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Enzymatic synthesis of high-purity structured lipids with caprylic acid at 1,3-positions and polyunsaturated fatty acid at 2-position

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Journal of the American Oil Chemists' Society

Abstract

We attempted to synthesize high-purity structured triacylglycerols (TAG) with caprylic acid (CA) at the 1,3-positions and a polyunsaturated fatty acid (PUFA) at the 2-position by a two-step enzymatic method. The first step was synthesis of TAG of PUFA (TriP), and the second step was acidolysis of TriP with CA. Candida antarctica lipase was effective for the first reaction. When a reaction medium of PUFA/glycerol (3∶1, mol/mol) and 5% immobilized Candida lipase was mixed for 24 h at 40°C and 15 mm Hg, syntheses of TAG of γ-linolenic, arachidonic, eicosapentaenoic, and docosahexaenoic acids reached 89, 89, 88, and 83%, respectively. In these reactions, the lipase could be used for at least 10 cycles without significant loss of activity. In the second step, the resulting trieicosapentaenoin was acidolyzed at 30°C for 48h with 15 mol parts CA using 7% of immobilized Rhizopus delemar lipase. The CA content in the acylglycerol fraction reached 40 mol%. To increase the content further, the acylglycerols were extracted from the reaction mixture with n-hexane and were allowed to react again with CA under conditions similar to those of the first acidolysis. After three successive acidolysis reactions, the CA content reached 66 mol%. The content of dicapryloyl-eicosapentaenoyl-glycerol reached 86 wt% of acylglycerols, and the ratio of 1,3-dicapryloyl-2-eicosapentaenoyl-glycerol to 1(3),2-dicapryloyl-3(1)-eicosapentaenoyl-glycerol was 98∶2 (w/w). In this reaction, the lipase could be used for at least 20 cycles without significant loss of activity. Repeated acidolysis of the other TriP with CA under similar conditions synthesized 1,3-dicapryloyl-2-γ-linolenoyl-glycerol, 1,3-dicapryloyl-2-arachidonoyl-glycerol, and 1,3-dicapryloyl-2-docosahexaenoyl-glycerol in yields of 58, 87, and 19 wt%, respectively.

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References

  1. Grundt, H., D.W.T. Nilsen, O. Hetland, T. Aarsland, I. Baksaas, and T. Grande, ™-3 Fatty Acids Was Not Associated with Changes in Insulin Levels in Subjects with Combined Hyperlipidaemia, J. Intern. Med. 237:249–259 (1995).

    Article  CAS  Google Scholar 

  2. Kromhout, D., E.B. Bosschietor, and C.D.L. Coulander, The Inverse Relation Between Fish Consumption and 20-Year Mortality from Coronary Heart Disease, New Engl. J. Med. 312:1205–1209 (1985).

    Article  CAS  Google Scholar 

  3. Pilipson, B.E., D.W. Rothrock, W.E. Connor, W.S. Harris, and D.R. Illingworth, Reduction of Plasma Lipids, Lipoproteins and Apoproteins by Dietary Fish Oils in Patients with Hypertriglyceridemia, Ibid. 312:1210–1216 (1985).

    Article  Google Scholar 

  4. Hara, K., Pharmaceutical Application of Eicosapentaenoic Acid, Yushi (in Japanese) 46:91–99 (1993).

    CAS  Google Scholar 

  5. Maruyama, K., and M. Nishikawa, Physiological Function of a Fish Oil Component and Its Application to Foods, Food Chemicals (in Japanese) 1995(4):31–37 (1995).

    Google Scholar 

  6. Fiocchi, A., M. Sala, P. Signoroni, G. Banderai, C. Agostoni, and E. Riva, The Efficacy and Safety of γ-Linolenic Acid in the Treatment of Infantile Atopic Dermatitis, J. Int. Med. Res. 22:2–32 (1994).

    Google Scholar 

  7. Zurier, R.B., P. DeLuca, and D. Rothman, γ-Linolenic Acid, Inflammation, Immune Responses, and Rheumatoid Arthritis, in γ-Linolenic Acid: Metabolism and Its Roles in Nutrition and Medicine, edited by Y.-S. Huang and D.E. Mills, AOCS Press, Champaign, 1996, pp. 129–136.

    Google Scholar 

  8. Carlson, S.E., S.H. Werkman, J.M. Peeples, R.J. Cooke, and E.A. Tolley, Arachidonic Acid Status Correlates with First Year Growth in Preterm Infants, Proc. Natl. Acad. Sci. USA 90:1073–1077 (1993).

    Article  CAS  Google Scholar 

  9. Lanting, C.I., V. Fidler, M. Huisman, B.C.L. Touwen, and E.R. Boersma, Neurological Differences Between 9-Year-Old Children Fed Breast-Milk as Babies, Lancet 344:1319–1322 (1994).

    Article  CAS  Google Scholar 

  10. Christensen, M.S., C.-E. Høy, C.C. Becker, and T.G. Redgrave, Intestinal Absorption and Lymphatic Transport of Eicosapentaenoic (EPA), Docosahexaenoic (DHA), and Decanoic Acids: Dependence on Intramolecular Triacylglycerol Structure, J. Clin. Nutr. 61:56–61 (1995).

    CAS  Google Scholar 

  11. Ikeda, I., Y. Tomari, M. Sugano, S. Watanabe, and J. Nagata, Lymphatic Absorption of Structured Glycerolipids Containing Medium-Chain Fatty Acids and Linoleic Acid, and Their Effect on Cholesterol Absorption in Rats, Lipids 26:369–373 (1991).

    CAS  Google Scholar 

  12. Irimescu, R., M. Yasui, Y. Iwasaki, N. Shimidzu, and T. Yamane, Enzymatic Synthesis of 1,3-Dicapryloyl-2-eicosapentaenoylglycerol, J. Am. Oil Chem. Soc. 77:501–506 (2000).

    CAS  Google Scholar 

  13. Shimada, Y., N. Sakai, A. Sugihara, H. Fujita, Y. Honda, and Y. Tominaga, Large-Scale Purification of γ-Linolenic Acid by Selective Esterification Using Rhizopus delemar Lipase, Ibid. 75:1539–1543 (1998).

    CAS  Google Scholar 

  14. Shimada, Y., T. Nagao, A. Kawashima, M. Yamamoto, A. Sugihara, S. Komemushi, and Y. Tominaga, Immobilization of Rhizopus delemar Lipase, Kagaku to Kogyo (in Japanese) 74:117–121 (2000).

    CAS  Google Scholar 

  15. Shimada, Y., A. Sugihara, K. Maruyama, T. Nagao, S. Nakayama, H. Nakano, and Y. Tominaga, Production of Structured Lipid Containing Docosahexaenoic and Caprylic Acid Using Immobilized Rhizopus delemar Lipase, J. Ferment. Bioeng. 81:299–303 (1996).

    Article  CAS  Google Scholar 

  16. Shimada, Y., K. Maruyama, S. Okazaki, M. Nakamura, A. Sugihara, and Y. Tominaga, Enrichment of Polyunsaturated Fatty Acids with Geotrichum candidum Lipase, J. Am. Oil Chem. Soc. 71:951–954 (1994).

    CAS  Google Scholar 

  17. Shimada, Y., T. Nagao, Y. Hamasaki, K. Akimoto, A. Sugihara, S. Fujikawa, S. Komemushi, and Y. Tominaga, Enzymatic Synthesis of Structured Lipid Containing Arachidonic and Palmitic Acids, Ibid. 77:89–93 (2000).

    CAS  Google Scholar 

  18. Xu, X., Enzymatic Production of Structured Lipids: Process Reactions and Acyl Migration, inform 11:1121–1131 (2000).

    Google Scholar 

  19. Nagao, T., Y. Shimada, A. Sugihara, A. Murata, S. Komemushi, and Y. Tominaga, Use of Thermostable Fusarium heterosporum Lipase for Production of Structured Lipid Containing Oleic and Palmitic Acids in Organic Solvent-Free Systems, J. Am. Oil Chem. Soc. 78:167–172 (2001).

    CAS  Google Scholar 

  20. Akoh, C.C., K.-T. Lee, and L.B. Fomuso, Synthesis of Positional Isomers of Structured Lipids with Lipases as Biocatalysts, in Structural Modified Food Fats: Synthesis, Biochemistry, and Use, edited by A.B. Christophe, AOCS Press, Champaign, 1998, pp. 46–72.

    Google Scholar 

  21. Shimada, Y., A. Sugihara, and Y. Tominaga, Production of Functional Lipids Containing Polyunsaturated Fatty Acids with Lipase, in Enzymes in Lipid Modification, edited by U.T. Bornscheuer, Wiley-VCH Verlag GmbH, Weinheim, 2000, pp. 128–147.

    Chapter  Google Scholar 

  22. Yamane, T., Lipase-Catalyzed Synthesis of Structured Triacylglycerols Containing Polyunsaturated Fatty Acids: Monitoring the Reaction and Increasing the Yield, Ibid., pp. 148–169.

    Chapter  Google Scholar 

  23. Shimada, Y., A. Sugihara, H. Nakano, T. Yokota, T. Nagao, S. Komemushi, and Y. Tominaga, Production of Structured Lipids Containing Essential Fatty Acids by Immobilized Rhizopus delemar Lipase, J. Am. Oil Chem. Soc. 73:1415–1420 (1996).

    Article  CAS  Google Scholar 

  24. Shimada, Y., A. Sugihara, H. Nakano, T. Nagao, M. Suenaga, S. Nakai, and Y. Tominaga, Fatty Acid Specificity of Rhizopus delemar Lipase in Acidolysis, J. Ferment. Bioeng. 83:321–327 (1997).

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Sonoda Women's Junior College, 661-8520, Hyogo, Japan

    Akiko Kawashima

  2. Department of Agricultural Chemistry, School of Agriculture, Kinki University, 631-8505, Nara, Japan

    Miwa Yamamoto & Sadao Komemushi

  3. Osaka Municipal Technical Research Institute, 1-6-50 Morinomiya, Joto-ku, 536-8553, Osaka, Japan

    Yuji Shimada, Akio Sugihara, Toshihiro Nagao & Yoshio Tominaga

Authors
  1. Akiko Kawashima
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  2. Yuji Shimada
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  3. Miwa Yamamoto
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  4. Akio Sugihara
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  5. Toshihiro Nagao
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  6. Sadao Komemushi
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  7. Yoshio Tominaga
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Correspondence to Yuji Shimada.

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Kawashima, A., Shimada, Y., Yamamoto, M. et al. Enzymatic synthesis of high-purity structured lipids with caprylic acid at 1,3-positions and polyunsaturated fatty acid at 2-position. J Amer Oil Chem Soc 78, 611–616 (2001). https://doi.org/10.1007/s11746-001-0313-0

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  • DOI: https://doi.org/10.1007/s11746-001-0313-0

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