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Synthesis, Purification, and Acyl Migration Kinetics of 2-Monoricinoleoylglycerol

  • Original Paper
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Journal of the American Oil Chemists' Society

Abstract

2-Monoricinoleoylglycerol (2-MRG) was synthesized by the Novozym 435 catalyzed alcoholysis of castor oil in excess ethanol (1:70 mol:mol) at ambient temperature. Due to the fatty acid C12-OH group, conventional liquid–liquid extraction methods developed for less polar, non-hydroxylated 2-monoacylglycerols (2-MAG) proved inadequate for 2-MRG purification. Alternatively, 2-MRG was purified by normal-phase flash chromatography (FC) on silica gel using a binary acetone-hexane gradient mobile phase. Gram quantities of 2-MRG were isolated in 63 % yield and contained no residual diacylglycerol (DAG), which fail to separate using liquid–liquid extraction methods. The 2-MRG was obtained at ~90 mol% relative to 1-MRG, proving that the FC method did not appreciably catalyze acyl migration. 1H-NMR spectroscopy was used to monitor the spontaneous acyl migration of isolated 2-MRG from 20 to 80 °C. The relative energy of activation calculated from the Arrhenius relationship of the 2-MRG acyl migration rate constants was 82.9 kJ/mol. This was ~two-fold higher than the theoretical ΔG 298.15 calculated from molecular modeling using density functional calculations (B3LYP/6−31 + G*) of 2-MRG, the ketal ring transition state, and 1-monoricinoleoylglycerol (1-MRG). The synthesis and isolation methods reported herein provide a convenient means to access useful intermediates for functionalized structured lipids.

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References

  1. Nunn JF (1996) Ancient Egyptian medicine. Oklahoma Press, Norman, pp 1–240

    Google Scholar 

  2. Tunaru S, Althoff TF, Nüsing RM, Diener M, Offermanns S (2012) Castor oil induces laxation and uterus contraction via ricinoleic acid activating prostaglandin EP3 receptors. Proc Natl Acad Sci USA 109:9179–9184

    Article  CAS  Google Scholar 

  3. Lin JT, Turner C, Liao LP, McKeon TA (2003) Identification and quantification of the molecular species of acylglycerols in castor oil by HPLC using ELSD. J Liq Chromatogr Relat Technol 26:773–780

    Article  CAS  Google Scholar 

  4. McKeon TA, Chen GQ, He X, Ahn Y-J, Lin J-T (2007) The enzymology of castor oil biosynthesis. In: Janick J, Whipkey A (eds) Issues in new crops and new uses. ASHS Press, Alexandria, pp 101–104

    Google Scholar 

  5. Zope DD (2010) Castor oil-based chemicals. Information 21:186–187

    Google Scholar 

  6. Green BA, Yu RJ, Van Scott EJ (2009) Clinical and cosmeceutical uses of hydroxyacids. Clin Dermatol 27:495–501

    Article  Google Scholar 

  7. Kornhauser A, Coelho S, Hearing V (2010) Applications of hydroxy acids: classification, mechanisms, and photoactivity. Clin Cosmet Investig Dermatol 3:135–142

    Article  CAS  Google Scholar 

  8. Delprete K (2010) Transdermal ricinoleic acid compositions, US Patent Application 2010/0034873 A1

  9. Camp RDR, Mallet AI, Wollard PM, Brain SD, Black AK, Greaves MW (1983) The identification of hydroxy fatty acids in psoriatic skin. Prostaglandins 26:431–447

    Article  CAS  Google Scholar 

  10. Miller CC, Ziboh VA (1990) Induction of epidermal hyperproliferation by topical n-3 polyunsaturated fatty acids on guinea pig skin linked to decreased levels of 13-hydroxyoctadecadienoic acid (13-HODE). J Invest Dermatol 94:353–358

    Article  CAS  Google Scholar 

  11. Jones PM, Bennett MJ (2011) Clinical applications of 3-hydroxy fatty acid analysis by gas chromatography–mass spectrometry. Biochim Biophys Acta 1811:657–662

    Article  CAS  Google Scholar 

  12. Mutlu H, Meier MAR (2010) Castor oil as a renewable resource for the chemical industry. Eur J Lipid Sci Technol 112:10–30

    Article  CAS  Google Scholar 

  13. Casper DM, Newbold T (2011) Methods of preparing hydroxy functional vegetable oils, US 7,893,287 B2

  14. Dierig DA, Wang G, McCloskey WB, Thorp KR, Isbell TA, Ray DT, Foster MA (2011) Lesquerella: new crop development and commercialization in the U.S. Ind Crop Prod 34:1381–1385

    Article  Google Scholar 

  15. Cermak SC, Brandon KB, Isbell TA (2006) Synthesis and physical properties of estolides from lesquerella and castor fatty acid esters. Ind Crop Prod 23:54–64

    Article  CAS  Google Scholar 

  16. Isbell TA, Lowery BA, DeKeyser SS, Winchell ML, Cermak SC (2006) Physical properties of triglyceride estolides from lesquerella and castor oils. Ind Crop Prod 23:256–263

    Article  CAS  Google Scholar 

  17. Biresaw G, Cermak SC, Isbell TA (2007) Film-forming properties of estolides. Tribol Lett 27:69–78

    Article  CAS  Google Scholar 

  18. Kremers FJ (1971) Sulfonation of castor oil with sulfur trioxide. J Am Chem Soc 48:314–317

    CAS  Google Scholar 

  19. Chen B, Zhang H, Cheong L-Z, Tan T, Xu X (2012) Enzymatic production of ABA-type structured lipids containing omega-3 and medium-chain fatty acids: effects of different acyl donors on the acyl migration rate. Food Bioprocess Technol 5:541–547

    Article  CAS  Google Scholar 

  20. Irimescu R, Iwasaki Y, Hou CT (2002) 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

    Article  CAS  Google Scholar 

  21. Shriver DF, Drezdon MA (1986) The manipulation of air-sensitive compounds, 2nd edn. Wiley, New York, pp 7–45

    Google Scholar 

  22. Sreenivasan B, Kamath NR, Kane JG (1956) Studies on castor oil. I. Fatty acid composition of castor oil. J Am Oil Chem Soc 33:61–66

    Article  CAS  Google Scholar 

  23. Achaya KT, Craig BM, Youngs CG (1964) The component fatty acids and glycerides of castor oil. J Am Oil Chem Soc 41:783–784

    CAS  Google Scholar 

  24. Sreenivasan B (1967) Fatty acid composition of castor oil by gas-liquid chromatography. J Am Oil Chem Soc 44:119–120

    Article  CAS  Google Scholar 

  25. Lin J-T (2008) Biosynthesis of castor oil studied by the regiospecific analysis of castor triacylglycerols by ESI-MS. In: Hou CT, Shaw J-F (eds) Biocatalysis and bioenergy. Wiley, Hoboken, pp 449–461

    Chapter  Google Scholar 

  26. Compton DL, Vermillion KE, Laszlo JA (2007) Acyl migration kinetics of 2-monoacylglycerols from soybean oil via 1H NMR. J Am Oil Chem Soc 84:343–348

    Article  CAS  Google Scholar 

  27. Compton D, Laszlo J, Appell M, Vermillion K, Evans K (2012) Influence of fatty acid desaturation on spontaneous acyl migration in 2-monoacylglycerols. J Am Oil Chem Soc 89:2259–2267

    Article  CAS  Google Scholar 

  28. Compton DL, Laszlo JA, Evans KO (2013) Influence of solid supports on acyl migration in 2-monoacylglycerols: purification of 2-MAG via flash chromatography. J Am Oil Chem Soc 90:1397–1403

    Article  CAS  Google Scholar 

  29. Hatzakis E, Agiomyrgianaki A, Kostidis S, Dais P (2011) High-resolution NMR spectroscopy: an alternative fast tool for qualitative and quantitative analysis of diacylglycerol (DAG) oil. J Am Oil Chem Soc 88:1695–1708

    Article  CAS  Google Scholar 

  30. Laszlo JA, Compton DL, Vermillion KE (2008) Acyl migration kinetics of vegetable oil 1,2-diacylglycerols. J Am Oil Chem Soc 85:307–312

    Article  CAS  Google Scholar 

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Acknowledgments

The authors thank Leslie Smith and Judy Blackburn for their excellent technical assistance.

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Authors and Affiliations

  1. Renewable Product Technology Research Unit, National Center for Agricultural Utilization Research, Agricultural Research Service, United States Department of Agriculture, Peoria, IL, 61604, USA

    David L. Compton, Joseph A. Laszlo & Kervin O. Evans

  2. Bacterial Foodborne Pathogens and Mycology Research Unit, National Center for Agricultural Utilization Research, Agricultural Research Service, United States Department of Agriculture, Peoria, IL, 61604, USA

    Michael Appell

  3. Functional Foods Research Unit, National Center for Agricultural Utilization Research, Agricultural Research Service, United States Department of Agriculture, Peoria, IL, 61604, USA

    Karl E. Vermillion

Authors
  1. David L. Compton
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  2. Joseph A. Laszlo
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  3. Michael Appell
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  4. Karl E. Vermillion
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  5. Kervin O. Evans
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Correspondence to David L. Compton.

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Compton, D.L., Laszlo, J.A., Appell, M. et al. Synthesis, Purification, and Acyl Migration Kinetics of 2-Monoricinoleoylglycerol. J Am Oil Chem Soc 91, 271–279 (2014). https://doi.org/10.1007/s11746-013-2373-2

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  • DOI: https://doi.org/10.1007/s11746-013-2373-2

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