Enzymatic interesterification of palm stearin and palm kernel olein

C: Food Chemistry

Enzymatic Interesterification of Palm Stearin with Cinnamomum camphora Seed Oil to Produce Zero-trans Medium-Chain Triacylglycerols-Enriched Plastic Fat Liang Tang, Jiang-ning Hu, Xue-mei Zhu, Li-ping Luo, Lin Lei, Ze-yuan Deng, and Ki-Teak Lee

It is known that Cinnamomum camphora seed oil (CCSO) is rich in medium-chain fatty acids (MCFAs) or medium-chain triacylglycerols (MCTs). The purpose of the present study was to produce zero-trans MCTs-enriched plastic fat from a lipid mixture (500 g) of palm stearin (PS) and CCSO at 3 weight ratios (PS:CCSO 60:40, 70:30, 80:20, wt/wt) by using lipase (Lipozyme TL IM, 10% of total substrate) as a catalyst at 65 ◦ C for 8 h. The major fatty acids of the products were palmitic acid (C16:0, 42.68% to 53.42%), oleic acid (C18:1, 22.41% to 23.46%), and MCFAs (8.67% to 18.73%). Alpha-tocopherol (0.48 to 2.51 mg/100 g), γ -tocopherol (1.70 to 3.88 mg/100 g), and δ-tocopherol (2.08 to 3.95 mg/100 g) were detected in the interesterified products. The physical properties including solid fat content (SFC), slip melting point (SMP), and crystal polymorphism of the products were evaluated for possible application in shortening or margarine. Results showed that the SFCs of interesterified products at 25 ◦ C were 9% (60:40, PS:CCSO), 18.50% (70:30, PS:CCSO), and 29.2% (80:20, PS:CCSO), respectively. The β crystal form was found in most of the interesterified products. Furthermore, no trans fatty acids were detected in the products. Such zero-trans MCT-enriched fats may have a potential functionality for shortenings and margarines which may become a new type of nutritional plastic fat for daily diet. Abstract:

Keywords: Cinnamomum camphora seed oil, interesterification, medium-chain triglycerides, plastic fat, structured lipids

Introduction Plastic fat (that is, margarine or shortening) is one of the highest economic sources of dietary semisolid fat. Commercially, plastic fat is prepared by partial hydrogenation of vegetable oils to obtain the desirable chemical and physical characteristics (Ghotra and others 2002). It is well known that hydrogenation processes can raise melting point, resulting in hardening of the oil (Zeitoun and others 1993; Remig and others 2010). Meanwhile, it also leads to the formation of trans fatty acids (TFAs). Up to 50% TFAs were generated in partially hydrogenated fats depending on the degree of hydrogenation (Aro and others 1998; Tekin and others 2002). Recently, studies revealed that TFAs in foods are unfavorably associated with cardiovascular disease (Ascherio and others 1999). TFAs can change plasma lipid levels, calcify cells, and cause inflammation of the arteries, which are known risk factors in heart disease (Kummerow and others 1999). Also trans fats inhibit cyclooxygenase (COX-2) activities, an enzyme which converts arachidonic acid to an eicosanoid that is necessary for

MS 20111258 Submitted 10/16/2011, Accepted 1/12/2012. Authors Tang, Hu, Zhu, Luo, Lei, and Deng are with State Key Laboratory of Food Science and Technology, Inst. for Advanced Study, Nanchang Univ., Nanchang, Jiangxi 330047, China. Authors Hu and Zhu are also with College of Life Science & Food Engineering, Nanchang Univ., Nanchang, JiangXi 330047, China. Author Lee is with Dept. of Food Science and Technology, Chungnam Natl. Univ., Daejeon 305-764, South Korea. Direct inquiries to authors Hu and Deng (E-mail: [email protected], [email protected]).

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the prevention of blood clots in the arteries and veins (Li and others 2005). As a result of the detrimental health effects of TFAs, many European countries, including Denmark, have banned the use of trans fat in food formulations. The U.S. Food and Drug Administration (FDA) also ruled that the amount of trans fats in a food item must be stated on the label; food item could be labeled 0% trans if they contain less than 0.5 g trans fats per serving. Hence, there is an urgent need to develop new technique to reduce TFAs content in plastic fat (Jianmin and others 2011). Many studies have shown that enzymatic interesterification could be a feasible way of producing low-trans plastic fat with advantages of mild conditions, low side products and region specificity, which can avoid the increase of TFAs content effectively (Xu 2000; Hu and others 2009; Shin and others 2010;). The interesterification reactions between a high melting fat and liquid oil lead to exchange of fatty acids within and between triacylglycerols (TAGs) resulting in new altered TAG molecules, and can produce semisolid fats with desirable tenderness, texture, mouthfeel, and extended shelf life (Kennedy 1991). Cinnamomum camphora (lauraceae) is widely distributed in Jiang Xi Province, China. In a previous study, we reported that the seed oil extracted from C. camphora (lauraceae) had a unique fatty acid profile (Hu and others 2011). Up to 94% of total fatty acids were medium-chain fatty acids (MCFAs) (capric acid, C10:0, 53.27%; lauric acid, C12:0, 39.93%). It is well known that the digestion, absorption, and metabolism of medium-chain triacylglycerol (MCT) oil are different from that of the oil composed of long-chain triacylglycerol (LCT) (Takeuchi and others 2008). MCTs that consist R C 2012 Institute of Food Technologists doi: 10.1111/j.1750-3841.2012.02637.x

Further reproduction without permission is prohibited

of 3 MCFAs on the skeleton of glycerol can be rapidly hydrolyzed in the gastrointestinal tract, and the resulting MCFAs are directly transported via the portal system and rapidly oxidized in the liver to provide quick energy (Papamandjaris and others 1998). In clinic experiments, MCT oil such as coconut oil was found to lower body fat deposition, enhance survival rate, and reduce tendency to form blood clots (Bruce 2006). Besides, recent research efforts have also tried to use MCT oil to produce commercial margarine because such diet can provide several health benefits from MCT (Zhang and others 2000; Jeyarani and others 2009). Unfortunately, to our knowledge, until now there is no information about C. camphora seed oil (CCSO) in food application. Meanwhile, the environmental problem caused by the falling of C. camphora seed is troublesome for the government and residents. Considering the high amount of MCFAs in CCSO, our interest in this study was to examine the possibility of using CCSO and palm stearin (PS) with different weight ratios for the formulation of trans-free plastic fat through enzymatic interesterification. After the reaction, the physical properties (fatty acids profile, TAG composition, solid fat content, melting points, polymorphic forms, and macrostructure) of the interesterified products and their physical blends were comparatively studied for consideration of their possible use for margarine and shortening.

Materials and Methods Materials and chemicals PS was purchased from Zi. B. J. Corp. (Guangzhou, China). C. camphora seeds were collected from Nanchang Univ. campus in Jiangxi province, China. The seeds were vacuum-dried to a constant weight, and then ground into pieces by a blender. Lipozyme TL IM from Thermomyces lanuginosus was purchased from Novozymes A/S (Bagsvaerd, Denmark). The specific activity of Lipozyme TL IM was 181 IU/g, having 0.54 g/mL bulk density, and 0.3 to 1.0 mm particle diameter. Carbon dioxide (99.9%) was purchased from Wanli Gas Corp. (Nanchang, China). A number of 463 standard fatty acid methyl esters (FAME) spiked with a mixture of 4 positional conjugated linoleic acid isomers (#UC-59M) were obtained from Nu-Chek Prep Inc. (Elysian, Minn., U.S.A.). All reagents were of analytical reagent grade. Tocopherols (α, γ , and δ) standards were purchased from Sigma Chemical Corp. (St. Louis, Mo., U.S.A.). Extract and refining of CCSO All SC-CO2 extraction trials were carried out in a Nantong supercritical fluid extraction system (1 L sample capacity) (Model HA120-50-01, Jiangsu, China). The schematic flow diagram was described in detail in a previous study (Sánchez and others 2009). Briefly, samples of 50.00 g camphor seeds powder were weighed accurately and placed into the stainless steel extraction vessel. The CO2 flow rate was maintained at about 45 L/h during extraction. The extraction pressure, temperature, and time were 21.16 MPa, 45.67 ◦ C, and 2.38 h, respectively. After the extraction, the extraction vessel was depressurized and oil was collected from the separation vessel. The extracted CCSO was stored at −20 ◦ C for further use. Interesterification In preliminary experiments, small-scale reactions (10 g mixture) in a shaking water bath were performed to obtain optimal reaction conditions for producing plastic fat. Then, a scaled-up reaction in a batch-type reactor was carried out with a lipid mixture

(500 g) of PS and CCSO with 3 weight ratios (60:40, 70:30, and 80:20, PS:CCSO), using lipase (Lipozyme TL IM, 10 wt.%) as a biocatalyst. The blended substrates were reacted at 65 ◦ C for 8 h and the mixing speed was set at 500 rpm. After the reaction, TL IM lipases were separated from the mixture. To remove free fatty acids, hexane (500 mL) and phenolphthalein solution (1 mL) were added, followed by titration with 0.5 N KOH in 95% ethanol until pink color appeared. The sample was washed several times with warm water until the pink color vanished. The organic layer was passed through an anhydrous sodium sulfate column and then completely evaporated under nitrogen flow at 40 ◦ C.

Fatty acid composition The fatty acid composition was determined by gas chromatography with slight modification (Zhu and others 2011). Briefly, the aliquots (1 μL) of the methylated fatty acids extracts were injected into a gas chromatograph equipped with an auto injector and a flame-ionization detector (Model 6890 N, Agilent Technologies, Santa Clara, CA. U.S.A.) using a fused-silica capillary column (CP-Sil 88, 100 m × 0.25 mm× 0.2 μm i.d., Chrompack, Middelburg, Netherlands). The initial temperature of the program was 45 ◦ C held for 4 min, and then increased at a rate of 13 ◦ C/min to 175 ◦ C, and held for 27 min. The oven temperature was then further increased to 215 ◦ C at a rate of 4 ◦ C/min and held for 35 min. Fatty acids compositions were identified by comparison with relative retention times of FAME standards. Duplicate analyses were performed. Slip melting point (SMP) and solid fat content (SFC) determination The SMPs of the samples were determined according to AOCS Official Method Cc. 3.25 (American Oil Chemist’s Society 1990). The SFC was measured by low resolution pulsed NMR using Maran SFC (MQC, Oxford, U.K.) according to AOCS (1989) Official Method Cd 16b-93. A constant resonance frequency of 20 MHz was used with an f -factor of 1.626, which was determined by measuring a set of predefined artificial standards that were designed to replicate approximately 0%, 30%, and 70%. The fat was melted at 80 ◦ C and placed in an ice-bath (0 ◦ C) for 60 min before the first SFC measurement. The samples were conditioned for 30 min at the desired temperature, followed by the measurements carried out at 10, 20, 25, 30, 35, 40, 45, 50, and 55 ◦ C. High-performance liquid chromatography (HPLC) The separation of triacylglycerols (TAGs) species from PS and CCSO was conducted by reversed-phase HPLC based on previous report (Raquel Costales 2009). Minor practical adjustments of the mobile phase composition and flow rate were made in order to improve TAGs separation in compliance with the above-mentioned method. The Agilent 1100 series HPLC system consisted of HPLC pump (Agilent) with an evaporative light-scattering detector (Alltech 2000ES, Alltech, U.S.A.) operating at 55 ◦ C. Samples were dissolved in methanol. Twenty microliters of filtered sample were injected on A Nova-Pak C18 column (150 mm × 3.9 mm, Waters, Milford, Mass., U.S.A.). Elution solvent consisted of (A) acetonitrile and (B) isopropanol/hexane (1:1, v/v) at a flow rate of 1.8 mL/min with the following profiles: 0 to 20 min 30% B; 21 to 36 min 60% B; 37 to 40 min, 100% B, and then back to the initial flow rate. The chromatograms were processed on Empower software. Individual peaks were identified by comparing the retention time and trending of peak with those standard references. The values are the means of 3 analyses, reported with standard deviations. The Vol. 77, Nr. 4, 2012 r Journal of Food Science C455

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Zero-trans MCTs-enriched plastic fat from PS and CCSO . . .


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equivalent carbon number (ECN) was used to predict the elution (Agilent 1100 series) coupled to a fluorimetric detector perorder. ECN = CN − 2DB, where CN is the total carbon number forming at an excitation wavelength of 295 nm and an emission and DB is the total number of double bonds on the fatty acids. wavelength of 325 nm. The column was Hypersil ODS2 (5 μm, 4.6 mm × 150 mm). The mobile phase was methanol/water (98/2, v/v), and the flow rate was 0.8 mL/min. The correspondPolymorphism by X-ray diffraction spectroscopy Each melted sample was placed on a rectangular plastic mould ing standards (α-, γ -, δ-tocopherol) for identification and quanand tempered at 24 ◦ C for 24 h. Polymorphic forms of the samples tification were prepared in hexane solution. (Hu and others 2011) were determined by X-ray diffraction, using a D8-focus (Bruker Co., Karlsruhe, Baden-Württemberg, Germany) with a fine cop- Statistical analysis per X-ray tube, operating at 40 kV and 35 mA (Adhikari and Statistical Analysis System software (SAS 2000, Cary, NC, others 2009). U.S.A) was used to perform statistical analysis. Duncan’s multiple range tests were performed to determine the significance of difference at P < 0.05. Analysis of tocopherols One gram of sample was weighed into a flask and diluted to 10 mL with hexane. After filtered with 0.45 μm nylon syringe Results and Discussion filter, 3 μL of sample was injected to the HPLC equipment

Fatty acid profile The fatty acid compositions of CCSO, PS, physical blends, and Table 1–Fatty acids composition (area%) of PS, CCSO, the phys- the interesterified products are presented in Table 1. The major ical blends and the interesterified products. fatty acids of CCSO were MCFAs including capric acid (C10:0, Interesterified 53.96%) and lauric acid (C12:0, 37.70%). PS contained a high Physical blend product amount of palmitic acid and oleic acid which were the most abun(PS:CCSO) (PS:CCSO) dant fatty acids in PS (62.96% and 25.55%, respectively). ComPS CCSO 60:40 70:30 80:20 60:40 70:30 80:20 pared to that of PS (0.12%), MCFAs of interesterified products and physical blends were much higher (17.93% to 35.71% and 17.82% C8:0 NDa 0.36 0.14 0.09 0.07 0.11 0.08 0.06 C10:0 0.00 53.96 21.15 16.30 10.76 21.26 15.94 10.14 to 35.73%, respectively) with no TFAs. The fatty acid composition C12:0 0.11 37.70 14.45 11.45 6.99 14.34 11.25 7.73 of interesterified products and physical blends had no significant C14:0 1.32 1.08 1.27 1.27 1.30 1.22 1.25 1.31 change as interesterification catalyses exchange of fatty acids beC16:0 62.96 0.89 38.78 44.02 50.35 38.85 45.12 50.59 tween and within the TAGs molecules and thereby all the fatty C18:0 4.91 0.23 3.07 3.74 3.98 3.39 3.67 4.06 9cC18:1 25.55 4.80 17.34 18.66 21.81 17.37 17.92 21.15 acids get distributed evenly (Mayamol and others 2007). Karabulut 9c12cC18:2 5.06 0.87 3.71 4.34 4.64 3.26 4.62 4.77 and Tarun (2006) have previously reported the contents of MCT C18:3n-3 0.09 0.11 0.09 0.13 0.10 0.20 0.15 0.19 (0.2% to 2%) and TFAs (2.0% to 16.5%) in several commercial 0.12 92.02 35.73 27.84 17.82 35.71 27.27 17.93 MCFA shortenings. Our high-MCT products with no TFAs as demonSFA 69.31 94.22 78.86 76.87 73.45 79.17 77.31 73.89 strated above may thus be potentially useful for the food industries 30.69 5.77 21.15 23.14 26.55 20.82 22.69 26.12 UFA TFA ND ND ND ND ND ND ND ND and desirable for the consumers due to the unique property of a Not detected. MCT. Table 2–Triacylglycerol (TAG) composition (area%) of PS, CCSO, the physical blends, and interesterified products. Physical blends(PS:CCSO)

ECNa 30 32 34 36 38 40 40 42 42 42 44 44 46 46 46 48 48 48 48 50 50 Unknown

TAG CCC LaCC/CLaC MCC/LaLaC LaLaLa/OCC MLaLa,/MMC MMLa/PMC/ SLaC/PLaLa LLLn/LLnL MMM/SMC/PPC/PMLa/SLaLa PLLn/PLnL/LnPL LLL LLO/LOL PLL/LPL OLO/LOO PLO/POL/OPL PLP/PPL OOO POO/OPO POP/PPO PPP POS PPS/PSP

PS b

ND ND ND ND ND ND ND ND ND ND ND ND ND 1.88 2.53 0.45 11.66 43.00 35.26 1.07 1.83 2.32

Interesterified products(PS:CCSO)

CCSO

80:20

70:30

60:40

80:20

70:30

60:40

3.59 88.43 7.98 ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND 0.00

0.51 14.39 1.01 ND ND ND ND ND ND ND ND ND ND 1.12 1.72 0.30 9.73 35.85 28.31 2.47 2.82 1.77



ND 1.09 0.41 1.92 4.51 0.21 1.01 0.49 ND 6.80 9.09 3.49 4.37 1.34 2.49 0.63 7.49 29.71 16.52 1.46 1.17 5.58

ND 1.46 0.46 1.48 2.45 1.21 2.53 1.02 3.56 11.25 15.04 5.78 6.75 1.21 0.71 0.81 6.11 21.41 8.04 1.09 0.59 6.01

ND 2.34 0.78 1.15 2.00 1.18 5.39 2.02 6.96 13.54 15.89 6.02 7.23 0.87 0.92 0.76 3.77 11.25 6.14 0.91 0.89 12.66

Abbreviations: Ca = caprylic acid; C = capric acid; La = lauric acid; M = myristic acid; P = palmitic acid; S = stearic acid; O = oleic acid. L = linoleic acid; Ln = linolenic acid. a Equivalent carbon number (ECN) = CN − 2DB, where CN is carbon number of TAG and DB is total number of double bonds in TAG. b ND = not detected.

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Triacylglycerol analysis The TAGs composition of oils is rather complex. Therefore, there is no perfect analytical technique to separate all the TAG species in the fats and oils clearly (Adhikari and others 2009). The TAGs compositions of PS, CCSO, physical blends, and interesterified products are shown in Table 2. The results showed that substantial changes in TAGs species occurred after the interesterification reaction (Figure 1). The predominant TAGs of PS were POP/PPO (43.00%), PPP (35.26%), POO/OPO (11.66%),

PLP/PPL (2.53%), and PLO/POL/OPL (1.88%), whereas CCSO contained appreciable amounts of LaCC/CLaC (88.43%), LaLaC/MCC (7.98%), and CCC (3.59%). Physical blend (that is, 60:40, PS:CCSO) also contained high levels of LaCC/CLaC (44.68%), POP/PPO (20.07%), PPP (18.76%) while other TAG species were also observed. Compared to the physical blends, some TAGs of interesterified products were increased (that is, LaLaLa, MLaLa/MMC/PLaC/SCC, MMLa/PMC/ SLaC/PLaLa, LLLn, MMM/SMC/PPC/PMLa/SLaLa, PLLn/

Figure 1–TAG of PS, CCSO, physical blend (70:30, PS:CCSO), and interesterified product (70:30, PS:CCSO) (peak top number represents ECN of the triaclyglycerol group).

Table 3–Contents of tocopherol (mg/100 g) and slip melting point (SMP) of PS, CCSO, physical blends, and interesterified products. Physical blend (PS:CCSO) α-Tocopherol γ -Tocopherol δ-Tocopherol Total SMP (◦ C)

PS

CCSO

2.74 ± 0.3b 0.25 ± 0.0g 1.29 ± 0.2d 4.28 ± 0.5e 52.10

7.13 ± 0.8a 20.76 ± 1.4a 8.22 ± 1.0a 36.12 ± 3.2a 16.02

80:20 2.34 ± 0.4b 4.35 ± 0.3d 2.30 ± 0.3c,d 8.99 ± 1.0c,d,e 49.80

Interesterified product (PS:CCSO)

70:30

60:40

80:20

70:30

60:40

2.62 ± 0.3b 6.40 ± 0.2c 3.29 ± 0.2b,c 12.31 ± 0.7b,c 48.00

3.44 ± 0.2b 8.45 ± 0.3b 4.03 ± 0.4b 15.92 ± 0.9b 43.05

0.48 ± 0.1c 1.70 ± 0.3f 2.08 ± 0.4c,d 4.26 ± 0.8e 28.50

0.50 ± 0.1c 2.70 ± 0.4e 2.93 ± 0.3b,c 6.14 ± 0.8d,e 31.80

2.51 ± 0.3b 3.88 ± 0.3d 3.95 ± 0.4b 10.34 ± 1.0c,d 38.50

All samples were analyzed in duplicate. a–g Values with the same letter in a row are not significantly different (P > 0.05).

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a group of major primary natural antioxidants in vegetable oils, prevent lipid peroxidation by scavenging radicals in membrane and lipoprotein particles (Esterbauer and others 1991). All the α-, γ -, δ-tocopherols were detected in all analyzed samples. CCSO (36.12 mg/100 g) showed a higher level of total tocopherols than PS (4.28 mg/100 g). α-tocopherol (0.48 to 2.51 mg/100 g), γ tocopherol (1.70 to 3.88 mg/100 g), and δ-tocopherol (2.08 to 3.95 mg/100 g) were detected in the interesterified products. Total tocopherols in the physical blends were 8.99 to 15.92 mg/100 g, while in the interesterified products were 4.26 to 10.34 mg/100 g. Compared to physical blends, the slight reduction in tocopherol Tocopherol analysis content of the interesterified products was observed, which genThe tocopherol contents in the PS, CCSO, physical blends, erally occurred during purification (that is, deacidification) and and interesterified products are shown in Table 3. Tocopherols, different processing of vegetable oils into solid fats (shortening PLnL/LnPL, LLL, LLO/LOL, PLL/LPL, and OOO) but some TAGs decreased (that is, CCC, LaCC/CLaL, MCC/LaLaC, POO/POP, POP/PPO, and PPP) after the interesterification. Meanwhile, in the interesterified products, it is clearly noticeable that the interesterified product showed an increased amount of several new types of TAG species (that is, LLL and LLO), indicating that interesterification has taken place. Bakery products, such as margarine and shortenings, require wide melting range achieved by using fats containing heterogeneous types of TAGs (Jeyarani and others 2009).

Figure 2–The solid fat content (SFC) of the physical blends (A, 60:40; B, 70:30; C, 80:20) and interesterified products (A , 60:40; B , 70:30; C , 80:20) with different ratios.

Figure 3–X-ray diffraction spectroscopy of interesterified products (A , 80:20; B , 70:30; C , 60:40) and physical blends (A, 80:20; B, 70:30; C, 60:40) with different ratios.


˚ and margarine). Such reduction of tocopherols was also reported fied product showed stronger intensities at 3.85, 4.18, or 4.30 A ˚ In the case of physical blends, strong intensities were (Senanayake and Shahidi 2002). than 4.59 A. ˚ The physical blend observed at 3.85, 4.18, or 4.30 and 4.59 A. ˚ and 23.2%, (80:20, PS:CCSO) showed 23.8% β form at 4.59 A Solid fat content and slip melting point ˚ SFC, the quantity of fat crystals in a fat or fat blend is significantly 21.3%, and 31.7% β form at 4.30, 4.18, and 3.85 A, whereas the responsible for many of their properties, such as general appear- interesterified product (80:20, PS:CCSO) demonstrated 2.5% β ˚ and 46.1%, 34.7%, and 16.7% β form at 4.30, 4.18, ance, organoleptic characters, oil exudation, and function (Dian form at 4.59 A ˚ and others 2007). Figure 2 showed SFCs of PS, CCSO, the physical and 3.85 A, respectively. During the process of interesterification, blends, and interesterified products as a function of temperature. the intensity of short spacing β form was reduced and β form was increased significantly (Figure 3). That could be caused by the reThe samples had different SFCs. The SFCs increased with increasing amounts of PS in the blends. All samples were found to have a arrangement of fatty acids in the TAGs after the interesterification wider melting range (Figure 2). At 5 ◦ C, most phases of PS were reaction. The TAGs species were increased obviously resulting in solid as shown by its SFC value. Even the temperature increased to decrease of the TAGs molecular symmetry. It was reported that the 40 ◦ C, SFC was 35.1%. In case of CCSO, SFC at 5 ◦ C was 77.5% contents of palmitic acid were 17% in β tending margarines and ◦ while most phases were liquid at 15 to 20 C (0.0% SFC). SFCs of 11% in β tending margarines (D’Souza and others 1991). In our the interesterified products (60:40, 70:30, and 80:20, PS:CCSO), study, the contents of palmitic acid in the experimental products a little lower than that of the physical blends at 30 ◦ C as shown in were from 38.78% to 50.59% and all the experimental samples Figure 2. When the temperature increased to 40 ◦ C, SFCs of the preferred the β polymorphs, suggesting that they may be suitable interesterified products decreased significantly, ranging from 0% for the production of margarines. to 3.9%. On the other hand, PS:CCSO 80:20 showed higher SFC values than other proportion in both interesterified products and Conclusion In conclusion, in the present study, the interesterified plastic fats physical blends (60:40 and 70:30, PS:CCSO) at each temperature. The result could be expected because the more addition of PS, were produced from PS and CCSO with different weight ratios of which is comparatively high melting fat, increased SFC values in 60:40, 70:30, and 80:20. The interesterified fats contained no trans the products. Meanwhile, compared to the physical blends, SMPs fatty acids, and had 17.93% to 35.71% MCFAs which have many of the interesterified products were reduced (Table 3). SMPs of health benefits. Meanwhile, desirable physical properties including the interesterified products (60:40, 70:30, and 80:20, PS:CCSO) a wide range of SFCs, SMPs, crystal polymorphs were observed were 28.5, 31.8, and 38.5 ◦ C, respectively. The changes in the in the produced fats. More β polymorphic forms were present in SFCs and SMPs of fats after interesterification were accompanied the interesterified products. The interesterified products could be by changes in the TAGs composition (Fabiana and others 2009). suitable for margarine while physical blends were more likely to In this study, the interesterified products could be suitable for be a source material of shortening according to their wide SFC margarine while physical blends were more likely to be a source range. material of shortening. Enough high melting temperature is one of the desirable properties in shortening because shortening should Acknowledgments The authors would like to thank Jiangxi Provincial Dept. of not melt quickly at baking temperature. Generally, a SFC of 15% Science and Technology, for financially supporting this research to 25% is agreeable for better creaming performance in cakes at under contract nr 2010AZX00500. the working temperature (Danthine and Deroanne 2003), which is also essential to the prevention of oiling off (Laia and others 2000). In addition, higher solids content was demonstrated in the References [AOCS] American Oil Chemist’s Society. 1989. Official methods and recommended practices physical blends, ranging from 16.3% to 24% at 40 ◦ C (Figure 2), of American Oil Chemists’ Society, 5th ed. Champaign, IL: AOCS Press. and is advantageous for use in cake manufacture as they can retain [AOCS] American Oil Chemist’s Society. 1990. Official and recommended methods of the Oil Chemist’s Society, 15th ed. Champaign, IL: AOCS Press. the air incorporated during baking (Nor and others 1992). The AroAmerican A, Amelsvoort V, Becker W, van Erp-Baart MA, Kafatos A, Leth T, van Poppel G. 1998. Trans fatty acids in dietary fats and oils from 14 European countries: the TRANSFAIR study. SFCs results suggested that the physical blends and interesterified J. Food Compos Anal 11:137–49. products might have a potential functionality for shortenings and Ascherio A, Katan MB, Stampfer MJ. 1999. Trans fatty acids and coronary heart disease. N Engl J Med 323:1994–8. margarines

Crystal polymorphism Polymorphic form is the most essential criteria and standard for the functional properties of margarine and shortenings (Reddy and Jayarani 2001). The main polymorphs of fat crystals are α, β , and β polymorphic forms (Prakash and others 2010). Each polymorph has different characteristic of which α form, very un˚ stable with the lowest melting point and short spacing at 4.15 A; β form, metastable with intermediate melting point and 2 strong ˚ as well as 3 minor short spacings short spacings at 3.80 and 4.20 A ˚ β form, very stable, highest melting point at 4.27, 3.97 and 3.71 A; ˚ (Sol´ıs and others 2005). The β form is and short spacings at 4.60 A preferred in shortenings and margarines due to its stable structure and moderate crystal sizes which allow for smooth products. The polymorphic forms of interesterified products and physical blends are shown in Figure 3 as determined by XRD. The interesteri-

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C: Food Chemistry

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Enzymatic interesterification of palm stearin and palm kernel olein

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