C16:0 fatty acids in some samples indicated the use of coconut and palm oils instead of partially hydrogenated fatty acids in order to decreased TFA content. Of the samples, 33% had less than 1 g/100 g of fat which could be considered as “free from TFA” according to the Danish Legislation. The ω6/ω3 ratio ranged between 5.85:1 and 25.85:1, the ideal relation being 5–10:1. The CLFA/CRFA ranged from 0.46 to 3.10, being the recommended ratio as high as possible. Of the 42 margarines, only five samples had an acceptable fatty acid profile, that is, low TFA and saturated fatty acids, high monounsaturated fatty acids content and adequate ω6/ω3 and CLFA/CRFA ratios.