Production of trans‐free margarine stock by enzymatic interesterification of rice bran oil,palm stearin and coconut oil

BACKGROUND: Trans‐free interesterified fat was produced for possible usage as a spreadable margarine stock. Rice bran oil, palm stearin and coconut oil were used as substrates for lipase‐catalyzed reaction. RESULTS: After interesterification, 137–150 g kg^?1 medium‐chain fatty acid was incorporated into the triacylglycerol (TAG) of the interesterified fats. Solid fat contents at 25 °C were 15.5–34.2%, and slip melting point ranged from 27.5 to 34.3 °C. POP and PPP (β‐tending TAG) in palm stearin decreased after interesterification. X‐ray diffraction analysis demonstrated that the interesterified fats contained mostly β′ polymorphic forms, which is a desirable property for margarines. CONCLUSIONS: The interesterified fats showed desirable physical properties and suitable crystal form (β′ polymorph) for possible use as a spreadable margarine stock. Therefore, our result suggested that the interesterified fat without trans fatty acid could be used as an alternative to partially hydrogenated fat. Copyright © 2010 Society of Chemical Industry     

Development of chemically interesterified healthy coconut oil blends

Edible vegetable oil blends, such as coconut:linseed; coconut:safflower; coconut:sunflower; coconut:rice‐bran oils; in the ratio of 70:30 and 60:40 v/v and pure coconut oil (CNO) were interesterified using sodium methoxide 0.5% and subsequently refined to prepare nutritionally superior flowable CNO blends which remained liquid even at sub‐zero temperatures. The slip melting point of chemically interesterified fats could not be determined as they are liquified just after removing from freezing chamber in comparison with the slip melting point of 21.5–26.5 °C for their uninteresterified counterparts. These interesterified fats were liquid and flowable at 6 °C for more than 4 h in a cooling chamber and their solidification temperature ranged between ?2.0 and ?5.5 °C. Free fatty acids showed an increasing trend from 0.35% to 2.0% resulting in decrease in triglycerides After refining these oil blends showed values similar to their controls. However, iodine value of interesterified and uninteresterified oils were close to each other. Differential scanning calorimetry showed the onset of crystallisation at lower temperatures and lower solid fat content for interesterified fats. A nutritionally superior combination of CNO blend which is flowable at low temperature could be prepared.     

Characterisation of zero‐trans margarine fats produced from camellia seed oil,palm stearin and coconut oil using enzymatic interesterification strategy

Zero‐trans interesterified fats were produced from camellia seed oil (CSO), palm stearin (PS) and coconut oil (CO) with three weight ratios (CSO/PS/CO, 50:50:10, 40:60:10 and 30:70:10) using Lipozyme TL IM. Results showed that the interesterified products contained palmitic acid (34.28–42.96%), stearic acid (3.96–4.72%), oleic acid (38.73–47.95%), linoleic acid (5.92–6.36%) and total medium‐chain fatty acids (MCFA)s (∑MCFAs, 5.03–5.50%). Compared with physical blends, triacylglycerols of OOO and PPP were decreased and formed new peaks of equivalent carbon number (ECN) 44 in the interesterified products. The product CPC3′ showed a slip melting point of 36.8 °C and a wide plastic range of solid fat content (SFC) (45.8–0.4%) at 20–40 °C. Also, the major β′ form was determined. These data indicated that the zero‐trans interesterified fats would have a potential functionality for margarine fats. Subsequently, the antioxidative stabilities of interesterified products with the addition of α‐tocopherol (α‐TOH) and ascorbyl palmitate (AP) were investigated. The results indicated that AP had a dose‐dependent effect at concentrations of 100, 200 and 400 ppm.     

Effects of chemical interesterification on solid fat content and slip melting point of fat/oil blends

Fat/oil blends, formulated by mixing fully hydrogenated palm oil stearin or palm oil stearin with vegetable oils (canola oil and cottonseed oil) in different ratios from 30:70 to 70:30 (w/w %), were subjected to chemical interesterification reactions on a laboratory scale. Fatty acid (FA) composition, iodine value, slip melting point (SMP) and solid fat content (SFC) of the starting blends were analysed and compared with those of the interesterified blends. SMPs of interesterified blends were decreased compared to starting blends because of extensive rearrangement of FAs among triacylglycerols. These changes in SMP were reflected in the SFCs of the blends after the interesterification. SFCs of the interesterified blends also decreased with respect to the starting blends, and the interesterified products were softer than starting blends. These interesterified blends can be used as an alternative to partial hydrogenation to produce a plastic fat phase that is suitable for the manufacture of margarines, shortenings and confectionary fats.     

Physicochemical properties and antioxidant activity of a synthetic cocoa butter equivalent obtained through modification of mango seed oil

This research describes the interesterification of Malaysian mango seed oil (MSO) and palm oil mid‐faction (POMF) to develop a cocoa butter equivalent. Fat blends, formulated by binary blends of palm oil mid‐fraction and mango seed oil at different ratios ({100:0}, {60:40}, {50:50}, {40:60}, {0:100}), were subjected to enzymatic interesterification. The solid fat content revealed that all interesterified blends except 100% POMF {0:100} melted completely at body temperature. The interesterified {50:50} blend exhibited a slip melting point (30.35 °C) and saponification value (186.89) close to cocoa butter (P < 0.05). Thermal behaviour analysis by differential scanning calorimetry showed fusion and crystallisation behaviour similar to cocoa butter. Moreover, both the blend and cocoa butter scavenging abilities were based on the 2,2‐diphenyl‐1‐picrylhydrazyl assay, with the concentration required to reduce radical absorbance by 50% (IC₅₀) of 43.08% and 41.1%, respectively. Therefore, the MSO: POMF blend may have use as a health‐promoting food in human diets.     

Improvement of palm oil and sunflower oil blends by enzymatic interestrification

Palm oil (PO) and sunflower oil (SFO) blends with varying proportions were subjected to enzymatic interesterification (EIE) using a 1,3‐specific immobilised lipase. The interesterified blends were evaluated for their slip melting point (SMP), solid fat content (SFC) at 10–40 °C, p‐anisidine value, peroxide value, free fatty acids (FFA), induction period of oxidation at 110 °C (IP110) and composition of fatty acids by gas chromatography. Under EIE treatment, the blends of PO and SFO in different proportions (20:80, 40:60, 50:50, 60:40 and 80:20) had saturated and unsaturated fatty acid content in the range of 37.6–52.0% and 48.0–62.4%, respectively. The blends showed a considerable reduction in their SFC, SMP, peroxide value and oxidative stability at 110 °C, but presented increase in FFA and p‐anisidine value. The optimum condition for minimising the fatty acid in oil was obtained, at 64 °C, using 8.9% enzyme and 3 h reaction time.     

Evaluation of shortenings based on various palm oil products

Several formulations based on blends of hydrogenated palm oil (MP 41·5°C) and palm stearin (IV 44) with other liquid oils, on direct blends of palm stearin with other liquid oils, and on 100% inter-esterified palm olein, were used as feedstocks in shortening production. The shortenings were stored at 20°C over a period of one month. Physicochemical characteristics, creaming properties and baking performance of the shortenings were evaluated and compared with the best shortening on the market. Slip melting point of the shortenings ranged from 41·5 to 46·4°C. Palm-cottonseed oil shortenings had higher solid fat contents at all temperatures than palm-soya bean or palm-low erucic acid rapeseed oil shortenings. The shortenings were rich in C₅₀, C₅₂and C₅₄ glycerides. Creaming power after 12 min of beating ranged from 1·55 to 1·77 cm³ g^?1. Palm stearin-cottonseed (3:2) oil shortening showed the best creaming performance. The specific volume of cakes ranged, for the experimental shortening, from 90% to 101% from the control, with low erucic acid-palm blends showing the best performance. In applications for both aerated cream and cakes, inter-esterified palm olein was excellent.     

<Emphasis Type="Italic">Trans</Emphasis>-free margarine fat produced using enzymatic interesterification of rice bran oil and hard palm stearin

Trans-free interesterified fats were prepared from blends of hard palm stearin (hPS) and rice bran oil (RBO) at 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, and 80:20 weight % using immobilized Mucor miehei lipase at 60°C for 6 h with a mixing speed of 300 rpm. Physical properties and crystallization and melting behaviors of interesterified blends were investigated and compared with commercial margarine fats. Lipase-catalyzed interesterification modified triacylglycerol compositions and physical and thermal properties of hPS:RBO blends. Slip melting point and solid fat contents (SFC) of all blends decreased after interesterification. Small, mostly β′ form, needle-shaped crystals, desirable for margarines were observed in interesterified fats. Interesterified blend 40:60 exhibited an SFC profile and crystallization and melting characteristics most similar to commercial margarine fats and also had small needle-like β′ crystals. Interesterified blend 40:60 was suitable for use as a transfree margarine fat.     

Use of enzymatic transesterified palm stearin-sunflower oil blends in the preparation of table margarine formulation

Palm stearin–sunflower oil (PS:SO) blends, formulated by mixing 40 to 80% palm stearin in increments of 10% (w/w), were subjected to transesterification catalysed by lipases from Pseudomonas sp. and Rhizomucor miehei (Lipozyme 1M 60). The physical properties of the transesterified products were evaluated by slip melting point (SMP), differential scanning calorimetry (DSC), solid fat content (SFC) and X-ray difflaction (XRD) analyses. SMP results indicate that Pseudomonas lipase caused a bigger drop in SMP (33%) in the PS–SO (40:60) blend than the R. miehei-lipase-catalysed reaction blend (13%). The Pseudomonas-catalyzed blends of PS-SO, at 40:60 and 50:50 ratios, showed complete melting at 37 and 40°C, respectively, while the R. miehei-catalyzed PS–SO blend at 40:60 ratio had a residual SFC of 3.9% at 40°C. Pseudomonas lipase also successfully changed the polymorphic form(s) in the unreacted PS–SO mixture from a predominantly β form to a predominantly β′ form in the transesterified blends. However, no changes in polymorphic forms were observed after transesterification with R. miehei lipase (as against to the unreacted PS–SO blends). These results suggest that the Pseudomonas lipase caused a greater randomization and diversification of fatty acids, particularly palmitic acids, in palm stearin with the unsaturated fatty acids from sunflower oil than did R. miehei lipase. Based on the physical characteristics, the Pseudomonas-catalyzed 40:60 and 50:50 PS:SO blends would be the two most suitable blends to be used as table margarine formulations.     

Utilization of interesterified oil blends in the production of frankfurters

Ten treatments of frankfurters were produced with interesterified oil and oil blends (palm oil, palm stearin, cottonseed oil, hazelnut oil and their mixtures) and were compared to control, produced with all animal fat. Addition of interesterified oil and oil blends affected (p < 0.05) the moisture and fat content and pH values of frankfurters. According to the colour measurements, the brightness value (L^∗) of most of the samples with interesterified oil and oil blends were higher (p < 0.05) than the control. The fatty acid composition of frankfurters was modified. The PUFA/SFA values of frankfurters were increased due to the presence of interesterified oil and oil blends in the formulation. Frankfurters with 100% interesterified cottonseed oil or with interesterified oil blends with 66.6% and 83.4% cottonseed oil had PUFA/SFA ratio higher than 0.4 and are considered better than all others from the health point of view. Frankfurters produced with 100% interesterified cottonseed and hazelnut oil or with interesterified hazelnut oil blends had the same (p > 0.05) scores for sensory attributes with the control, while all other treatments were also acceptable.     

Structured lipids obtained by chemical interesterification of olive oil and palm stearin

Interesterification of palm stearin (PS) with liquid vegetable oils could yield a good solid fat stock that may impart desirable physical properties, because PS is a useful source of vegetable hard fat, providing β′ stable solid fats. Dietary ingestion of olive oil (OO) has been reported to have physiological benefits such as lowering serum cholesterol levels. Fat blends, formulated by binary blends of palm stearin and olive oil in different ratios, were subjected to chemical interesterification with sodium methoxide. The original and interesterified blends were examined for fatty acid and triacylglycerol composition, melting point, solid fat content (SFC) and consistency. Interesterification caused rearrangement of triacylglycerol species, reduction of trisaturated and triunsaturated triacylglycerols content and increase in diunsaturated-monosaturated triacylglycerols of all blends, resulting in lowering of melting point and solid fat content. The incorporation of OO to PS reduced consistency, producing more plastic blends. The mixture and chemical interesterification allowed obtaining fats with various degrees of plasticity, increasing the possibilities for the commercial use of palm stearin and olive oil.     

MELTING CHARACTERISTIC AND SOLID FAT CONTENT OF MILK FAT AND PALM STEARIN BLENDS BEFORE AND AFTER ENZYMATIC INTERESTERIFICATION

Melting characteristics and solid fat content of anhydrous milk fat (AMF), soft palm oil stearin (SPOs), hard palm oil stearin (HPOs) and their blends were studied by differential scanning calorimetry (DSC) and nuclear magnetic resonance (NMR) spectroscopy, respectively. Solid fat contents (SFC) determined by NMR were used to construct isosolid diagrams; these indicated the presence of an eutectic effect along the binary blends of AMF:SPOs which only could be observed at 5 and 10C. The effect was reduced after interesterification by sn-1,3-specific lipase. The modification also reduced the number of the distinct DSC melting peaks, demonstrating a better miscibility among the blended fats. A substantial decrease in DSC melting enthalpy of interesterified blends was found to be parallel to a decrease in SFC that was observed at 25–40C. Fatty acid composition showed that improved functionality of AMF may be due to an enrichment in long-chain saturated fatty acids contributed both by SPOs and HPOs.     

Zero trans shortening using rice bran oil, palm oil and palm stearin through interesterification at pilot scale

Fat blends, formulated by mixing refined, bleached and deodorised (RBD) palm oil (PO) or RBD palm stearin (PS) with RBD rice bran oil (RBO) in various ratios were subjected to chemical interesterification (CIE) at pilot scale using sodium methoxide (NaOMe) as catalyst. The resultant interesterified fat was processed through a margarine crystalliser under optimised conditions. The blends before and after CIE were investigated for triacylglycerol (TAG) composition, solid fat content (SFC) and melting characteristics, polymorphic form, fatty acid composition (FAC), bioactive (tocols, sterols, oryzanol) constituents and trans fatty acids (TFA). CIE was found to be very effective in terms of rearrangement of fatty acids (FAs) among TAGs and consequent changes in the physical characteristics. The SFC of the interesterified PS/RBO blends decreased significantly ( P  ≤ 0.05) when compared with those of PO/RBO blends. The interesterified binary blends with 50–60% PS and 40–50% RBO, and 70–80% PO and 20–30% RBO had SFC curves in the range of all-purpose type shortenings. CIE facilitated the formation of β' polymorphic forms. FAC of shortenings prepared using the optimised blends contained 15–20% C_18:2 polyunsaturated fatty acid (PUFA) and no TFA. Total tocol, sterol and oryzanol content of zero trans shortenings were 650–1145, 408–17 583 and 1309–14 430 ppm. CIE using NaOMe did not affect the bioactive constituents significantly ( P  ≤ 0.05).     

Directed interesterification of a brazilian palm oil and analysis of the original and interesterified oil and its fractions

A commercial sample of the Brazilian palm oil from the north eastern State of Bahia after neutralisation, washing and drying was interesterified in the presence of sodium-potassium alloy (NaK) at 30°C in a nitrogen atmosphere. The catalyst was destroyed by addition of water in a carbon dioxide atmosphere and the interesterified oil was crystallised from light petroleum, yielding an olein and stearin fraction. The fatty acid and triacylglycerol composition of the neutralised oil was determined by gas chromatography (g.c.) and high-performance liquid chromatography (h.p.l.c.) respectively and was shown to be similar to that of Malaysian and African palm oil. The compositions of the interesterified Brazilian oil and its liquid and solid fractions were also determined. The physicochemical characteristics of the olein obtained by interesterification with NaK, such as iodine value (96.8) and its softening point (below ?8°C) indicated its suitability for the use as salad oil.     

Application of hydrogenated palm kernel oil and palm stearin in whipping cream

Non-dairy creams made from hydrogenated palm kernel oil (HPKO) are generally more stable than dairy creams. However, in summer the emulsion tends to separate. This paper outlines some steps that were taken to modify the HPKO with the intention of increasing the stability without affecting whipping performance. This was achieved by blending HPKO with palm stearin (POs). Interesterification was employed to eliminate the increase in solid fat content at 37°C and 40°C. Results of the experiment showed that an interesterified HPKO: POs 66:34 blend proved to have satisfactory whipping performance when compared to creams made with HPKO alone.     

Scaled-up production of zero-trans margarine fat using pine nut oil and palm stearin

An interesterified structured lipid was produced with a lipid mixture (600 g) of pine nut oil (PN) and palm stearin (PS) at two weight ratios (PN:PS 40:60 and 30:70) using lipase (Lipozyme TL IM, 30 wt.%) as a catalyst at 65 ^°C for 24 h. Major fatty acids in the interesterified products were palmitic (35.1–40.4%), oleic (29.5%), and pinolenic acid (cis-5, cis-9, cis-12 18:3; 4.2–5.9%). α-Tocopherol (1.1–1.3 mg/100 g) and γ-tocopherol (0.3–0.4 mg/100 g) were detected in the interesterified products. Total phytosterols (campesterol, stigmasterol, and β-sitosterol) in the interesterified products (PN:PS 40:60 and 30:70) were 63.2 and 49.6 mg/100 g, respectively. Solid fat contents at 25 ^°C were 23.6% (PN:PS 40:60) and 36.2% (PN:PS 30:70). Mostly β′ crystal form was found in the interesterified products. Zero-trans margarine fat stock with desirable properties could be successfully produced from pine nut oil and palm stearin.     

Thermal and crystal characteristics of enzymatically interesterified fats of fatty acid-balanced oil and fully hydrogenated soybean oil in supercritical CO2 system

Blends of fatty acid-balanced oil that was prepared by the aqueous enzymatic extraction, and with fully hydrogenated soybean oil in different weight ratios from 30:70 to 80:20 (wt%) were interesterified using Lipozyme RM IM in a supercritical CO₂ system. The optimal immobilized enzyme dosage, pressure, substrate ratio, temperature, and time were 6% (w/w) of initial substrates, 8 MPa, blend ratio with 60:40 (wt%) of fatty acid-balanced oil and fully hydrogenated soybean oil, a temperature of 70°C, and reaction time of 2 h, respectively. It was observed that at the optimal conditions, under supercritical CO₂ conditions, the reaction time of the interesterification was shorter than that of conventional enzymatic interesterification. The slip melting point, solid fat content, fatty acid composition, differential scanning calorimetry, polymorphic form and crystal morphology of the enzymatically interesterified fats were evaluated. The results indicated that the interesterified fats showed desirable physical properties with lower slip melting point and solid fat content, suitable crystal form (β′ polymorph), and without trans-fatty acid for possible use as a shortening and margarine stock.     

SEMI-SOLID FAT BY INTERESTERIFICATION OF RED PALM OIL WITH OTHER VEGETABLE OILS

Interesterification of appropriate blends of vegetable oils offers an alternative method for obtaining semi-solid fats without hydrogenation. Random interesterification was carried out on blends of different oils, namely palm oil and sunflower oil (8:2, 7:3 and 6:4 w/w), palm oil and rice bran oil (8:2 and 7:3 w/w), palm oil and coconut oil (9:1 and 6:4 w/w), as well as palm oil and soybean oil (7:3 w/w), in the presence of sodium methoxide as a catalyst (0.2% w/v). The melting characteristic of the interesterified fat obtained from a blend of refined red palm oil and sunflower oil blend, in the ratio of 4:1 (w/w; slip melting point 41C) indicated that this combination could be an ideal margarine fat base.     

Production of lipase‐catalyzed solid fat from mustard oil and palm stearin with linoleic acid by response surface methodology

BACKGROUND: Solid fat was produced from mustard oil and palm stearin through lipase‐catalyzed reaction, in which linoleic acid was intentionally incorporated. For optimizing the reaction condition of melting point and ω6/ω3 fatty acids, response surface methodology (RSM) was employed with three reaction variables such as substrate mole ratio of mustard oil (MO) to palm stearin (PS) (X₁), reaction temperature (X₂) and reaction time (X₃). RESULTS: The predictive model for melting point of solid fat was adequate and reproducible due to no significant lack of fit (P = 0.0764), P‐value (0.0037) of the model, and satisfactory level of coefficient of determination (R² = 0.92). For the ω6/ω3 ratio model, R² and P‐value were 0.89 and 0.0132, respectively, but lack of fit was significant (P = 0.0389). The melting point of the produced solid fat was affected by substrate mole ratio, whereas reaction temperature and time had no significant effect. The ω6/ω3 ratio of solid fat was influenced by substrate mole ratio and reaction temperature but not by reaction time. Based on ridge analysis, lower ω6/ω3 ratio was predicted by decreasing substrate mole ratio and reaction time, and by increasing reaction temperature. CONCLUSIONS: For producing solid fat with a specific melting point of 34.57 °C, a combination of 1:2 (X₁), 65.17 °C (X₂) and 21.46 h (X₃) was optimized, and the optimization was confirmed under the same reaction conditions. The solid fat contained palmitic (37.8%), linoleic (24.8%), oleic (21.3%), and erucic acid (9.7%), and its solid fat content was 30.3% and 10.3% at 20 and 30 °C, respectively. Copyright © 2009 Society of Chemical Industry     

Physicochemical Properties and Sensory Attributes of Medium- and Long-Chain Triacylglycerols (MLCT)-Enriched Bakery Shortening

Six binary formulations of medium- and long-chain triacylglycerols (MLCT) fat and palm stearin and four ternary formulations of MLCT fat, palm stearin, and palm olein were produced. MLCT fat and palm stearin were mixed in ranges of 40–90% with 10% increments (w/w), while for the ternary formulations, 10% and 20% palm olein were substituted to palm stearin in MS 46 and MS 55 formulations. The solid fat content (SFC) by pulsed nuclear magnetic resonance and heating profiles using differential scanning calorimeter of these formulations were determined. Results obtained from SFC and heating profiles found that all the formulations melted completely at 55 °C. The high complete melting temperature is due to the stearic acid content in MLCT fat. Generally, increasing % MLCT fat (40–90%) in the formulations lowers the SFC curves at the measured temperatures (0–60 °C). The binary samples of MS 73, MS 82, and MS 91 showed SFC between 15% and 25% at room temperature (25 °C), which indicated that these formulations were suitable for shortening production. As the production cost of MLCT fat is high (approximately USD 3/kg), an attempt to reduce the proportion of MLCT fat in the shortening formulations was done by developing the ternary formulations. Shortenings formulated with 40:40:20 (MSO 442), 50:40:10 (MSO 541), and 50:30:20 (MSO 532) of MLCT fat/palm stearin/palm olein formulations had similar SFC% at 25 °C, and they were subsequently chosen to produce shortening. Using multivariate analysis, taste attribute showed positively and highly correlated to the melting temperature and SFC at 25 °C of the MLCT-enriched shortenings. In acceptance test, high correlation (R ² = 0.98) was only found on cakes made from MSO 442 and MSO 541 shortenings. Both untrained and trained panelists rated the Madeira cakes made from MSO 532 shortening the highest for overall acceptability.