بررسی تاثیر اسید گالیک، متیل گالات و ترکیب آنها بر پایداری اکسایشی روغن طی فرآیند سرخ کردن

نوع مقاله : مقاله پژوهشی

نویسندگان

• مائده حسینخانی آبادچی
• رضا فرهوش

گروه علوم و صنایع غذایی، دانشکده کشاورزی، دانشگاه فردوسی مشهد، مشهد، ایران

https://doi.org/10.22067/ifstrj.2022.75114.1144

چکیده

تغییرات شیمیایی، پایداری اکسایشی و شاخص‌های کیفی نمونه ترکیبی روغن آفتابگردان (SO) و نخل (PO) (PO 35: SO 65 وزنی/وزنی) در دمای°C 180 طی تیمار حرارتی 8 ساعته در حضور آنتی‌اکسیدان‌های اسید گالیک (GA)، متیل گالات (MG)، ترکیب GA+MG (75:25، 50:50 و 25:75) و ترسیوبوتیل هیدروکینون (TBHQ) مورد بررسی قرار گرفت. میانگین داده­ها بر اساس آزمون چند دامنه­ای دانکن در سطح 5 درصد (05/0p<) مقایسه شدند. بررسی خواص شیمیایی نشان داد ساختار اسیدهای چرب SO عمدتا حاوی اسید‌ چرب لینولئیک (53/61 درصد) و اولئیک (50/25 درصد) و برای PO اولئیک (90/41) و پالمیتیک (9/38) می‌باشد؛ همچنین، محتوی کل ترکیبات فنولی (TPC) و توکوفرولی (TTC) نمونه PO به ترتیب 12/53 و 185 و نمونه SO برابر با 01/36 و 490 (µg.g^-1) بدست آمد. نتایج آزمون پایداری اکسایشی مبنی بر پارامترهای عدد کربونیل (CV)، عدد دی­ان مزدوج (CDV) و اسیدیته (FFA) مورد تجزیه و تحلیل قرار گرفت. طبق یافته­ها، تمامی پارامترهای CV، CDV و FFA طی فرآیند سرخ کردن با گذشت زمان با سرعت­های متفاوت به طور معناداری افزایش یافتند (05/0>p). همچنین، رابطه معناداری بین 7 تیمار مشاهده شد؛ بدین­صورت که تیمار شاهد و تیمار حاوی آنتی‌اکسیدان سنتزی TBHQ به­ترتیب دارای بیشترین و کمترین میزان اسیدیته بودند. همچنین، محتوی CDV روغن مورد آزمون بدون آنتی‌اکسیدان در حضور GA75+MG25 به اندازه 6/68 درصد کاهش یافت. علاوه­بر­این، سرعت تغییر CV روغن مورد آزمون بدون آنتی­اکسیدان در حضور TBHQ به اندازه 2/70 درصد کاهش یافت. در نتیجه، افزودن جزئی از آنتی­اکسیدان­های طبیعی می­تواند عملکردی رقابتی با آنتی­اکسیدان TBHQ داشته باشد.

کلیدواژه‌ها

• اسید گالیک
• اسیدهای چرب
• پایداری اکسایشی
• عدد دی‌ان مزدوج
• عدد کربونیل
• متیل گالات
• TBHQ

موضوعات

• شیمی مواد غذایی

عنوان مقاله [English]

Investigation of the Impact of Gallic Acid, Methyl Gallate and their Combination on the Oxidative Stability of Frying Oli

نویسندگان [English]

• Maedeh Hosseinkhani Abadchi
• Reza Farhoosh

Department of Food Science and Technology, Faculty of Agriculture, Ferdowsi University of Mashhad, Mashhad, Iran

چکیده [English]

Introduction
 Thermal process is the most prominent option for treating foods. During the heat treatment, food nutrients response simultaneously but adversely under pH, temperature, moisture, and other provided conditions. It might result in an irreversible transformation of composition and structure that influences oxidative stability and sensory properties. The use of antioxidants is one of the most common methods to prevent edible oils oxidation. Safety concerns of synthetic antioxidants including tert-butylhydroquinone (TBHQ) as food additives have led to increasing demands for natural ones. Phenolic compounds such as Gallic Acid (GA) and Methyl Gallate (MG) represent to possess markedly high activity to scavenge free radicals which are among the most powerful natural sources of oxidative inhibitors in foods. Apart from their antioxidant activity, GA and MG also exhibit multiple biological characteristics such as anti-atherogenic, anti-spasmodic, and anti-microbial activities. This study aimed to investigate the oxidative stability of the in-use sunflower (S) and palm (P) oils as affected by the GA, MG, (GA+MG), and TBHQ to clarify their antioxidant behavior.
Materials and Methods
Antioxidants Gallic acid, Methyl gallate and TBHQ (Purity>98%) were purchased from Sigma Aldrich, USA. All solvents and chemicals were provided from Merck, Germany and Sigma Aldrich, USA with analytical grade. Antioxidant-free sunflower and palm oil were prepared from Three Goals factory, Neyshabur, and potatoes (Agria variety) from Fariman region, Khorasan Razavi.
 
Results and Discussion
Chemical changes, oxidative stability and quality indices of the in-use sunflower oil (S) and palm (P) (65:35 w.t. %) were evaluated during 8-hour heat treatment at 180 °C through GA, MG, GA/MG (25:75, 50:50 and 25:75) and TBHQ. All experiments were carried out in quadruplicate, and data were subjected to analysis of variance (One-way-ANOVA). Mean data were compared based on Duncan's multiple range test at 5% level (p<0.05). Observations of the chemical properties showed that sample S mainly contained Linoleic fatty acid (61.53%) and Oleic acid (25.50%) and for sample P, Oleic acid (41.90%) and the saturated long-chain fatty acid of Palmitic acid (38.9%). Also, the total phenolic content (TPC) and tocopherol (TTC) of sample P were 53.12 and 185)µg.g^-1(, respectively, and sample S were 36.01 and 490 )µg.g^-1(. The results of oxidation stability test were analyzed based on Carbonyl value (CV), Conjugated diene value (CDV) and acidity (FFA) parameters. According to our findings, all parameters increased significantly at different speeds during the heat treatment (p<0.05). Moreover, the oxidative stability of the in-use oil was significantly promoted by the antioxidants added, meaning that the control treatment and the treatment containing synthetic antioxidant TBHQ had the highest and lowest FFA%, respectively. The CDV of the antioxidant-free treatment was reduced by 68.6% in the presence of GA75+MG25.In addition, the CV change rate of the antioxidant-free sample in the presence of TBHQ was reduced by 70.2%. It was concluded that the natural antioxidants were capable of being competed with TBHQ antioxidants.
 
Conclusion
The results of this study showed that the heat treatment affected the nutritional value, quality indexes and chemical structure of the treatments, decreasing the quality and stability of the oil. As observed, all FFA, CDV and CV parameters increased significantly at different speeds during 8-hour frying process. The analysis also indicated that the oxidative stability of the treatments increased at the presence of antioxidants during the heat treatment at 180 °C. Thus, the control treatment and the treatment containing synthetic antioxidant TBHQ had the highest and lowest acidity, respectively. Also, the CDV of the antioxidant-free treatment decreased by 68.6% in the presence of GA75+ MG25. In addition, the rate of CV changes was declined by 70.2% through the TBHQ. The results indicated the key role of this synthetic antioxidant in preventing the formation of secondary compounds in the advanced stages of oxidation.
It is evident that most synthetic antioxidants are volatile and heat sensitive. Furthermore, there are some limitations in applying TBHQ to promote oxidative stability of food products due to its toxic potential. Evidences have also been reported on the mutation caused by  the synthetic antioxidant TBHQ in the living organism's body. Compared to synthetic antioxidants, natural polyphenolic antioxidants such as MG and GA which widely distribute in plants mainly have antioxidative properties. Compared to GA and MG, GA+MG antioxidants have a longer induction period and higher oxidative stability. Promoting oxidative stability with such an arrangement of antioxidants is a good option in taking advantage of this class of natural antioxidants. According to the results of this study, it can be inferred that with a slight increase in natural antioxidants levels, we might be able to obtain the oxidative stability level comparable to the behavior of synthetic antioxidant TBHQ. Of course, it is worth noting that the addition of natural antioxidants to food such as edible oils should also be done according to national and international standards.

کلیدواژه‌ها [English]

• Carbonyl value
• Conjugated diene value
• Gallic acid
• Fatty acids
• Methyl gallate
• Oxidative stability
• TBHQ

مراجع

1. Alavi Rafiee, S., Farhoosh, R., & Sharif, A. (2018). Antioxidant activity of gallic acid as affected by an extra carboxyl group than pyrogallol in various oxidative environments. European Journal of Lipid Science and Technology, 120(11), 1800319. https://doi.org/10.1002/ejlt.201800319.
2. Bordin, K., Kunitake, M.T., Aracava, K.K., & Trindade, C.S.F. (2013). Changes in food caused by deep fat frying-a review. Archivos Latinoamericanos de Nutricion, 63(1), 5-13.
3. Budilarto, E.S., & Kamal‐Eldin, A. (2015). The supramolecular chemistry of lipid oxidation and antioxidation in bulk oils. European Journal of Lipid Science and Technology, 117(8), 1095-1137. http://doi.org/10.1002/ejlt.201400200.
4. Crespo, Y.A., Sánchez, L.R.B., Quintana, Y.G., Cabrera, A.S.T., Del Sol, A.B., & Mayancha, D.M.G. (2019). Evaluation of the synergistic effects of antioxidant activity on mixtures of the essential oil from Apium graveolens, Thymus vulgaris L. and Coriandrum sativum L. using simplex-lattice design. Heliyon, 5(6), e01942. https://doi.org/10.1016/j.heliyon.2019.e01942.
5. Fahimdanesh, M., Ghavami, M., Hemasi, A.H., & Aberomand, P. (2008). Evaluation of phenolic compounds and tocopherols content in some trade Iranian olive oils by HPLC. Iranian Journal of Food Science and Technology, 5(3), 53-59. http://fsct.modares.ac.ir/article-7-1871-en.html.
6. Farahmandfar, R., & Asnaashari, M. (2018). Assessment of antioxidant activity and kinetic oxidative parameters of syringic acid and gallic acid in sunflower oil. Food Science and Technology, 15(83), 1-14.
7. Farhoosh, R., Pazhouhanmehr, S., & Poorazrang, H. (2010). Heat stability of the oils from current canola cultivars in Iran. Journal of Food Science and Technology(Iran). http://fsct.modares.ac.ir/article-7-3334-en.html.
8. Farhoosh, R., & Esmaeilzadeh Kenari, R. (2009). Anti‐rancidity effects of sesame and rice bran oils on canola oil during deep frying. Journal of the American Oil Chemists' Society, 86(6), 539-544. https://doi.org/10.1007/s11746-009-1382-7.
9. Farhoosh, R., & Kafrani, M.H.T. (2010). Frying performance of the hull oil unsaponifiable matter of Pistacia atlantica mutica. European Journal of Lipid Science and Technology, 112(3), 343-348. https://doi.org/10.1002/ejlt.200900178.
10. Farhoosh, R., & Moosavi, S.M.R. (2008). Carbonyl value in monitoring of the quality of used frying oils. Analytica Chimica Acta, 617(1-2), 18-21. https://doi.org/10.1016/j.aca.2007.11.049.
11. Farhoosh, R., & Nyström, L. (2018). Antioxidant potency of gallic acid, methyl gallate and their combinations in sunflower oil triacylglycerols at high temperature. Food Chemistry, 244, 29-35. https://doi.org/1016/j.foodchem.2017.10.025.
12. Gad, A.S., & El‐Salam, M.H.A. (2010). The antioxidant properties of skim milk supplemented with rosemary and green tea extracts in response to pasteurisation, homogenisation and the addition of salts. International Journal of Dairy Technology, 63(3), 349-355. http://doi.org/1111/j.1471-0307.2010.00585.x.
13. Gavahian, M., Khaneghah, A.M., Lorenzo, J.M., Munekata, P.E., Garcia-Mantrana, I., Collado, M.C., & Barba, F.J. (2019). Health benefits of olive oil and its components: Impacts on gut microbiota antioxidant activities, and prevention of noncommunicable diseases. Trends in Food Science & Technology, 88, 220-227. https://doi.org/10.1016/j.tifs.2019.03.008.
14. Hajeb, B. (2018). Comparison of thermal resistance of frying oil and canola oil by principal component of chemometrics analysis. Thesis for receiving «M.Sc» degree On Chemical Engineering, Faculty of Chemical Engineering and Department of Engineering, Islamic Azad University،Science and Research Branch, Tehran, Iran.
15. Hamedani, F., & Haddad Khodaparast, M.H. (2014). Investigating chemical properties and oxidative stability of kernel oil from Pistacia Khinjuk growing-wild in Iran. Iranian Journal of Research and Innovation in Food Science and Technology, 2(3): 265-278. http://doi.org/1007/s11746-016-2817-6.
16. https://www.fao.org/3/y2774e/y2774e04.htm.
17. Huang, C.Y., Chang, Y.J., Wei, P.L., Hung, C.S., & Wang, W. (2021). Methyl gallate, gallic acid-derived compound, inhibit cell proliferation through increasing ROS production and apoptosis in hepatocellular carcinoma cells. PloS One, 16(3), e0248521. https://doi.org/10.1371/journal.pone.0248521.
18. Jung, M.Y., & Choi, D.S. (2016). Protective effect of gallic acid on the thermal oxidation of corn and soybean oils during high temperature heating. Food Science and Biotechnology, 25, 1577-1582. http://doi.org/1007/s10068-016-0243-z.
19. Kaviani, M., Niazmand, R., & Shahidi Noghabi, M. (2013). Discarding time evaluation of canola oil based on oxidation indexes during potato deep frying. Research and Innovation in Food Science and Technology, 2(1), 37-50. https://doi.org/10.22101/JRIFST.2013.07.03.213.
20. Kharazi, S.H., Kenari, R.E., & Amiri, Z.R. (2014). Effect of thermal treatment on chemical changes and oxidative stability of Iranian common virgin olive oil of roodbar region: a study on Zard, Mari and Phishomi. Iranian Food Science & Technology Research Journal, 9(4).
21. Meda, A., Lamien, C.E., Romito, M., Millogo, J., & Nacoulma, O.G. (2005). Determination of the total phenolic, flavonoid and proline contents in Burkina Fasan honey, as well as their radical scavenging activity. Food Chemistry, 91(3), 571-577. https://doi.org/10.1016/j.foodchem.2004.10.006.
22. Mehdi Nia Lichani, B., Esmaeilzadeh Kenari, R., & Dinpanah, G. (2018). Extraction of phenolic and tocopherol compounds of Mottaka plant and study of the effect of its extract on the stability of sunflower oil as a synthetic antioxidant substitute. Journal of Food Technology and Nutrition, 15(4): 81-90.
23. Morelló, J.R., Motilva, M.J., Tovar, M.J., & Romero, M.P. (2004). Changes in commercial virgin olive oil (cv Arbequina) during storage, with special emphasis on the phenolic fraction. Food Chemistry, 85(3), 357-364. http://doi.org/1016/j.foodchem.2003.07.012
24. Pinho, O., Ferreira, I.M.P.L.V.O., Oliveira, M.B.P.P., & Ferreira, M. A. (2000). Quantification of synthetic phenolic antioxidants in liver pâtés. Food Chemistry, 68(3), 353-357. https://doi.org/10.1016/S0308-8146(99)00205-8
25. Sepehry, N., Mortazavi, S.A., Sadeghian, A., Mohammadi, M., & Pedram nia, A. (2022). Evaluation of antioxidant and antibacterial properties of essential oil and black cumin extract extracted by clevenger and ultrasound methods. Journal of Food Science and Technology (Iran), 18(121), 57-68. URL:http://fsct.modares.ac.ir/article-7-53459-en.html
26. Tavakoli, K. (2013). Antioxidant effect of Medlar peel extract on stability of sunflower oil during storage condition and thermal process. Thesis for receiving «M.Sc» degree On Food Science and Technology, Faculty of Science-Department Agricultura, Islamic Azad University، Damghan Branch, Iran.
27. Wen, Y., Xu, L., Xue, C., Jiang, X., & Wei, Z. (2020). Assessing the impact of oil types and grades on tocopherol and tocotrienol contents in vegetable oils with chemometric methods. Molecules, 25(21), 5076. http://doi.org/3390/molecules25215076
28. Williams, G.M., Wang, C.X., & Iatropoulos, M.J. (1990). Toxicity studies of butylated hydroxyanisole and butylated hydroxytoluene. II. Chronic feeding studies. Food and Chemical Toxicology, 28(12), 799-806. http://doi.org/1016/0278-6915(90)90052-o
29. Xu, E., Wang, J., Tang, J., Ruan, S., Ma, S., Qin, Y., & Liu, D. (2022). Heat-induced conversion of multiscale molecular structure of natural food nutrients: A review. Food Chemistry, 369, 130900. http://doi.org/1016/j.foodchem.2021.130900
30. Xu, Z., Leong, S.Y., Farid, M., Silcock, P., Bremer, P., & Oey, I. (2020). Understanding the frying process of plant-based foods pretreated with pulsed electric fields using frying models. Foods, 9(7), 949. https://doi.org/10.3390/foods9070949
31. Yanishlieva, N.V., Kamal‐Eldin, A., Marinova, E.M., & Toneva, A.G. (2002). Kinetics of antioxidant action of α- and γ- toco- pherols in sunflower and soybean triacylglycerols. European Journal of Lipid Science and Technology, 104(5), 262-270. https://doi.org/10.1002/1438-9312(200205)104:5<262::AID-EJLT262>3.0.CO;2-B