Physical properties of interesterified fat blends

Fat blends, formulated by mixing fully hydrogenated soybean oil with nine different commonly used vegetable oils in a ratio of 1:1 (w/w), were subjected to interesterification (also commonly referred to as rearrangement or randomization) with sodium methoxide catalyst. Fatty acid composition and triacylglycerol molecular species of each fat blend and the interesterified product were determined and correlated with the following physical properties: melting, crystallization characteristics and solid fat content. The differences in the endothermic and exothermic peak temperatures, total heat of fusion and crystallization (β and β′ crystalline content) and solid fat content among the fat blends clearly showed the effect of the composition of each oil on the physical properties. Oils that contained a considerable amount of palmitic acid had a favorable influence on the crystallization and polymorphic form of interesterified fat blends.     

Chemical and enzymatic interesterification of tristearin/ triolein-rich blends: Chemical composition,solid fat content and thermal properties

Blends of high-oleic sunflower oil and fully hydrogenated canola oil were subjected to enzymatic and chemical interesterification using Candida antarctica lipase (5%) and sodium methoxide (0.3%), respectively. The effect of each interesterification process was determined by comparing the triacylglycerol (TAG) composition, solid fat content (SFC) profiles and thermal properties of the blends before and after interesterification. Interesterification resulted in a decrease in the concentration of triunsaturated and trisaturated TAG and an increase in the proportion of mono- and disaturated TAG. These alterations in TAG composition and the presence of a greater variety of TAG species upon interesterification was correlated with a broader melting transition by differential scanning calorimetry and, ultimately, a lower melting point for the interesterified blends. Much broader ranges in plasticity were observed for the interesterified blends (chemically and enzymatically) compared to the physical blends. Even though ideal solubility of stearin in oil was observed, the value predicted by the Hildebrand model was higher than the actual amount. Crystallization kinetic parameters (Avrami index and rate constant) were similar for the non-interesterified, enzymatically interesterified and chemically interesterified blends when compared as a function of SFC. Results from this work will aid in the formulation of more healthy fat and oil products and address a critical industrial demand in terms of formulation options for spreads, margarines and shortenings.     

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.     

Fats from Chemically Interesterified High-Oleic Sunflower Oil and Fully Hydrogenated Palm Oil

Chemical interesterification of different lipid materials has considerable potential for the production of a wide variety of special fats with improved functional and nutritional properties. The present study aimed to evaluate the chemical interesterification of blends of high-oleic sunflower oil (HOSO) and fully hydrogenated palm oil (FHPO) in the ratios (% w/w) of 80:20, 70:30, 60:40 and 50:50. The blends were characterized in triacylglycerol composition, melting point, solid fat content and crystallization behavior, and some applications in food products were suggested. The interesterification altered the solid fat content, melting point and crystallization isotherm of the samples, after the levels of trisaturated triacylglycerols decreased and disaturated–monounsaturated and monosaturated–diunsaturated triacylglycerol contents increased, due to the randomization of fatty acids. The modification in the triacylglycerol composition promoted greater miscibility between the HOSO and FHPO fractions, creating new application possibilities for the food industry.     

“Zerotrans” margarines: Preparation,structure, and properties of interesterified soybean oil-Soy trisaturate blends

The sodium methoxide-catalyzed random interesterification of liquid soybean oil-soy trisaturate blends was explored as a possible route to zerotrans margarine oils. Lipase hydrolysis of the rearranged fats showed that with 0.2% catalyst, interesterification is complete within 30 min at 75-80 C. The glyceride structures of natural and randomized soybean oil-soy trisaturate blends are presented, and relationships between their structure and physical properties are discussed. Organoleptic evaluations showed that randomization of the glyceride structure had no adverse effects on flavor and oxidative stability. Flavor evaluations made against a commercially hardened tub margarine oil showed that interesterified oil had comparable initial and aged flavor scores. X-ray diffraction studies demonstrated that randomized soybean oil-soy trisaturate blends possess the beta-prime crystal structure desirable for use in margarine production. Dilatometric data indicate that random interesterification of 20% by weight of soy trisaturate into the glyceride structure of soybean oil provides a product having a solid fat index suitable for use in a soft tub margarine. Presented at the AOCS Meeting, Chicago, September 1976.     

Monitoring chemical interesterification

Chemical interesterification has long been used to modify oils and fats into functional products. Many chemical compounds can be used as the catalysts, such as sodium metal and sodium methoxide. With addition of the catalyst, the oil turns a well documented distinctive reddish brown. Many believe that this color compound may be the real catalyst in interesterification. The spectral changes of an oil undergoing interesterification were examined in the visible and ultraviolet wavelength ranges. An absorbance peak was found from 320–450 nm. Because this range is the wavelength of blue light, this absorption gives the oil a reddish brown color, the compensated color of blue light. The peak increases as the amount of sodium methoxide increases. To initiate and complete interesterification, the oil absorbance must reach levels of 0.4 and 1.0 at 374 nm, respectively. Controlled partial interesterification is now also possible by controlling the absorbance between 0.4 and 1.0. A novel patent-pending technology, based on this observation, was developed to monitor the progress of interesterification on-line using fiber optic technology. The reaction time and the dosage of sodium methoxide used for randomization have been significantly reduced on bench-scale when using this new tool. Furthermore, the oils interesterified with monitoring have higher oxidative stability and tocopherol contents compared to those by conventional randomization. Presented at the 89th American Oil Chemists’ Society Annual Meeting, Chicago, IL, May 10–13, 1998.     

Crystallization of fully hydrogenated and interesterified fat and vegetable oil

Owing to public concern regarding the adverse health effects of trans fatty acids, an alternative technology to trans fats has recently become an important issue. The interesterification of fully hydrogenated vegetable oil and liquid oil blends is one of the most versatile options. This paper reports a physical analysis of high-melting fat (HMF) prepared through the interesterification of fully hydrogenated soybean oil and regular soybean oil, and through fractionation. The thermal and structural properties of the HMF blended with salad oil at a mass ratio of 4:1 (called the HMF blend, hereafter), which was prepared as a model fat blend for margarine, were assessed using X-ray diffraction (XRD), differential scanning calorimetry (DSC), and polarized light microscopy (POM). To observe the polymorphic transformation, all samples were aged after crystallization, and the development of granular crystals during the aging process was observed. We found that the granular crystals are made of SOS/SSO, POS/PSO, and (SOS+POS)/(SSO+PSO) molecular compounds, all of which easily transform into β form with a double-chain-length structure.     

Trans‐free fats through interesterification of canola oil/palm olein or fully hydrogenated soybean oil blends

Binary blends of canola oil (CO) and palm olein (POo) or fully hydrogenated soybean oil (FHSBO) were interesterified using commercial lipase, Lypozyme TL IM, or sodium methoxide. Free fatty acids (FFA) and soap content increased and peroxide value (PV) decreased after enzymatic or chemical interesterification. No difference was observed between the PV of enzymatically and chemically interesterified blends. Enzymatically interesterified fats contained higher FFA and lower soap content than chemically prepared fats. Slip melting point (SMP) and solid‐fat content (SFC) of CO and POo blends increased, whereas those of CO and FHSBO blends decreased after chemical or enzymatic interesterification. Enzymatically interesterified CO and POo blends had lower SMP and SFC (at some temperatures) than chemically interesterified blends. The status was reverse when comparing chemically and enzymatically interesterified CO and FHSBO blends. The induction period for oxidation at 120°C of blends decreased after interesterification. However, chemically interesterified blends were more oxidatively stable than enzymatically interesterified blends. Interesterified blends of CO and POo or FHSBO displayed characteristics suited to application as trans‐free soft tub, stick, roll‐in and baker's margarine, cake shortening and vanaspati fat.     

Physicochemical Properties of Interesterified Blends of Fully Hydrogenated Crambe abyssinica Oil and Soybean Oil

The chemical interesterification of blends of soybean (SO) and fully hydrogenated crambe oil (FHCO) in the ratios of 80:20, 75:25, 70:30, 65:35, and 60:40 (w/w), respectively, was investigated. FHCO is a source of behenic acid. The blends and the interesterified fats were analyzed for fatty acid and triacylglycerol composition, regiospecific distribution, slip melting point, solid profile, and consistency. The regiospecific analysis of the TAG indicated random insertion of saturated fatty acids at sn-2 of the glycerol of the interesterified blends with more significant alterations at sn-2 than at sn-1 and sn-3. The gradual addition of FHCO increased the solid fat content and the slip melting point. The chemical interesterification formed new TAG facilitating the miscibility between SO and FHCO. The 70:30 interesterified blend was suitable for general use, 60:40 for use as a base stock. At 35 °C, the 65:35 interesterified blend showed suitable plasticity for use in products with fat contents below 80 %. FHCO, rich in behenic acid, is not associated with increased total cholesterol and LDL cholesterol, and it can be used as a low trans fat. FHCO is not associated with increased total cholesterol and LDL cholesterol, and it can be used as a low trans fat alternative.     

Cocoa Butter Alternatives from Enzymatic Interesterification of Palm Kernel Stearin,Coconut Oil,and Fully Hydrogenated Palm Stearin Blends

Structured lipids (SL) were produced from enzymatic interesterification (EIE) of palm kernel stearin (PKS), coconut oil (CNO), and fully hydrogenated palm stearin (FHPS) blends in various mass ratios. The EIE reactions were performed at 60 °C for 6 hours using immobilized Lipozyme RM IM with a mixing speed of 300 rpm. The physicochemical properties, crystallization and melting behavior, solid fat content (SFC), crystal morphology and polymorphism of the physical blends (PB), and the SL were characterized and compared with commercial cocoa butter and cocoa butter alternatives (CBA). EIE significantly modified the triacylglycerol compositions of the fat blends, resulting in changes in the physical properties and the crystallization and melting behavior. SFC and slip melting point of all SL decreased from those of their counterpart PB. In particular, SL obtained from EIE of blends 60:10:30 and 70:10:20 (PKS:CNO:FHPS) exhibited a high potential to be used as trans-free CBA as they showed similar melting ranges, melting peak temperatures, and SFC curves to the commercial CBA with fine needle-like crystals and desirable β' polymorph.     

Effect of Lard Quality on Chemical Interesterification Catalyzed by KOH/Glycerol

The effects of water content, acid value, and peroxide value on interesterification catalyzed by potassium glycerolate (in situ KOH/glycerol) were investigated using lard as a model fat. SEM analysis of KOH/glycerol powder showed that numerous 0.5‐ to 5‐μm porous structures were formed and may play an important role in the interesterification reaction. Water content (up to 10 %, oil weight) and peroxide value (4.29 and 7.11 mmol/kg) significantly extended the induction period of interesterification but complete randomization was still achievable. However, when the acid value reached 5.13 mg KOH/g, complete deactivation of the catalyst was observed at 1 % catalyst content (by oil weight). The sn‐2 fatty acid composition of fully randomized lard was similar to that of non‐randomized lard. Interesterification resulted in substantial rearrangement of the triacylglycerol species and alteration of thermal behaviors. The interesterified lard exhibited a predominant β′ polymorph, as opposed to the dominating β‐form crystals found in the original lard.     

Plastic fats with zero trans fatty acids by interesterification of mango,mahua and palm oils

Speciality plastic fats with no trans fatty acids suitable for use in bakery and as vanaspati are prepared by interesterification of blends of palm hard fraction (PSt) with mahua and mango fats at various proportions. It was found that the interesterified samples did not show significant differences in solid fat content (SFC) after 0.5 or 1 h reaction time. The blends containing PSt/mahua (1:1) showed three distinct endotherms, indicating a heterogeneity of triacylglycerols (TG), the proportions of which altered after interesterification. The SFC also showed improved plasticity after interesterification. Similar results were observed with other blends of PSt/mahua (1:2). These changes in melting behavior are due to alterations in TG composition, as the trisaturated‐type TG were reduced and the low‐melting TG increased after interesterification. The blends containing PSt/mango (1:1) showed improvement in plasticity after interesterification, whereas those containing PSt/mango (2:1) were hard and showed high solid contents at higher temperature and hence may not be suitable for bakery or as vanaspati. The blends with palm and mahua oils were softer and may be suitable for margarine‐type products. The results showed that the blends of PSt/mahua (1:1, 1:2) and PSt/mango (1:1) after interesterification for 1 h at 80 °C showed an SFC similar to those of commercial hydrogenated bakery shortenings and vanaspati. Hence, they could be used in these applications in place of hydrogenated fats as they are free from trans acids, which are reported to be risk factors involved in coronary heart disease. For softer consistency like margarine applications, the blends containing palm oil and mahua oil are suitable.     

Application of Multivariate Analysis in Mid-Infrared Spectroscopy as a Tool for the Evaluation of Waste Frying Oil Blends

Mid-infrared spectroscopy, in association with multivariate chemometric techniques, was employed for pattern recognition and the determination of the composition of waste frying oils (WFO); data are presented in terms of the percentage of soybean oil, palm oil and hydrogenated vegetable fat in frying oil blends. Principal component analysis (PCA) was performed using spectral data (3,000–600 cm⁻¹) to discriminate between the samples containing 100% soybean oil, 100% palm oil, 100% hydrogenated vegetable fat groups and their blends. Additionally, the results indicated that partial least squares (PLS) models based on mid-infrared spectra were suitable as practical analytical methods for predicting the oil contents in WFO blends. PLS models were validated by a representative prediction set, and the root mean square errors of prediction (RMSEP) were 2.8, 4.7 and 5.5% for palm oil, soybean oil and hydrogenated vegetable fat, respectively. The proposed methodology can be very useful for the rapid and low cost determination of waste frying oil composition while also aiding in decisions regarding the management of oil pretreatment and production routes for biodiesel production.     

Über Margarine aus Sojaöl

Margarine from Soybean Oil Fat compositions for the manufacture of margarines of all sorts can be produced from soybean oil alone as the only raw material by indirected interesterification (randomization) of this oil with suitable proportions of hydrogenated soybean fat of definite degree of hardening. The resulting product is then mixed with soybean oil and possibly hardened soybean fat. Especially, the melting behaviour of such compositions has to be adjusted according to the nature of utilization of the individual margarine concerned. The dilatation ranges of household margarine, i. e., for cream-, cake- and pastry-margarine are reported. The keeping properties of a household margarine, which partly contained interesterified fat that consisted of 55% hardened soybean fat and 45% soybean oil, was examined for a longer period, during which its smell, taste structure, consistency, colour as well as autoxidative behaviour were observed. The keeping properties of this margarine were as good as those of high quality vegetable margarines. The same is true for cream-, cake- and pastry-margarines of corresponding compositions.     

Interesterification of Lard and Soybean Oil Blends Catalyzed by Immobilized Lipase in a Continuous Packed Bed Reactor

Structured lipids (SL), formulated by blends of lard and soybean oil in different ratios, were subjected to continuous enzymatic interesterification catalyzed by an immobilized lipase from Thermomyces lanuginosus (Lipozyme TL IM) in a continuous packed bed reactor. The original and interesterified blends were examined for fatty acid and triacylglycerol composition, regiospecific distribution, and solid fat content. Blends of lard and soybean oil in the proportions 80:20 and 70:30 (w/w), respectively, demonstrated a fatty acid composition, and proportions of polyunsaturated/saturated fatty acids (PUFA/SFA) and monounsaturated/polyunsaturated fatty acids (MUFA/PUFA), that are appropriate for the formulation of pediatric products. These same blends were suited for this purpose after interesterification because their sn-2 positions were occupied by saturated fatty acids (52.5 and 45.4%, respectively), while unsaturated fatty acids predominantly occupied sn-1,3 positions, akin to human milk fat. Interesterification caused rearrangement of triacylglycerol species.     

Effect of Interesterified Fats and Isolated trans Fatty Acids on Serum Lipid Classes in Cholesterol-Bile Salt Stressed Rats

Interesterified plastic fat products based on a) sal fat and groundnut oil (30: 70, w/w;P/S,0.8) (sal-GNO);b) vanaspati, partially hydrogenated vegetable oil and groundnut oil (40:60; P/S, 1.0; isolated trans fatty acid content 17%) (vanaspati-GNO);c) cottonseed oil (P/S, 1.5) (CSO) and d) sal fat and safflower oil (50:50, P/S, 1.3) (sal-saff) were prepared using dry sodium methoxide as the catalyst. The products had slip points of 33?34°C. These products, their original blends, safflower oil (P/S, 8.5) and a blend of vanaspati and safflower oil (50 : 50, P/S, 2.8 and isolated trans fatty acid content 22%) (vanaspati-saff) were tested for hypolipidaemic effect (serum total cholesterol, total lipids, triglycerides and phospholipids) in cholesterol-bile salt stressed rats. All the test fats having linoleic acid content varying from 21.9-76.6% and P/S ratio from 0.8 to 8.5 and fed at 10% level providing 23% calorie were found to be superior to vanaspati (P/S, 0.16, 3% linoleic, 43% isolated trans fatty acids). P/S ratio of 1.5 and linoleic content of 30% in fat were found to be optimum for maximum hypolipidaemic effect at above dietary regimen. Fat and cholesterol contents of liver of animals, fed test lipids were significantly lower than that of animals fed vanaspati. when linoleic acid content of the product was comparatively low (e.g. sal-GNO, 25%), the process of rearrangement reduced the cholesterol content of liver. With high linoleic acid content (CSO, 48.2% or sal-saff, 40.4%) interesterification was without any effect. Hypolipidaemic effect of interesterified products was similar to that observed with original materials. Thus, the above quality of a fat having characteristics within the above ranges does not depend upon the distribution of acyl groups in glyceride molecules. Isolated trans fatty acids behaved more or less like a saturated fatty acid in elevating serum lipids. Vanaspati was found to be highly hyperlipidaemic.     

Margarine and shortening oils by interesterification of liquid and trisaturated triglycerides

Liquid vegetable oils (VO), including cottonseed, peanut, soybean, corn, and canola, were randomly interesterified with completely hydrogenated soybean or cottonseed hardstocks (vegetable oil trisaturate; VOTS) in ratios of four parts VO and one part VOTS. Analysis of the reaction products by high-performance liquid chromatography showed that at 70°C and vigorous agitation, with 0.5% sodium methoxide catalyst, the reactions were complete after 15 min. Solid-fat index (SFI) measurements made at 50, 70, 80, 92, and 104°F, along with drop melting points, indicated that the interesterified fats possess plasticity curves in the range of commercial soft tub margarine oils prepared by blending hydrogenated stocks. Shortening basestocks were prepared by randomly interesterifying palm or soybean oil with VOTS in ratios of 1:1 or 3:1 or 4:1, respectively. Blending of the interesterified basestocks with additional liquid VO yielded products having SFI curves very similar to commercial all purpose-type shortening oils made by blending hydrogenated stocks. Other studies show that fluid-type shortening oils can be prepared through blending of interesterified basestocks with liquid VO. X-ray diffraction studies showed that the desirable β′ crystal structure is achieved through interesterification and blending. Presented at AOCS Annual Meeting & Expo, Atlanta, Georgia, May 8–12, 1994.     

Oxidative stability of blends and interesterified blends of soybean oil and palm olein

Improvement of oxidative stability of soybean oil by blending with a more stable oil was investigated. Autoxidation of blends and interesterified blends (9∶1, 8∶2, 7∶3 and 1∶1, w/w) of soybean oil and palm olein was studied with respect to fatty acid composition, fatty acid location and triacylglycerol composition. Rates of formation of triacylglycerol hydroproxides, peroxide value and volatiles were evaluated. The fatty acid composition of soybean oil was changed by blending. Linolenic and linoleic acids decreased and oleic acid increased. The triacylglycerol composition of blends and interesterified blends was different from that of soybean oil. Relative to soybean oil, LnLL, LLL, LLO, LLP, LOO and LLS triacylglycerols were lowered and POO, POP and PLP were higher in blends and interesterified blends (where Ln, L, O, P and S represent linolenic, linoleic, oleic, palmitic and stearic acids, respectively). Interesterification of the blends leads to a decrease in POO and POP and an increase in LOP. Linoleic acid concentration at triacylglycerol carbon-2 was decreased by blending and interesterification. Rates of change for peroxide value and oxidation product formation confirmed the improvement of soybean oil stability by blending and interesterification. But, blends were more stable than interesterified blends. Also, the formation of hexanal, the major volatile of linoleate hydroperoxides of soybean oil, was decreased by blending and interesterification.     

Enzymatic interesterification of olive oil with fully hydrogenated palm oil: Characterization of fats

Seven different reaction products were prepared via enzymatic interesterification of extra‐virgin olive oil (EVOO) and fully hydrogenated palm oil (FHPO), by varying the initial weight ratio of EVOO to FHPO from 80 : 20 to 20 : 80. The chemical, physical and functional properties of both the semi‐solid reaction products and the corresponding physical blends of the precursor starting materials were characterized. Fats prepared using large proportions of FHPO contained high levels of TAG species containing only saturated fatty acid residues. By contrast, high levels of TAG species containing both saturated and unsaturated fatty acid residues were found in fat products obtained with the lowest proportions of FHPO. Independently of the initial weight ratio of EVOO to FHPO, the interesterified products were characterized by a higher molar ratio of unsaturated to saturated fatty acid residues at the sn‐2 position, were softer over a wide temperature range, exhibited lower oxidative stabilities and were completely melted at lower temperatures than the corresponding physical blends. Potential applications of the reaction products range from margarines (highest weight ratios of EVOO to FHPO) to frying fats (lowest weight ratios of EVOO to FHPO).     

Modification of karanja oil (Pongamia glabra) by fractionation,blending, and transesterification

In the present study the modification of detoxified and completely refined karanja oil (Pongamia glabra) was studied by physical and chemical means. Karanja oil was fractionated by the detergent fractionation process at low temperature (3 °C). Astearin fraction was obtained with a yield of 11.0 %. The stearin fraction as such or after bioacidolysis, was found to be suitable as margarine fat bases. Karanja oil was also blended with fats like palm stearin, vanaspati, hydrogenated rice bran oil, and hydrogenated soybean oil in various proportions. The blended products as such or after interesterification were found to be suitable as shortenings, margarine fat bases, or vanaspati substitute.