Skip to main content
SpringerLink
Log in

Preparation of regioisomers of structured TAG consisting of one mole of CLA and two moles of caprylic acid

  • Published:
Journal of the American Oil Chemists' Society

Abstract

TAG (MLM) with medium-chain FA (MCFA) at the 1,3-positions and long-chain FA (LCFA) at the 2-position, and TAG (LMM) with LCFA at the 1(3)-position and MCFA at 2,3(1)-positions are a pair of TAG regioisomers. Large-scale preparation of the two TAG regioisomers was attempted. A commercially available FFA mixture (FFA-CLA) containing 9-cis, 11-trans (9c, 11t)- and 10t,12c-CLA was selected as LCFA, and caprylic acid (C8FA) was selected as MCFA. The MLM isomer was synthesized by acidolysis of acyglycerols (AG) containing two CLA isomers with C8FA: A mixture of AG-CLA/C8 FA (1∶10, mol/mol) and 4 wt% immobilized Rhizomucor miehei lipase was agitated at 30°C for 72 h. The ratio of MLM to total AG was 51.1 wt%. Meanwhile, LMM isomer was synthesized by acidolysis of tricaprylin with FFA-CLA: A mixture of tricaprylin/FFA-CLA (1∶2, mol/mol) and 4 wt% immobilized R. miehei lipase was agitated at 30°C for 24 h. The ratio of LMM to total AG was 51.8 wt%. MLM and LMM were purified from 1,968 and 813 g reaction mixtures by stepwise short-path distillation, respectively. Consequently, MLM was purified to 92.3% with 49.1% recovery, and LMM was purified to 93.2% with 52.3% recovery. Regiospecific analyses of MLM and LMM indicated that the 2-positions of MLM and LMM were 95.1 mol% LCFA and 98.3 mol% C8 FA, respectively. The results showed that a process comprising lipase reaction and short-path distillation is effective for large-scale preparation of high-purity regiospecific TAG isomers.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Akoh, C.C., K.T. Lee, and L. 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 

  2. Xu, X., A.R.H. Skands, C.-E. Høy, H. Mu, S. Balchen, and J. Adler-Nissen, Production of Specific-Structured Lipids by Enzymatic Interesterification: Elucidation of Acyl Migration by Response Surface Design, J. Am. Oil Chem. Soc. 75:1179–1186 (1998).

    CAS  Google Scholar 

  3. Han, J.J., and T. Yamane, Enhancement of Both Reaction Yield and Rate of Synthesis of Structured Triacylglycerol Containing Eicosapentaenoic Acid Under Vacuum with Water Activity Control, Lipids 34:989–995 (1999).

    Article  CAS  Google Scholar 

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

    Google Scholar 

  5. 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, Weinheim, Germany, 2000, pp. 128–147.

    Chapter  Google Scholar 

  6. Kawashima, A., Y. Shimada, M. Yamamoto, A. Sugihara, T. Nagao S. Komemoshi, and Y. Tominaga, Enzymatic Synthesis of High-Purity Structured Lipids with Caprylic Acid at 1,3-Positions and Polyunsaturated Fatty Acid at 2-Position, J. Am. Oil Chem. Soc. 78:611–616 (2001).

    CAS  Google Scholar 

  7. Mu, H., J.-P. Kurvinen, H. Kallio, X. Xu, and C.-E. Høy, Quantitation of Acyl Migration During Lipase-Catalyzed Acidolysis and of the Regioisomers of Structured Triacylglycerols Formed, 78:959–964 (2001).

    CAS  Google Scholar 

  8. Xu, X., A. Skands, and J. Adler-Nissen, Purification of Specific Structured Lipids by Distillation: Effects on Acyl Migration, 78:715–718 (2001).

    CAS  Google Scholar 

  9. Negishi, S., Y. Arai, S. Arimoto, K. Tsuchiya, and I. Takahashi, Synthesis of 1,3-Dicapryloyl-2-docasahexaenoylglycerol by a Combination of Nonselective and sn-1,3-Selective Lipase Reactions, 80:971–974 (2003).

    CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  11. 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 

  12. Mu, H., and C.-E. Høy, Effect of Different Medium-Chain Fatty Acids on Intestinal Absorption of Structured Triacylglycerols, Lipids 35:83–89 (2000).

    Article  CAS  Google Scholar 

  13. Hamosh, M., and P. Hamosh, Specificity of Lipases: Developmental Physiology with Aspects—The Role of Lipase Selectivity in the Digestion of Milk Fat, in Enzyme Engineering of/with Lipases, edited by F.X. Malcata, Kluwer, Dordrecht, The Netherlands, 1996, pp. 31–49.

    Google Scholar 

  14. Iverson, S.J., C.L. Kirk, M. Harmosh, and J. Newsome, Milk Lipid Digestion in the Neonatal Dog: The Combined Actions of Gastric and Bile Salt Stimulated Lipases, Biochim. Biophys. Acta 1083:109–119 (1991).

    CAS  Google Scholar 

  15. 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, Am. J. Clin. Nutr. 61:56–61 (1995).

    CAS  Google Scholar 

  16. Pariza, M.W., CLA, A New Cancer Inhibitor in Dairy Products, Bull. Int. Dairy Fed. 257:29–30 (1991).

    CAS  Google Scholar 

  17. Ha, Y.L., N.K. Grimm, and M.W. Pariza, Anticarcinogens from Fried Ground Beef: Heat-Altered Derivatives of Linoleic Acid, Carcinogenesis 8:1881–1887 (1987).

    CAS  Google Scholar 

  18. Park, Y., K.J. Albright, W. Liu, J.M. Storkson, M.E. Cook, and M.W. Pariza, Effect of Conjugated Linoleic Acid on Body composition in Mice, Lipids 32:853–858 (1997).

    Article  CAS  Google Scholar 

  19. Ostrowska, E., M. Muralitharan, R.F. Cross, D.E. Bauman, and F.R. Dunshea, Dietary Conjugated Linoleic Acids Increase Lean Tissue and Decrease Fat Deposition in Growing Pigs, J. Nutr. 129:2037–2042 (1999).

    CAS  Google Scholar 

  20. Rahman, S.M., Y.-M. Wang, H. Yotsumoto, J.-Y. Cha, S.-Y. Han, S. Inoue, and T. Yanagita, Effect of Conjugated Linoleic Acid on Serum Leptin Concentration, Body-Fat Accumulation, and β-Oxidation of Fatty Acid in OLETF Rats, Nutrition 17:385–390 (2001).

    Article  CAS  Google Scholar 

  21. Lee, K.N., D. Kritchevsky, and M.W. Pariza, Conjugated Linoleic Acid and Atherosclerosis in Rabbits, Atherosclerosis 108:19–25 (1994).

    Article  CAS  Google Scholar 

  22. Nicolosi, R.J., E.J. Rogers, D. Kritchevsky, J.A. Scimeca, and P.J. Huth, Dietary Conjugated Linoleic Acid Residues Plasma Lipoproteins and Early Aortic Atherosclerosis in Hypercholesterolemic Hamsters, Artery 22:266–277 (1997).

    CAS  Google Scholar 

  23. Sugano, M., A. Tsujita, M. Yamasaki, M. Noguchi, and K. Yamada, Conjugated Linoleic Acid Modulates Tissue Levels of Chemical Mediators and Immunoglobulins in Rats, Lipids 33:521–527 (1998).

    Article  CAS  Google Scholar 

  24. Yamauchi-Sato, Y., T. Nagao, T. Yamamoto, T. Terai, A. Sugihara, and Y. Shimada, Fractionation of Conjugated Linoleic Acid Isomers by Selective Hydrolysis with Candida rugosa Lipase, J. Oleo Sci. 52:367–374 (2003).

    CAS  Google Scholar 

  25. Nagao, T., Y. Shimada, Y. Yamauchi-Sato, T. Yamamoto, M. Kasai, K. Tsutsumi, A. Sugihara, and Y. Tominaga, Fractionation and Enrichment of CLA Isomers by Selective Esterification with Candida rugosa Lipase, J. Am. Oil Chem. Soc. 79:303–308 (2002).

    CAS  Google Scholar 

  26. Shimada, Y., J. Ogawa, Y. Watanabe, T. Nagao, A. Kawashima, T. Kobayashi, and S. Shimizu, Regiospecific Analysis by Ethanolysis of Oil with Immobilized Candida antarctica Lipase, Lipids 38:1281–1286 (2003).

    Article  CAS  Google Scholar 

  27. Kawashima, A., Y. Shimada, T. Nagao, A. Ohara, T. Matsuhisa, A. Sugihara, and Y. Tominaga, Production of Structured TAG Rich in 1,3-Dicapryloyl-2-γ-linolenoyl Glycerol from Borage Oil, J. Am. Oil Chem. Soc. 79:871–877 (2002).

    CAS  Google Scholar 

  28. Nagao, T., A. Kawashima, M. Sumida, Y. Watanabe, K. Akimoto, H. Fukami, A. Sugihara, and Y. Shimada, Production of Structured TAG Rich in 1,3-Dicapryloyl-2-arachidonoyl Glycerol from Mortierella Single-Cell Oil, 79:871–877 (2002).

    Google Scholar 

  29. Becker, C.C., A. Rosenquist, and G. Hølmer, Regiospecific Analysis of Triacylglycerols Using Allyl Magnesium Bromide, Lipids 28:147–149 (1993).

    Google Scholar 

  30. Luddy, F.E., R.A. Barford, S.F. Herb, P. Magidman, and R.W. Riemenschneider, Pancreatic Lipase Hydrolysis of Triglycerides by a Semimicro Technique, J. Am. Oil Chem. Soc. 41:693–696 (1964).

    CAS  Google Scholar 

  31. Kallio, H., and G. Currie, Analysis of Natural Fats and Oils by Ammonia Negative Ion Tandem Mass Spectrometry—Triacylglycerols and Positional Distribution of Their Acyl Groups, in CRC Handbook of Chromatography, Analysis of Lipids, edited by K.D. Mukherjee and N. Weber, CRC Press, Boca Raton, Florida, 1993, pp. 435–458.

    Google Scholar 

  32. Irimescu, R., Y. Iwasaki, and C.T. Hou, Study of TAG Ethanolysis to 2-MAG by Immobilized Candida antarctica Lipase and Synthesis of Symmetrically Structured TAG, J. Am. Oil Chem. Soc. 79:879–883 (2002).

    CAS  Google Scholar 

  33. Irimescu, R., K. Furihata, K. Hata, Y. Iwasaki, and T. Yamane, Utilization of Reaction Medium-Dependent Regiospecificity of Candida antarctica Lipase (Novozym 435) for the Synthesis of 1,3-Dicapryloyl-2-docosahexaenoyl (or eicosapentaenoyl) Glycerol, 78:285–289 (2001).

    CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Food and Nutrition, Sonoda Women's University, 661-8520, Hyogo, Japan

    Akiko Kawashima & Yoshio Tominaga

  2. Department of Bioscience and Biotechnology, Faculty of Agriculture, Graduate School of Kyushu University, 812-8581, Fukuoka, Japan

    Ikuo Ikeda

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

    Toshihiro Nagao, Yomi Watanabe, Takashi Kobayashi & Yuji Shimada

Authors
  1. Akiko Kawashima
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Toshihiro Nagao
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yomi Watanabe
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Takashi Kobayashi
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Ikuo Ikeda
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Yoshio Tominaga
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Yuji Shimada
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Toshihiro Nagao.

About this article

Cite this article

Kawashima, A., Nagao, T., Watanabe, Y. et al. Preparation of regioisomers of structured TAG consisting of one mole of CLA and two moles of caprylic acid. J Amer Oil Chem Soc 81, 1013–1020 (2004). https://doi.org/10.1007/s11746-004-1015-3

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11746-004-1015-3

Key words

Search

Navigation