Polymorphic stability of some shortenings as influenced by the fatty acid and glyceride composition of the solid phase

A number of North American vegetable and animal fat shortenings, which had been analyzed previously for their physical and textural characteristics, were analyzed also for their chemical composition. The fatty acid and triglyceride composition of the solids were calculated by analyzing the composition of the original product and the liquid phase, and by determination of the solid fat content (SFC) of the fat. The solids were also isolated by isopropanol (IP) separation, and the high melting glycerides (HMG) by acetone crystallization at 15°C. There was not much difference in total saturates andtrans content between vegetable and animal fat shortenings. Changing formulations from soy-palm to soy-cottonseed does not change the total saturates plustrans content. The solids of the vegetable shortenings in the β form contained about 20% of 16:0, those in the β′ form 30% or more. The animal fat shortenings were mainly in the β form, their solids contained 30% or more of 16:0. C54 triglyceride content of the solids of β vegetable shortenings (calculated and IP-separated) was >45%, that of all animal fats was <25%. Solids of animal fat shortenings contain high levels of C52. The C54 triglycerides are β-tending and should be kept low in vegetable shortening. In the HMG the C54 should not exceed 30%. This can only be achieved by incorporation of a β′ hard fat, preferably palm hard fat. Animal fat, especially lard, crystallizes in the β form because the palmitic acid in the glyceride molecule is located in the 2-position, whereas those of vegetable fats are in the 1- and 3-position.     

Chemical composition and physical properties of soft (tub) margarines sold in Malaysia

Seven samples of domestic and imported Malaysian tub margarines were analyzed for their fatty acid and triglyceride (carbon number) composition, solid fat content, dropping and softening points, crystallization temperature, polymorphic form, color, and textural attributes. Domestic margarines were formulated from palm oil or palm olein and palm kernel oil with a liquid oil but no hydrogenated oils. Two imported products contained hydrogenated palm oil product, which resulted in a high level of β′ crystals, whereas the domestic nonhydrogenated products contained more β than β′ crystals. Crystal habit was related to the fatty acid and triglyceride composition of the high-melting glycerides. Domestic products were firmer in texture, probably because they were formulated to be sold in a tropical climate.     

Physical properties of shortenings with low‐trans fatty acids as affected by emulsifiers and storage conditions

The quality of shortenings, such as solid fat content (SFC) and texture, strongly depends on temperature fluctuations during storage and handling. The quality of a shortening might be affected not only by temperature fluctuations but also by its chemical composition and the presence of emulsifiers. The objective of this work was to investigate the effect of emulsifier addition and storage conditions on the texture, thermal behavior and SFC of low‐trans shortenings formulated with palm oil, palm kernel oil, and vegetable oils such as sunflower and soybean oils. Several conclusions can be drawn from this study: (a) The crystallization behavior of fat blends strongly depends on the type of emulsifier used and the chemical composition of the sample; (b) the addition of emulsifiers affects not only the type of crystals formed (fractionation) but also the amount of crystals obtained (enthalpy, SFC), inducing or delaying the crystallization process; (c) emulsifiers affect the texture of the crystalline structure formed by making it softer; (d) the storage conditions affect both the texture and the SFC of the materials. This study shows that samples that are highly super‐cooled during storage become harder while samples that are less super‐cooled become softer with storage conditions.     

Physical and textural evaluation of some shortenings and margarines

Solid fat content of shortening and margarine was estimated by pulsed NMR. These values were compared with those of the melted fats using different cooling methods. Solid fat content of shortenings measured at 10 and 20 C followed the same trend as those measured on the melted fat tempered at 30 C. Solid fat content of margarines followed the same trend as those measured on the nontempered fats. Softening points of the products were similar to the dropping points of the fats, as were the temperatures of the DSC major melting peaks. Compression tests of cylindrical samples provided more information about textural characteristics of the products than one penetration tests.     

Physical Properties of <Emphasis Type="Italic">trans</Emphasis>-Free Bakery Shortening Produced by Lipase-Catalyzed Interesterification

Lipase-catalyzed interesterified solid fat was produced with fully hydrogenated soybean oil (FHSBO), and rapeseed oil (RSO) and palm stearin (PS) in a weight ratio of 15:20:65, 15:40:45 and 15:50:35. The interesterified fats contained palmitic (27.8–44.6%), stearic (15.6–16.2%), oleic (27.5–36.5%) and linoleic acids (8.0–13.5%). After interesterification of the blends, the physical properties of the products changed and showed lower melting points and solid fat contents, different melting and crystallization behaviors as well as the formation of more stable crystals. The produced interesterified fats (FHSBO:RSO:PS 15:20:65, 15:40:45 and 15:50:35 blends) contained desirable crystal polymorphism (β′ form) as determined by X-ray diffraction spectroscopy, a long plastic range with solid fat content of 51–63% at 10 °C to 4–12% at 40 °C, and melting points of 39 (15:50:35), 42 (15:50:45) and 45 °C (15:20:65). However, a reduction in tocopherols (α and γ) content and a reduced oxidative stability were observed in the interesterified fats. The physical properties of the interesterifed fats were influenced by the amount of PS, resulting in more hardness and higher solid fat contents for 15:20:65 than 15:40:45 and 15:50:35 blends. The present study suggested that the produced interesterified fats containing trans-free fatty acids could be used as alternatives to hydrogenated types of bakery shortenings.     

<Emphasis Type="Italic">Trans</Emphasis>-Free Plastic Shortenings Prepared with Palm Stearin and Rice Bran Oil Structured Lipid

Rice bran oil structured lipid (RBOSL) was produced from rice bran oil (RBO) and the medium chain fatty acid (MCFA), caprylic acid, with Lipozyme RM IM as biocatalyst. RBOSL and RBO were mixed with palm stearin (PS) in ratios of 30:70, 40:60, 50:50, 60:40 and 70:30 v/v (RBOSL to PS) to formulate trans-free shortenings. Fatty acid profiles, solid fat content (SFC), melting and crystallization curves and crystal morphology were determined. The content of caprylic acid in shortening blends with RBOSL ranged from 9.92 to 22.14 mol%. Shortening blends containing 30:70 and 60:40 RBOSL or RBO and PS had fatty acid profiles similar to a commercial shortening (CS). SFCs for blends were within the desired range for CS of 10–50% at 10–40 °C. Shortening blends containing higher amounts of RBOSL or RBO had melting and crystallization curves similar to CS. All shortening blends contained primarily β′ crystals. RBOSL blended with PS was comparable to RBO in producing shortenings with fatty acid profiles, SFC, melting and crystallization profiles and crystal morphologies that were similar. RBOSL blended with PS can possibly provide healthier alternative to some oils currently blended with PS and commercial shortening to produce trans-free shortening because of the health benefits of the MCFA in RBOSL.     

Comparison of lipase-transesterified blend with some commercial solid frying shortenings in Malaysia

A transesterified experimental solid frying shortening was prepared from a palm stearin/palm kernel olein blend at 1∶1 ratio (by weight) by using Rhizomucor miehei lipase at 60°C for 6 h. The fatty acid (FA) and triacylglycerol compositions, polymorphic forms, melting and cooling characteristics, slip melting point (SMP), and solid fat content (SFC) of the transesterified blend were then compared with five commercial solid frying shortenings (three domestic and two imported) found in Malaysia. All the domestic shortenings contained nonhydrogenated palm oil or palm olein and palm stearin as the hard stock, whereas the imported frying shortenings were formulated from soybean oil and cottonseed oil and contained high level of β′ crystals. Trans FA were also found in these samples. The lipase-transesterified blend was found to be more β′-tending than the domestic samples. The SMP of the transesterified blend (47.0°C) fell within the range of the domestic samples (37.8–49.7°C) but was higher than the imported ones (42.3–43.0°C). All samples exhibited similar differential scanning calorimetry cooling profiles, with a narrow peak at the higher temperatures and a broad peak at the lower temperatures, even though their heating thermograms were quite different. Imported samples had flatter SFC curves than both the experimental and domestic samples. The domestic samples were found to have better workability or plasticity at higher temperatures than the imported ones, probably because they were formulated for a tropical climate.     

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

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

Zero‐Trans Cake Shortening: Formulation and Characterization of Physicochemical,Rheological, and Textural Properties

Cake shortening is an important ingredient that imparts taste and texture in the cake as the final product. Hydrogenated shortenings contain high amounts of trans fatty acids, which is considered a risk factor for obesity, cancers, and cardiovascular diseases. In this research, chemically interesterified blends of canola oil (CO) and palm stearin (PS) were recruited in order to formulate zero‐trans shortening, specifically for cake application. The optimization of shortening formulation was performed by Design‐Expert software, considering melting, congelation, textural, and rheological properties of cake shortening as responses. The formulated shortening in the weight ratio of 66.41:33.58 (PS:CO) (%, w/w) was analyzed and compared with two commercial cake shortenings in terms of fatty acid and triacylglycerol composition, slip melting point (SMP), solid fat content (SFC), and rheological and textural properties. The results showed that the formulated zero‐trans cake shortening with 0.2% trans, 47.2% saturated fatty acids, SMP of 40.9 °C, SFC of 10.51% at 37 °C, firmness of 1522.5 g, and linear viscoelastic range of 0.035% had the most acceptable criteria among cake‐shortening samples. The findings of this study offer insights into the relationship between shortening functionality and physicochemical properties and serve as a base for future studies on zero‐trans shortenings formulation.     

Polymorphic behavior of some fully hydrogenated oils and their mixtures with liquid oil

Fully hydrogenated soybean oil, beef fat, rapeseed oil, a rapeseed, palm and soybean oil blend, cottonseed oil and palm oil were characterized by fatty acid composition, glyceride carbon number and partial glyceride content, as well as melting and crystallization properties. The latter were established by differential scanning calorimetry. Polymorphic behavior was analyzed by X-ray diffraction of the products in the flake or granulated form and when freshly crystallized from a melt. The hard fats were dissolved in canola oil at levels of 20, 50 and 80% and crystallized from the melt. Palm oil had the lowest crystallization temperature and the lowest melting temperature; rapessed had the highest crystallization temperature and soybean the highest melting temperature. All of the hard fats crystallized initially in the =00 form. When diluted with canola oil, only palm oil was able to maintain β′ stability.     

Physicochemical Properties of Palm Oil-Based Puff Pastry Model Margarines Related to Their Baking Performance in Long-Term Storage

Developing trans-free alternative fat solutions suitable for specific applications remains a challenge in edible fats and other domains. This is particularly true for palm oil-based puff pastry margarines, which suffer from post crystallization problems, leading to dramatic loss of functionality. This research is aimed at investigating the influence of triacylglycerol (TAG) compositions of palm oil-based puff pastry margarines on the physical properties of the fat crystal network, which determine the functionality of such products. Three model puff pastry margarines are produced at pilot scale under the same crystallization conditions. They share the same fatty acid composition and close solid fat content (SFC) profiles, whereas the proportions of major TAG (tripalmitoylglycerol (PPP), 1,3-di-palmitoyl-2-oleoylglycerol (POP), 1,2-di-palmitoyl-3-oleoylglycerol (PPO), 1,2-dioleoyl-3-palmitoylglycerol (POO)) are different. Polymorphism, melting profile, hardness, microscopic structures, and baking performance (puffing effect) of the model fats are examined during a period of 6 months. The following results are obtained: 1) The TAG composition significantly influences the post crystallization processes occurring in palm oil-based margarines. 2) High amounts of POP show negative influences. 3) The proportions of POP, PPO, and PPP should be carefully balanced to prevent detrimental crystal network rearrangements, leading to textural modifications (hardness increase) and significant reduction in baking performance. Practical Applications : The results presented in this work could be helpful for edible fat products developers, especially for roll-in fat applications. This research provides an overview of the relevant properties to study for the assessment of puff pastry margarine functionality. It also highlights the importance of ensuring long-term stability of palm oil-based fat products. Finally, it emphasizes that certain combinations of fat materials should be avoided to maintain the quality of palm oil-based puff pastry margarines.     

Application of palm olein in the production of zero‐trans Iranian vanaspati through enzymatic interesterification

The utilization of palm olein in the production of zero‐trans Iranian vanaspati through enzymatic interesterification was studied. Vanaspati fat was made from ternary blends of palm olein (POL), low‐erucic acid rapeseed oil (RSO) and sunflower oil (SFO) through direct interesterification of the blends or by blending interesterified POL with RSO and SFO. The slip melting point (SMP), the solid fat content (SFC) at 10–40 °C, the carbon number (CN) triacylglycerol (TAG) composition, the induction period (IP) of oxidation at 120 °C (IP₁₂₀) and the IP of crystallization at 20 °C of the final products and non‐interesterified blends were evaluated. Results indicated that all the final products had higher SMP, SFC, IP of crystallization and CN 48 TAG (trisaturated TAG), and lower IP₁₂₀, than their non‐interesterified blends. However, SMP, SFC, IP₁₂₀, IP of crystallization and CN 48 TAG were higher for fats prepared by blending interesterified POL with RSO and SFO. A comparison between the SFC at 20–30 °C of the final products and those of a commercial low‐trans Iranian vanaspati showed that the least saturated fatty acid content necessary to achieve a zero‐trans fat suitable for use as Iranian vanaspati was 37.2% for directly interesterified blends and 28.8% for fats prepared by blending interesterified POL with liquid oils.     

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.     

Trans-free bakery shortenings from mango kernel and mahua fats by fractionation and blending

Bakery shortenings prepared by hydrogenation contain high levels of trans fatty acids, which are considered to be risk factors for cardiovascular disease. The shortenings prepared from maogo kernel and mahua fats have no trans fatty acids. Mahua fat was fractionated by dry fractionation to obtain a high-melting fraction (10% yield, Mh1). Mango fat was fractionated by two-stage solvent fractionation, separating about 15% high-melting fraction (Mk1) in the first stage, followed by 40% stearin (Mk2) in the second stage. The formulation containing 80% Mh1 and 20% of mango middle stearin fraction (Mk2) showed melting characteristics and onset and enthalpy of crystallization similar to those of commercial hydrogenated shortenings designed for cakes and biscuits. The formulation suitable for puff pastry shortening was prepared by blending 50% mango 1st stearin (Mk1) and 50% mahua fat with addition of 5–7% of fully hydrogenated vegetable oil. The formulations having melting characteristics similar to those of commercial cake and biscuit shortenings were also prepared by blending 40% mango fat and 60% mahua fat with 5–7% incorporation of fully hydrogenated peanut oil. However, these formulations showed delayed transition to the stable forms compared to those of commercial samples. Fatty acid composition revealed that commercial hydrogenated shortenings consisted of 18–29% trans oleic acid, whereas the formulations we prepared did not contain any trans acids. The iodine values of commercial samples were 57–58, whereas the value for the formulations prepared were 47–53. The consistency of the prepared samples as measured by cone penetrometer was slightly harder than commercial samples. These studies showed that it is possible to prepare bakery shortenings with no trans fatty acids by using mango and mahua fats and their fractions.     

Physical properties of Pseudomonas and Rhizomucor miehei lipase-catalyzed transesterified blends of palm stearin:palm kernel olein

The physical properties of Pseudomonas and Rhizomucor miehei lipase-catalyzed transesterified blends of palm stearin:palm kernel olein (PS:PKO), ranging from 40% palm stearin to 80% palm stearin in 10% increments, were analyzed for their slip melting points (SMP), solid fat content (SFC), melting thermograms, and polymorphic forms. The Pseudomonas lipase caused a greater decrease in SMP (15°C) in the PS:PKO (40:60) blend than the R. miehei lipase (10.5°C). Generally, all transesterified blends had lower SMP than their unreacted blends. Pseudomonas lipase-catalyzed blends at 40:60 and 50:50 ratio also showed complete melting at 37°C and 40°C, respectively, whereas for the R. miehei lipase-catalyzed 40:60 blend, a residual SFC of 3.9% was observed at 40°C. Randomization of fatty acids by Pseudomonas lipase also led to a greater decrease in SFC than the rearrangement of fatty acids by R. miehei lipase. Differential scanning calorimetry results confirmed this observation. Pseudomonas lipase also successfully changed the polymorphic forms of the unreacted blends from a predominantly β form to that of an exclusively β′ form. Both β and β′ forms existed in the R. miehei lipase-catalyzed reaction blends, with β′ being the dominant form.     

Zero-<Emphasis Type="Italic">trans</Emphasis> shortening using palm stearin and rice bran oil

Several pilot-scale trials reported in this paper, using palm stearin-rice bran oil (PS-RBO) blends, obviously did not contain trans FA (TFA), whereas the commercial products were found to contain 18–27% TFA. The effects of processing conditions such as rate of agitation, crystallization temperature, and composition of the blends on the crystal structure of shortenings were studied. The products were evaluated for their physicochemical characteristics using DSC, X-ray diffraction (XRD), HPLC, and FTIR techniques. The formulation containing 50% PS and 50% RBO showed melting and cooling characteristics similar to those of hydrogenated commercial “vanaspati” samples. Analysis of the FA composition revealed that the formulated shortenings contained 15–19% C_18∶2 PUFA. Tocopherol and tocotrienol contents of the experimental shortenings were in the range of 850–1000 ppm with oryzanol content up to 0.6%. XRD studies demonstrated that the crystal form in the shortenings was predominantly the most stable β′ form, and there was less of the undesirable β form.     

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.     

On the formation of granular crystals in fat blends containing palm oil

The use of palm oil for plastic fats has encountered serious difficulty due to its crystallization properties, one of which is the formation of granular crystals. The granular crystals cause sandy teste and inhomogeneity of fat crystal morphology of end products. In the present study, we analyzed the formation process of these granular crystals. Chemical and physical analyses for triacylglycerol (TAG) compositions, polymorphism and melting points of the granular crystals led to the conclusion that the granular crystals are of the most stable polymorph, β₁, of POP (1,3-dipalmitoyl 2-oleoyl glycerol) with triple chainlength fat blend consisting of POP and reapeseed oil. The following characteristics of β₁ polymorph of POP contribute to the formation of granular crystals in fat blends containing palm oil: (i) β₁ reveals well-defined plate-like crystal morphology, which grows easily into the bulky granular from; (ii) the triple chainlength structure of POP has a tendency to segregate and does not from a solid solution together with other TAGs.     

Phase Behavior of Palm Oil in Blends with Palm-Based Diacylglycerol

Phase behavior of palm oil (PO) in blends with different concentrations (10% intervals) of palm-based diacylglycerol oil (PO-DAG) was studied using the iso-solid diagram, solid fat content (SFC) with the hardness thermal protocol, DSC melting and crystallization curves, X-ray diffraction curves, and texture analysis (hardness). Minor eutectic effects were observed at around 20–50% PO-DAG in 20–50% SFC iso-lines. The phase behavior predicted by the iso-solid diagram as well as SFC with the hardness thermal protocol did not account for hardness variations observed between PO and PO blends with 10–40% PO-DAG. Nevertheless, the latter could be attributed to the corresponding DSC data as well as crystal polymorphism. However, as the concentration of PO-DAG increased from 40% to 100%, iso-line temperatures, SFC with the hardness thermal protocol, and also hardness were found to steadily increase. PO-DAG at 10% concentration was found to have a β′-stabilizing effect on the polymorphism of PO, while a β-tending effect was observed as the concentration of PO-DAG increased from 10% to 90%.     

Physico-chemical properties and performance of high oleic and palm-based shortenings

Solid fat from fractionation of palm-based products was converted into cake shortening at different processing conditions. High oleic palm stearin with an oleic content of 48.2 % was obtained from fractionation of high oleic palm oil which was produced locally. Palm product was blended with different soft oils at pre-determined ratio and further fractionated to obtain the solid fractions. These fractions were then converted into cake shortenings named as high oleic, N1 and N2 blends. The physico-chemical properties of the experimental shortenings were compared with those of control shortenings in terms of fatty acid composition (FAC), iodine value (IV), slip melting point (SMP), solid fat content (SFC) and polymorphic forms. Unlike the imported commercial shortenings as reported by other studies and the control, experimental shortenings were trans-free. The SMP and SFC of experimental samples, except for the N2 sample, fell within the ranges of commercial and control shortenings. The IV was higher than those of domestic shortenings but lower when compared to imported and control shortenings. They were also observed to be beta tending even though a mixture of beta and beta' was observed in the samples after 3 months of storage. The shortenings were also used in the making of pound cake and sensory evaluation showed the good performance of high oleic sample as compared to the other shortenings.