GC/FID tekniğiyle krill yağı ticari takviyelerindeki yağ asidi içeriğinin belirlenmesi

Öz

Krill yağı, yüksek biyoyararlanımı ve astaksantin gibi güçlü antioksidanların varlığı nedeniyle son zamanlarda popüler bir besin takviyesi olarak dikkat çekmiştir. Bu çalışmada, farklı ticari krill yağı takviyelerinin (KOs) yağ asidi profilleri Gaz Kromatografisi-Alev İyonizasyon Dedektörü (GC-FID) tekniği kullanılarak belirlenmiştir. Sonuçlara göre, toplam doymuş yağ asitleri (SFA) %11.70 ile %51.59 arasında, tekli doymamış yağ asitleri (MUFA) %32.13 ile %52.50 arasında ve çoklu doymamış yağ asitleri (PUFA) %9.22 ile %55.17 arasında değişim göstermiştir. Belirlenen başlıca yağ asitleri palmitik asit (C16:0), oleik asit (C18:1 ω−9), linoleik asit (C18:2 ω−6), eikosapentaenoik asit (EPA, C20:5) ve dokosaheksaenoik asit (DHA, C22:6) ‘den oluşmaktadır. Ayrıca, tüm örneklerde çok düşük miktarlarda trans yağ asidi (%0.28–3.96) tespit edilmiştir. Elde edilen bulgular, ticari krill yağı ürünlerinin yağ asidi bileşiminin, hammadde kaynağına ve kullanılan spesifik üretim parametrelerine bağlı olarak önemli ölçüde değiştiğini göstermektedir. Bu araştırma, krill yağı takviyelerinin besin sınıflandırması ve ticari geliştirme potansiyeli için önemli veriler sağlamaktadır.

Anahtar Kelimeler

• Krill Yağı
• Yağ Asidi Profili
• GC-FID

Determination of fatty acid content in krill oil commercial supplements by GC/FID technique

Abstract

Krill oil has recently gained attention as a popular dietary supplement due to its high bioavailability and the presence of potent antioxidants such as astaxanthin. In this study, the fatty acid profiles of different commercial krill oil supplements (KOs) were determined using the Gas Chromatography-Flame Ionization Detector (GC-FID) technique. Based on the results, the total saturated fatty acids (SFA) ranged from 11.70% to 51.59%, monounsaturated fatty acids (MUFA) from 32.13% to 52.50%, and polyunsaturated fatty acids (PUFA) from 9.22% to 55.17%. The predominant fatty acids identified were palmitic acid (C16:0), linoleic acid (C18:2 ω−6), oleic acid (C18:1 ω−9), docosahexaenoic acid (DHA, C22:6) and eicosapentaenoic acid (EPA, C20:5). Additionally, very low levels of trans fatty acids (0.28–3.96%) were observed across all samples. The findings demonstrate that the fatty acid composition of KOs varies significantly depending on the source of raw materials and the specific production parameters employed. This research provides valuable data for the nutritional classification and commercial development potential of krill oil supplements.

Keywords

• Krill Oil
• Fatty Acid Profile
• GC-FID

Kaynakça

1. M. P. Castro-Gómez, F. Holgado, L. M. Rodríguez-Alcalá, O. Montero, J. Fontecha, Comprehensive study of the lipid classes of krill oil by fractionation and identification of triacylglycerols, diacylglycerols, and phospholipid molecular species by using UPLC/QToF-MS. Food Anal. Methods, 8, 2568–2580, 2015. https://doi.org/10.1007/s12161-015-0150-6.
2. O. Saether, T. E. Ellingsen, V. Mohr, Lipids of North Atlantic krill. J Lipid Res 27:274–285, 1987. https://doi.org/10.1016/S0022-2275(20)38835-0
3. A. Kolakowska, E. Kolakowski, M. Szczygielski, Winter season krill (Euphausia superba D.) as a source of n-3 polyunsaturated fatty acids. Food Nahrung, 38, 128–134, 1994. https://doi.org/10.1002/food.19940380204
4. N. I. Svetlova, R. V. Golovnya, I. L. Zhuravleva, D. N. Grigorieva, A. L. Samusenko, Gas chromatographic investigation of volatile nitrogen containing bases of Antarctic krill Euphausia superba. Dana Die Nahrung, 29, 143–151, 1985. https://doi.org/10.1002/food.19850290207
5. S. A. Murzina, V. P. Voronin, D. G. Bityutskii, Academician N. N. Nemova, Fatty acid content and lipid nutritional indexes in the Antarctic krill euphausia superba collected from three regions of the Atlantic sector of Antarctica. Doklady Biological Sciences, 519, 309–317, 2024. https://doi.org/10.1134/S0012496624600386.
6. D. O. Sologub, Current features of distribution, biolo- gy and horizontal migrations of Antarctic krill (Euphausia superba) in the Atlantic sector of Antarctica. Ph.D. Thesis, Cand. Sci. (Biol.) Dissertation, Moscow: VNIRO, 2016.
7. S. Nicol and J. Foster, The fishery for Antarctic krill: its current status and management regime, in Biology and Ecology of Antarctic Krill, Siegel, V., Ed., Cham: Springer-Verlag, 387-421, 2016. https://doi.org/ 10.1007/978-3-319-29279-3_11
8. J. Y. Lee, J. B. Hong, B. K. Kim, S. B. Shim, H. W. Jang, J. B. Lee, Analysis of fatty acid compositions and acid values of krill oil supplementary products from the Korean market. J. Microbiol. Biotechnol., 34(10), 1988–1994, 2024. https://doi.org/10.4014/jmb.2406.06026

9. F. S. H. Lu, I. Bruheim, C. Jacobsen, New parameters for evaluating the quality of commercial krill oil capsules from the aspect of lipid oxidation and non-enzymatic browning reactions. Eur. J. Lipid Sci. Technol., 117, 1214–1224, 2015. https://doi.org/10.1002/ejlt.201400512
10. J. Le Grandois, E. Marchioni, M. Zhao, F. Giuffrida, Investigation of natural phosphatidylcholine sources: separation and identification by liquid chromatography- electrospray ionization-tandem mass spectrometry (LC- DSI-MS2) of molecular species. J. Agric. Food Chem., 57, 6014–6020, 2009. https://doi.org/10.1021/jf900903e
11. L. Burri, The power of omega-3 phospholipids omega-3 fatty acids from Superba TM krill oil show increased bioavailability compared to triglyceride omega-3s. Agro Food Ind. Hi Tech., 22, 10–12, 2011.
12. B. R. Thomsen, B. O. Haugsgjerd, M. Griinari, H. F. S. Lu, Investigation of oxidative degradation and non- enzymatic browning reactions in krill and fish oils. Eur. J. Lipid Sci. Tech., 115, 1357–1366, 2013. https://doi.org/10.1002/ejlt.201300141
13. S. M. Ulven, K. B. Holven, Comparison of bioavailability of krill oil versus fish oil and health effect. Vasc Health Risk Manag., 11, 511–524, 2015. https://doi.org/10.2147/VHRM.S85165
14. J. P. Schuchardt, A. Hahn, Bioavailability of long-chain omega-3 fatty acids. Prostagland Leukot Essent Fat Acids, 89(1), 1–8, 2013. https://dx.doi.org/10.1016/j.plefa.2013.03.010
15. A. Zartmann, L. Völcker, S. Hammann, Quantitative analysis of fatty acids and vitamin E and total lipid profiling of dietary supplements from the German market. European Food Research and Technology, 249, 1035–1048, 2023. https://doi.org/10.1007/s00217-022-04193-7
16. M. D. Grynbaum, P. Hentschel, K. Putzbach, J. Rehbein, Unambiguous detection of astaxanthin and astax- anthin fatty acid esters in krill (Euphausia superba Dana). J. Sep. Sci., 28, 1685–1693, 2005. 1 https://doi.org/10.1002/jssc.200500152
17. S. Takaichi, K. Matsui, M. Nakamura, M. Muramatsu, S. Hanada, Fatty acids of astaxanthin esters in krill determined by mild mass spectrometry. Comp. Biochem. Phys. B., 136, 317–322, 2003. https://doi.org/10.1016/S1096-4959(03)00209-4
18. M. Kobayashi, Y. Sakamoto, Singlet oxygen quenching ability of astaxanthin esters from the green algae Haemato- coccus pluvialis. Biotech letter, 21, 265–269, 1999.
19. W. S. Harris, P. M. Kris-Etherton, K. A. Harris, Intakes of long-chain omega-3 fatty acid associated with reduced risk for death from cor- onary heart disease in healthy adults. Curr Atheroscler Rep., 10, 503– 509, 2008.
20. G. D. Eslick, P. R. C. Howe, C. Smith, R. Priest, A. Bensoussan, Benefits of fish oil supplementation in hyperlipidemia: a systematic review and meta-analysis. Int J Cardiol, 136, 4–16, 2009. https://doi.org/10.1016/j.ijcard.2008.03.092
21. E. M. Balk, A. H. Lichtenstein, M. Chung, B. Kupelnick, P. Chew, J. Lau, Effects of omega-3 fatty acids on serum markers of cardio- vascular disease risk: A systematic review. Atherosclerosis, 189, 19–30, 2006. https://doi.org/10.1016/j.atherosclerosis.2006.02.012
22. M. H. Davidson, E. A. Stein, H. E. Bays, K. C. Maki, R. T. Doyle, R. A. Shalwitz, C. M. Ballantyne, H. N. Ginsberg, Efficacy and tolerability of adding prescription Omega-3 fatty acids 4 g/d to Simvastatin 40 mg/d in hypertriglyceridemic patients: An 8-week, randomized, double-blind, placebo-controlled study. Clin Ther., 29, 1354–1367, 2007. https://doi.org/10.1016/j.clinthera.2007.07.018
23. J. L. Breslow, n–3 Fatty acids and cardiovascular disease. Am J Clin Nutr., 83, 1477–1482, 2006. https://doi.org/10.1093/ajcn/83.6.1477S
24. G. Akın, Ş.N. Karuk Elmas, F. N. Arslan, I. Yılmaz, A. Kenar, Chemometric classification and quantification of cold pressed grape seed oil in blends with refined soybean oils using attenuated total reflectance–mid infrared (ATR–MIR) spectroscopy. LWT – Food Science and Technology, 100, 126–137, 2019. https://doi.org/10.1016/j.lwt.2018.10.046
25. A. Kenar, B. Cicek, F. N. Arslan, G. Akın, Ş.N. Karuk Elmas, I. Yılmaz, Electron impact-mass spectrometry fingerprinting and chemometrics for rapid assessment of authenticity of edible oils based on fatty acid profiling. Food Analytical Methods., 12, 355–370, 2019. https://doi.org/10.1007/s12161-019-01472-0
26. F. N. Arslan, F. Çağlar, Attenuated total reflectance–Fourier transform infrared (ATR–FTIR) spectroscopy combined with chemometrics for rapid determination of cold–pressed wheat germ oil adulteration. Food Analytical Methods., 12, 355–370, 2019. https://doi.org/10.1007/s12161-018-1368-x
27. C. T. Srigley and I. C. Orr-Tokle, Presence of fatty-acid ethyl esters in krill oil dietary supplements. Lipids, 2018. https://doi.org/10.1002/lipd.12078