Comparative Degradation Effects of Sesame and Soybean Oil during Heating using Microwave Irradiation

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1 Journal of Scientific & Industrial Research Vol 73, August 2014, pp Comparative Degradation Effects of Sesame and Soybean Oil during Heating using Microwave Irradiation J Ghosh*, A Banerjee, S S Gupta, A Sengupta and M Ghosh Deptartment of Chemical Technology, University College of Science & Technology, University of Calcutta Kolkata , India Received 6 June 2013; revised 25 March 2014; accepted 10 May 2014 Changes of quality parameters upon heating were evaluated at different times of microwave heating on refined sesame and soybean oil high and compared to the results obtained for standard chemical indices (free fatty acids, peroxide, p-anisidine, nonenal content). Soybean oil was more extensively oxidised by microwave heating than the other oil probably as a consequence of absence of natural antioxidants. Microwave heating also induced alterations in heating profiles of the oils [Acid value of (0.67±0.04) and (1.8±0.01); peroxide value of (1.86±0.09) and (37.83±0.23); p-anisidine value of (16.46±0.12) and (18.23±0.23) after 10 minutes at high power for sesame and soybean oils respectively]. Presence of frying components in soybean oil like polyunsaturated fatty acids (almost 58%) enhanced thermo-oxidation and resulted in its poor stability. The analysis of heating profiles and related thermal properties like response to nonenal appeared to be a valuable tool to assess different degrees of lipid oxidation induced by microwave heating in vegetable oils. Nonenal content of (13.08±0.02) µmol/gm for sesame oil and (17.28±0.08) µmol/gm for soybean oil at high power showed their comparative thermal stability. Keywords: Microwave heating; 4-hydroxynonenal; Frying oil; Sesame oil; Soybean oil Introduction Lipid components of food are particularly sensitive to the heating treatment, as the specific heat of lipids is low and they get heated quickly. In fact, the development of oxidative alterations in vegetable oil was found during heating and among them the formation of reactive free radicals that rapidly reacted with the atmospheric oxygen to produce primary and secondary oxidation products 1, the moderate increase of free fatty acids by fat hydrolysis; the decrease of tocopherols are predominating 2. Overall, lipid oxidation not only produces characteristic undesirable odours and flavours, but also decreases the nutritional. In the food industry, microwave heating operations have been used with increasing success in baking, blanching, cooking, drying, pasteurization, sterilization, and thawing of various food products 3,4. There are some reviews which established the effects of microwave heating on the nutritional constituents of foods and concluded that it does not change the nutrient content of food to any greater extent than conventional cooking. But study, particularly regarding the vegetable oils which are more susceptible to oxidation at temperatures above *Author for correspondence mahuag@gmail.com 150 C than other food components are specially needed. This, in combination with the fact that microwave heating is faster and more uniform, will results in significant increase in microwave usage and in most cases a more economical final product 5. During the study of deterioration of oil during microwave heating, special attention should be given for the compound 4-hydroxy-2-nonenal (HNE) [CH 3 (CH2) 4 CH(OH)C=CCO] which is an oxygenated α,β-unsaturated aldehyde. Now it is well known that HNE can be formed as a result of peroxidation of n-6 polyunsaturated fatty acids during the heating of oils containing this fatty acid 6. Sesame and soybean - these two oils are widely used in India for producing various kinds snack items. Soybean oil is characterized for its n-6 polyunsaturated fatty acid (linoleic acid) content and tocopherol content. The PUFA makes it susceptible for oxidation where as tocopherol, in addition to possessing vitamin E function can provide protection for the oil. Sesame oil is characterised by the presence of monounsaturated and polyunsaturated fatty acids (MUFA & PUFA) and a number of antioxidative component (lignans) present in it. The aim of this study was to examine the oxidative stability of these two vegetable oils when heated in a microwave oven and

2 548 J SCI IND RES VOL 73 AUGUST 2014 the standard oxidative stability indices were determined. The general quality deterioration of oil during heating or frying is estimated primarily from the four parameters, Acid value (AV), Peroxide value (POV), p-anisidine value (PAV) and HNE content, especially for oils containing PUFA. Acid value gives the idea about high temperature scission of ester bond and simultaneously serves as an indicator of the amount of generation of free fatty acids. Peroxide value helps to assess the amount of oxidation that has occurred in the oil due to the high temperature generated by microwave irradiation. Again p-anisidine value helps in detecting the amount of unsaturated aldehydes generated in the medium due to high temperature oxidation, which leads to the formation of unacceptable flavors. 4-HNE is generated by the oxidation of lipids especially the ones containing polyunsaturated fatty acids like linoleic acid. Therefore, these tests helped to estimate the amount of oxidation that has occurred in the lipids due to high temperature. Materials and Methods Refined sesame and soybean oils (without any added antioxidant) were collected from Edible Products Ltd., Kolkata. Samples were checked for initial quality parameters of the oil like acid value, peroxide value, p-anisidine value and HNE and stored in a refrigerator. For each experiment, different samples of each type of oil were subjected to microwave heating and analysed. 2,4-dinitrophenyl hydrazine reagent was procured from Sigma Aldich Chemical Company. All other reagents were of Analytical grade and purchased from E-Merck India Ltd. Microwave treatments of oil samples A domestic microwave oven (Make: Electrolux, Model: EM17MS80WH) was used in this study. All oil samples were simultaneously exposed at a frequency of 2450 MHz. There were three settings of heating corresponding to low, medium, and high power. When operated at high power the oven provided ca. 800 W, at medium power it provided 650 W and at low power it provided 500W. Each sample of oil was taken in a conical flask, sealed with polyethylene film (40 g each; 4 cm i.d.), which were placed on the rotary turntable plate of the microwave oven. The oil samples were heated with and without 4 pieces of 2 inch potato chips for various periods (5, 10, 15 and 20 min) at each power setting. The moisture content of the potatoes used for frying was about 83%. The potato:oil ratio was maintained at 1:5 (w/v) for both types of oil in case of all the different studies All oil samples were prepared in replicate. Each experiment was performed in a separate day to maintain the uniformity of initial temperature. The temperatures of the heated oils immediately after exposure for each time period were determined with a calibrated chromel-alumel thermocouple. Treated oil samples were stored under nitrogen at 18 C for further analyses and all the analyses were completed within 2 days. Oil sample analysis The following oil quality parameters were determined for the oil samples collected at different times: Fatty acid composition by gas-liquid chromatography. Methyl esters of the corresponding fatty acids were prepared by BF 3 -Methanol 7 and subjected to GC instrument (Agitent 6890 Series Gas Chromatograph) equipped with a flame ionization detector (FID). Acid Value, Peroxide value, p-anisidine were determined following the AOCS Official Method Te 1a Estimation of 4-hydroxy-2-trans-nonenal (HNE) by DNPH derivatization 9. Standard HNE-DNPH derivative was prepared by the reaction of HNE and DNPH. HNE-DNPH was separated from the reaction mixture by thin layer chromatography (TLC) using CH 2 Cl 2 as developing solvent. The HNE-DNPH band was scraped off and extracted with methanol. The extract was filtered, dried with anhydrous sodium sulphate followed by stream of nitrogen, and redissolved in methanol. The concentration of HNE- DNPH was measured by spectrophotometer (UV-VIS Shimadzu 1700) at 370 nm and calculated by using the molar absorptivity ε370 nm = 28,000 M 1 cm 1. Statistical Analysis All the experiments were conducted thrice and the values are expressed as Mean±SEM. Results and Discussions The fatty acid compositions of two experimental oils showed that both the oils possess almost 85% of unsaturated fatty acids while higher amount of polyunsaturated fatty acid was present in soybean oil (10.1% palmitic, 4.3% stearic, 24.2% oleic, 54.1%

3 GHOSH et al.: COMPARATIVE DEGRADATION EFFECTS OF SESAME AND SOYBEAN OIL 549 linoleic, 7.3% linolenic acids and 9.6% palmitic, 3.1% stearic, 43.2% oleic, 44.1% linoleic acids in soybean and sesame oil respectively). Initially the temperature was 30 C at all the power treatments. Thereafter duration of 5, 10, 15 and 20 minutes the temperatures of the oil was 50 C, 70 C, 72 C and 76 C at low power; 105 C, 140 C, 180 C and 185 C at medium power and 180 C, 300 C and undetected at 15 and 20 minutes for high power respectively. The increased microwave power and duration caused charring of the oil samples. In case of sesame oil, major change of acid value was noted after 15 min of heating at high power (Table 1). At low and medium power the acidvalue (AV) did not show much alteration from that of the initial data. In contrast, for soybean oil (Table 1), changes in acid value with time were detected even at Table 1- Change of AV*, POV* and PAV* (meq/kg) during heating at different power for different time period Time (min) AV Heating Power Sesame Oil Low Power 0.25± ± ± ± ±0.01 Medium Power 0.25± ± ± ± ±0.01 High Power 0.25± ± ±0.04 nd nd Soybean Oi l Low Power 0.70± ± ± ± ±0.01 Medium Power 0.70± ± ± ± ±0.05 High Power 0.70± ± ±0.01 nd nd Time (min) PV Heating Power Sesame Oil Low Power 3.57± ± ± ± ±0.09 Medium Power 3.57± ± ± ± ±0.17 High Power 3.57± ± ±0.09 nd nd Soybean Oil Low Power 5.94± ± ± ± ±0.33 Medium Power 5.94± ± ± ± ±0.43 High Power 5.94± ± ±0.23 nd nd Time (min) Heating Power r PAV Sesame Oil Low Power 0.67± ± ± ± ±0.10 Medium Power 0.67± ± ± ± ±0.16 High Power 0.67± ± ±0.12 nd nd Soybean Oil Low Power 3.92± ± ± ± ±0.20 Medium Power 3.92± ± ± ± ±0.27 High Power 3.92± ± ±0.23 nd nd nd: not determined as charring of oil occurred at this point Values are mean of triplicate study *Where AV = acid value *Where POV = peroxide value *Where PAV = p-anisidine value

4 550 J SCI IND RES VOL 73 AUGUST 2014 medium power. The AV for medium power as was observed initially (0.7) changed rapidly after 5 min (1.01). Thereafter the acid value increased gradually to 1.2. However in case of high power heating of soybean oil, AV drastically increased after 5 min and further increased exponentially after 10 min from 0.7 to 1.8 (Figures 1 and 2). The increasing AV indicated the degradation of the oil by hydrolytic scission. AVs data for soybean oil indicates that this oil is more prone to oxidative damage on heat treatment such as microwave heating than the sesame oil. This is due tothe presence of lignans in sesame oil which help to resist the hydrolytic oxidation. Changes in POV during the heating of both the oils are given in Table 1. POVs increased steadily for medium and high power rangesfor both sesame and soybean oils. However, the peroxide values for soybean oil were markedly higher Fig. 1- Change in acid values with time in case of low power, medium power and high power microwave heating for sesame oil Fig. 2- Change in acid values with time in case of low power, medium power and high power microwave heating for soybean oil than those for sesame. From the results, it is evident that the primary oxidation products generate rapidly in soybean oil than the sesame oil. The oxidation of oils and fats is one of the main causes of the deterioration of the organoleptic and nutritional characteristics of foodstuffs, due to the development of rancidity. The complex oxidation process can actually be summarized into two phases. In the first phase the fatty acids react with oxygen to form peroxides. These primary oxidation products are measured by POV. In the second step peroxides degrade into volatile substances. These secondary oxidation products are estimated by PAV. The generation of secondary oxidation occurred rapidly for soybean oil in comparison to sesame oil. The oxidative status of a fat should be evaluated considering both its primary and secondary oxidation. Due to the presence of lignan antioxidants in sesame they are able to prevent the oxidation of fatty acids in sesame oil better than tocopherol which is present in soybean oil. Hence sesame lignans showed better heat resistance than tocopherol. Tocopherol content of soybean oil is almost 0.5-1% and PUFA content about 60%. In comparison the lignan content of sesame oil is almost 1-2% with PUFA content of about 50% 10. The data generated during frying of potato chips in both oils for 5 min at different microwave power are presented in Table 2. On frying potatoes with both the oils at different powers for 5 minutes, remarkable results were observed. AVs of the oils did not show much change on heating at different powers. However, as before, AVs were higher for soybean oil (1.39 at low power, 1.8 at medium power and 1.9 at high power) than that for sesame oil (0.27 at low power, 0.29 at medium power and 0.33 at high power). POVs and PAVs showed a trend as before. Soybean oil showed higher POVs and higher PAVs than sesame oil. Like PAV, HNE content showed a similar trend when the potato pieces were fried with either of the oils. Initial values increased rapidly on the initiation of microwave treatment. Thereby the HNE contents in case of both sesame and soybean oils did not show any drastic alterations. There are some general trends of HNE formation, regardless of the food being fried. It was initially hypothesized that frying in heated oil would form as much or even more HNE then heating alone. Culinary oils that have been

5 GHOSH et al.: COMPARATIVE DEGRADATION EFFECTS OF SESAME AND SOYBEAN OIL 551 Table 2 - Changes in AV, POV, PAV & HNE* content during heating with cut potatoes at different power for 5 min Heating Power Parameters Initial (no heating) Low power Medium Power High Power heated but not used to fry food had reported HNE concentrations ranging from 2 to 42 ppm 11,12 and HNE concentrations in frying oils range from to 60 ppm. It should be noted that HNE formation is temperature dependent for many of the oils that have been tested. The data indicate that the addition of potato chips to the oil during heating substantially increased the amount of HNE in frying oil during microwave heating and the amount increased with degree of frying. Since most previously published studies on HNE formation over time were limited to heated oils (without the addition of food), the present results provide novel information that helps to explain the extent to which HNE forms in oil used for frying food. Study of HNE content in our study revealed that lipid peroxidation occurs at a greater extent in case of soybean oil during the frying process. Sesame oil on the other hand shows less amount of HNE generation compared to soybean oil leading to the conclusion that less lipid peroxidation occurs in the case of sesame oil. In the next phase of experiment we used these oils for frying purposes that means some components were added to it for frying. Here potato slices were used for frying which contained appreciable amount of moisture in it which facilitates faster and higher heat rise when exposed to the same period of microwave excitation and therefore a new set of indices were expected. Sesame oil showed better stability than soybean oil. Conclusion In conclusion it can be said that the microwave heating somehow changes the qualitative values of Sesame oil AV 0.25± ± ± ±0.02 POV 3.57± ± ± ±0.07 PAV 0.67± ± ± ±0.11 HNE content (µmol/gm) 4.57± ± ± ±0.02 Soybean oil AV 0.98± ± ± ±0.15 POV 5.94± ± ± ±0.01 PAV 3.92± ± ± ±0.11 HNE content (µmol/gm) 5.61± ± ± ±0.08 Values are mean of triplicate study *Where AV = acid value; PAV = p-anisidine value; POV = peroxide value & HNE = 4-hydroxy nonenal edible vegetable oils. This stability however varies from oil to oil. Present study dealt with two major oils, soybean and sesame. It was observed that after high microwave heating of soybean oil, its AV, POV, PAV increased much higher than sesame oil. Therefore, it can be concluded that sesame oil is much more stable oil even at high microwave heating than soybean oil. The same conclusion can be drawn from the observed HNE content. It was observed that in case of soybean oil the HNE formation was higher than that of sesame oil in microwave heating with potato. It is presumably due to the presence of sesame lignans in sesame oil which imparted antioxidant property to the oil made the oil microwave heat resistant. As per refining practice, oils are used to undergo through various heating process such as heat bleaching or deodorization where contact with high temperature saturated steam can degrade the quality of the oil, and result in the formation of HNE in the heating process. In such cases, soybean oil is more susceptible for degradation than sesame oil. References 1 Hassanein M M, El-Shami S M & El-Mallah M H, Changes occurring in vegetable oils composition due to microwave heating, Grasas y Aceites, 54 (2003) Yoshida H & Takagi S, Antioxidative effects of sesamol and tocopherols at various concentrations in oils during microwave heating, J. Sci. Food Agric., 79 (1999) Tan C P, Che Man Y B, Jinap S & Yusoff M S A, Effects of microwave heating on changes in thermal properties of RBD palm olein by differential scanning calorimetry, Innovative Food Science & Emerging Technologies, 3 (2002)

6 552 J SCI IND RES VOL 73 AUGUST Tan C P, Che Man Y B, Jinap S & Yusoff M S A, Effects of microwave heating on changes in chemical and thermal properties of vegetable oils, J. Am. Oil Chem. Soc., 78 (2001) Chiavaro E, Rodriguez-Estrada M T, Vittadini E & Pellegrini N, Microwave heating of different vegetable oils: Relation between chemical and thermal parameters, LWT - Food Science and Technology, 43 (2010) Seppanen C M & Csallany A S, Formation of 4- hydroxynonenal, a toxic aldehyde, in soybean oil at frying temperature, J. Am. Oil Chem. Soc., 79 (2002) Banerjee A, Ghosh S & Ghosh M, Anti-oxidative effect of turmeric on frying characteristics of soybean oil, Journal of Food Science and Technology, DoI : /s y 8 Official Methods and Recommended Practices of the American Oil Chemists Society 4th edn., edited by D. Firestone, American Oil Chemists Society, Champaign (1993) 9 Tatsuhiro U, Naohiro G & Shun W, Method for Analysis of 4-Hydroxy 2-(E) nonenal with Solid-Phase Microextraction, Lipids, 37 (2002) Cerretani L, Bendini A, Rodriguez-Estrada M T, Vittadini E & Chiavaro, E. Microwave heating of different commercial categories of olive oil: part I. Effect on chemical oxidative stability indices and phenolic compounds, Food Chemistry, 115 (2009) Seppanen C.M & Csallany A S, Incorporation of the toxic aldehyde 4-hydroxy-2-trans-nonenal into food fried in thermally oxidized soybean oil, J. Am. Oil Chem. Soc., 81 (2004) Matthaus B, 4-Hydroxy-2-trans-nonenal an oxidation product of heated edible oils, J. Am. Oil Chem. Soc., 88 (2011)

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