Effect of chemical interesterification on Some Selected Chemical Characteristics of blends of Butter and palm olein A. Khurshid *M. Nadeem1, T.N. Pasha1, M. Abdullah1 and M.A. Jabar1 1 Department of Dairy Technology, University of Veterinary and Animal Sciences, Lahore (Pakistan) *Corresponding Author: sheikhnadeem@live.com Cell #: 0313-4283954 Abstract: A study was carried out to determine the effect of chemical interesterification on some chemical characteristics of butter and palm olein blends. Butter and palm olein were mixed at different concentrations i.e. T0 (100% butter) which served as control, T1 (80% butter and 20% palm olein) T2 (60% butter and 40% palm olein) T3 (50% butter and 50% palm olein) T4 (40% butter and 60% palm olein) T5 (20% butter and 80% palm olein) T6 (100% palm olein). The effect of interesterification process on fatty acid composition, triglyceride rearrangement, melting point and free fatty acids were determined. Incorporation of 50% of palm olein to butter reduced the level of saturated fatty acids by 20% and increased mono unsaturated fatty acids by 48% and 50% the levels of poly unsaturated fatty acids and increased melting point up to 23.10C. Free fatty acids decreased in all the treatments including control. Addition of palm olein up to 50% level in butter can be used for the manufacturing of tailored fats that can be used for the manufacturing of large number of food preparations. Keywords: Butter, Palm olein, Chemical interesterification, physicochemical properties INTRODUCTION The awareness about the benefits to consume low cholesterol foods is mounting across the globe due to increased interest and consciousness in consumers for food related health disparities. The fatty acids composition of milk fat is characterized by high proportion of saturated fatty acids (60-70%), Milk fat is also known to contain certain amount of cholesterol (0.25-0.38 mg/kg) which posses many health risks Butter is a popular dairy product in this part of world and used in many food preparations. Milk fat is characterized by high percentages of saturated fatty acids. Saturated fatty acids increase the LDL cholesterol and decrease the beneficial HDL cholesterol when metabolized in the body. Palm olein is the liquid fraction obtained by fractionation of palm oil after crystallization at a controlled temperature. Palm olein has low iodine value and melting point; pure palm olein cannot be incorporated in butter. However, can be used after some modification by interesterification with others fats or oils (Aini & Miskandar, 2007, 2006). Chemical interesterification causes modifications in the properties of natural fats. This means that fatty acids are not randomly distributed in triacylglycerols of natural fats (Rodrigues & Gioielli, 2003). Chemical interesterification is less expensive and leads to a random distribution of fatty acids on the triacylglycerols (Marangoni & Rousseau, 1998). For the reason the present investigation was planed to evaluate the suitability of chemically interesterified blend of palm olein butter and appreciable quantity of mono and poly unsaturated fatty acids to prepare functional butter with increased health benefits. MATERIALS AND METHODS Materials: Butter was procured from Haleeb Foods and palm olein was obtained from United Industries Ltd. Faisalabad. The fats were stored at 0C prior to use. Sodium Methylate (Merck) was purchased from a scientific store of Lahore. The following treatments were prepared. Experimental: Palm olein was incorporated in butter at five different levels i.e. T0 (100% butter) which served as control, T1 (80% butter and 20% palm olein) T2 (60% butter and 40% palm olein) T3 (50% butter and 50% palm olein) T4 (40% butter and 60% palm olein) T5 (20% butter and 80% palm olein) T6 (100% palm olein). All the treatments were performed duplicate. Chemical interesterification: Chemical interesterification of different blends of butter and palm olein were carried out according to the method of (Sreenivasan, 1978). 500 mL of the samples were dried in a flask, under reduced pressure, fitted with a vacuum pump in a waterbath at 95 0C. The portions were mixed with 0.2% (w/w) of sodium methylate. Interesterification reaction was performed under reduced pressure at 70 0C in a 500 mL stoppered flask in a waterbath with constant agitation for one hour. To terminate the reaction, 5 mL of distilled water was added. Fatty acid composition: Fatty acid composition was determined after conversion of fatty acids into their corresponding methyl esters on a gas chromatograph by the method described by Hartman and Lago (1973). Iodine value: Iodine value was calculated from the fatty acid composition, according to the procedure described in the AOCS official method (AOCS, 1990). Melting point: Melting point was determined by the closed tube melting point method, according to the AOCS official method (AOCS,1990). Three replicates of this analysis were performed. Triacylglycerol composition: Triacylglycerol compositions of butter and palm olein (blends 1 and 7) were obtained from the literature and were used for the calculation of the blends. For interesterified blends, the 1, 2, 3 - random theory, for random interesterification, was applied. Trisaturated, disaturated–monounsaturated and monosaturated–diunsaturated triacylglycerols percentages were calculated according to the method prescribed by (Chrysam, 1985). RESULTS AND DISUCSSION Fatty acid composition: The fatty acid composition of different blends of butter and palm olein is shown in Table 1. Incorporation of 50% of palm olein to butter reduced the level of saturated fatty acids in 20% and increased in 48% and 50% the levels of poly unsaturated fatty acids and mono unsaturated fatty acids, respectively. But, from a nutritional point of view, blends containing more than 50% of palm olein proved to be interesting to make healthy food and this is due to the content of poly unsaturated fatty acids and mono unsaturated fatty acids of these blends (WHO/FAO, 2003). Composition of butter and palm olein are in agreement with the results published in the literature (Aini & Miskandar, 2007). Triacylglycerol composition: The trisaturated (S3), disaturated–monounsaturated (S2U),monosaturated–diunsaturated (SU2) and triunsaturated (U3) contents of triacylglycerols for the non-interesterified (NIE) and interesterified (IE) blends are shown in Table 3. Chemical interesterification distributes fatty acids equally through in the three positions of the glycerol backbone (Rodrigues & Gioielli, 2003). In butter, palm olein and their blends, chemical interesterification increased trisaturated and decreased monosaturated–diunsaturated triacylglycerols, due to the probabilistic distribution of fatty acids. Palm olein showed an increase in trisaturated and triunsaturated triacylglycerols and decrease in disaturated– monounsaturated and monosaturated–diunsaturaded triacylglycerols, accompanied by considerable changes in physical characteristics. The triacylglycerol fraction of a fat is responsible for most of its physical properties that affect lubricity (pourability, holding together at room temperature or melting in the mouth to give a pleasant cooling effect). Lubricity is dependent on melting temperature, solid fat content and texture. Fats that have composition with TAGs predominantly SUU, melt in temperatures between 6 and 23 _C. These products provide appropriate lubricity at 25 _C and are easy to handle and pour over temperatures ranging from 5 to 25_C. The functional properties of margarine oils, such asholding together at room temperature and mouth melting characteristics, are all influenced by disaturated and trisaturated TAGs. These TAGs melt between 27–42 _C and 56–65 _C, respectively. (Liu & White, 1992), In this study, interesterified fats that have more than 50% of palm olein presented a good relation between trisaturated, disatu- rated, diunsaturated and triunsaturated TAGs, increasing the possibilities of use of these fats. Table 2-Fatty acid composition of butter, palm olein and their blends in various ratios. Treatments Fatty acidsc (%) IV SFA(%) PUFA(%) MUFA (%) 14:0 16:0 18:0 18:1 18:2 T0 2.4 ± 0.3a 64.4 ± 0.1 4.5 ± 0.1 23.8 ± 0.1 4.9 ± 0.0 28.5 ± 0.1 71.3 ± 0.4 4.9 ± 0.1 23.8 ± 0.1 T1 2.0 ± 0.5 a 59.5 ± 0.1 4.3 ± 0.2 27.6 ± 0.3 6.6 ± 0.1 38.0 ± 0.7 66.6 ± 0.1 6.6 ± 0.2 27.6 ± 0.3 T2 1.6 ± 0.4b 54.3 ± 0.4 4.2 ± 0.5 32.9 ± 0.8 7.0 ± 0.6 39.2 ± 0. 9 60.1 ± 0.5 7.0 ± 0.6 32.9 ± 0.8 T3 1.5 ± 0.1c 50.9 ± 0.5 5.7 ± 0.1 34.6 ± 0.5 7.3 ± 0.1 42.5 ± 0.6 58.1 ± 0.6 7.3 ± 0.1 34.6 ± 0.5 T4 1.3 ± 0.4c 48.9 ± 0.7 5.0 ± 0.5 36.4 ± 0.9 8.4 ± 0.7 47.7 ± 0.9 55.2 ± 0.9 8.4 ± 0.7 36.4 ± 0.9 T5 1.1 ± 0.2d 44.9 ± 0.7 4.6 ± 0.4 40.1 ± 0.5 9.4 ± 0.9 50.0 ± 1.1 51.2 ± 0.8 9.4 ± 0.9 40.1 ± 0.5 T6 0.8 ± 0.4e 38.0 ± 0.2 5.0 ± 0.8 45.4 ± 0.2 10.2 ± 0.1 56.7 ± 0.1 43.8 ± 0.4 10.2 ± 0.1 45.4 ± 0.2 Table 3Triacylglycerol composition of non-interesterified and interesterified blends. Type of triacylglycerol(%) Butter NIE 80:20 IE NIE IE 60:40 NIE 50:50 40:60 20:80 Palm olein IE NIE IE NIE IE NIE IE NIE IE S3 34.1 37.2 27.7 28.2 21.3 22.5 18.1 19.1 14.9 16.8 8.5 1 4.6 2.1 8.4 S2U 40.7 43.6 42.2 44.4 43.7 43.5 44.5 42.2 45.3 41.0 46.8 39.3 48.3 32.3 U2S 21.8 17.0 26.0 23.3 30.2 28.0 32.4 31.1 34.5 33.2 38.8 35.5 42.9 41.5 U3 3.4 2.2 4.1 4.1 4.7 6.0 5.1 7.6 5.4 9.0 6.0 10.6 6.7 17.8 S3, trisaturated. S2U, disaturated–monounsaturated (SSU/USS + SUS). U2S, monosaturated–diunsaturated (UUS/SUU + USU). Table 3- Effect of chemical interesterification on melting pointof butter and palm olein blends. Treatments Melting Point (0C) Before After a To (100%) butter 34.4±0.33 35.6±0.18a b T1 (80% butter: 20% palm olein) 30.3±0.18 30.9±0.20b T2 (60% butter: 40% palm olein) 26.0±0.31c 26.4±0.19c d T3 (50% butter: 50% palm olein) 24.2±0.45 24.7±0.34d T4 (40% butter: 60% palm olein) 22.1±0.23e 27.9±0.48e f T5 (20% butter: 80% palm olein) 18.0±0.11 30.5±0.22f T6 (100% palm olein) 14.2±0.14g 37.3±0.43a Mean values of duplicate experiment; means with same superscript letter in columns are statistically non significant. Table 4- Effect of chemical interesterification on free fatty acids of butter and palm olein blends. Treatments To (100%) butter T1 (80% butter: 20% palm olein) T2 (60% butter: 40% palm olein) T3 (50% butter: 50% palm olein) T4 (40% butter: 60% palm olein) T5 (20% butter: 80% palm olein) T6 (100% palm olein) Free Fatty Acids (%) After Before 0.110±0.11a 0.104±0.97a 0.098±0.45b 0.092±0.78b 0.090±0.89b 0.064±0.84d 0.080±0.78c 0.020±0.66a 0.024±0.71a 0.018±0.34a 0.022±0.45a 0.020±0.56a 0.022±0.89a 0.020±0.99a Mean values of duplicate experiment; means with same superscript letter in columns are statistically non significant. Melting Point: The melting points of the blends before and after interesterification are shown in Table 3. The melting point of the blends before interesterification increased with the addition of butter in a nonlinear relationship. On the other hand, after the interestererification the relationship was linear. The melting point before interesterification was dependent on butter, on palm olein and on the positive interactions between them. After interesterification the melting point were dependent only on butter and palm olein, as a consequence of the randorm rearrangement, that increased the compatibility between the fats. There were no significant changes in melting point caused by chemical interesterification for fats with up to 60% of palm olein. The largest increases were observed for fats with 80 and 100% of palm olein. This behavior is due to the random distribution of fatty acids in triacylglycerols after interesterification, causing increase in trisaturated triacylglycerols (Lago & Hartman, 1986). The addition of over 50% of butter to blends caused an increase in melting point. The observed trend is consistent with the findings made by other researches which reported that as the percentage of liquid oil in a blend increases, occurs the dilution and solubilization of the triacylglycerols with higher melting points (Farmani et al., 2006). Free Fatty Acids: The results of free fatty acids are given in Table 4. The addition of palm olein in butter at all concentrations decreased the free fatty acids. This may be due to the reason of using refined, bleached and deodorized palm olein in this experiment. After interesterification reaction free fatty acids in all treatments were less than before the reaction. This may be due to the alkaline nature of catalyst which neutralizes the free fatty acids. The results of this study are in line with the findings of Erickson (1999) who stated that before the start of interesterification reaction free fatty acids are neutralized Conclusions The main aim of this research work was to develop butter and palm olein blend by the process of interesterification. Addition of palm olein in butter increased the melting point and unsaturated fatty acids (Table 2). Free fatty acids decreased after interesterification. Chemical interesterification is an effective way to modify the physical and chemical properties of butter, palm olein and their blends. The chemical interesterification allows obtaining fats with various degrees of plasticity, increasing the possibilities for the commercial use of butter and palm olein. REFERENCES Aini, I. N. and M.S. Miskandar (2007). Utilization of palm oil and palm products in shortenings and margarines. European Journal Lipid Science Technology. 109(4), 422–432. AOCS. (1990).Official methods and recommended practices of the American Oil Chemists’ Society. Chrysam, M. M. (1985). Table spreads and shortenings. In T. H. Applewhite (Ed.). Bailey’s industrial oil and fat products (4th ed., Vol. 3, pp. 41–126). New York: Wiley Interscience. Farmani, J., Safari, M., & Hamedi, M. (2006). Application of palm olein in the production of zero-trans Iranian vanaspati through enzymatic interesterification. European Journal Lipid Science Technology, 108(8), 636–643. Erickson, D.R.(1999). Practical Hand Book of Soybean Processing and Utilization. Mc Graw Hill Publishing Company. N.Y. Hartman, L. and R.C.A. Lago (1973). Rapid preparation of fatty acid methyl esters from lipids. Laboratory Practice, 22, 475–476. 494. Lago, R. C. A. and L. Hartman (1986). Directed interesterification of a Brazilian palm oil and analysis of the original and interesterified oil and it’s fractions. Journal Science Food Agriculture, 37(7), 689–693. Liu, H. R. and P.J. White, (1992). Oxidative stability of soybean oils with altered fatty acid compositions. Journal of the American Oil Chemists’ Society, 69, 528–532. Marangoni, A. G. and D. Rousseau (1998). Chemical and enzymatic modification of butterfat and butterfat-canola oil blends. Food Research International, 31(8), 595–599. Rodrigues, J. N. and L.A. Gioielli, (2003). Chemical interesterification of milkfat-corn oil blends. Food Research International, 36(2), 149–159. Sreenivasan, B. (1978). Interesterification of fats. Journal of the American Oil Chemists’ Society, 55(11), 796–805. WHO/FAO (2003). Diet, nutrition and prevention of chronic diseases. Report of the joint WHO/FAO expert consulation. Technical Report Series, 916.