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Multi-length-Scale Elucidation of Kinetic and Symmetry Effects on the Behavior of Stearic and Oleic TAG. I. SOS and SSO

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Journal of the American Oil Chemists' Society

Abstract

Positional isomerism in triacylglycerols (TAG), present in a molecular ensemble arising from genetic, environmental or processing-induced changes, can result in significant differences in the macroscopic physico-chemical functionality of crystallized networks of the ensemble. The differences in phase behavior induced by positional isomerism and levels of unsaturation of pure oleoyl-distearoyl TAG (SOS, SSO) were detailed at different length scales. The effect of cooling rate on the polymorphism, thermal properties and microstructure were systematically investigated between 0.1 and 5 °C/min. The symmetrical SOS presented a complex polymorphism and microstructure, which varied predictively with cooling rate. The crystal phases and transitions observed for this TAG are similar to those of cocoa butter. In contrast, the cooling rate had limited effect on the phase behavior of the asymmetrical SSO. The differences between the crystallization of SSO and SOS induced by kinetics are related to the kinked oleic acid at the outer position in the SSO molecule and favorable end group structure for SOS. The fundamental understanding gained from such model systems can be used in many industrial formulations, particularly foods.

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References

  1. O’Brien RD (2004) Fats and oils: formulating and processing for applications. CRC Press, Boca Raton

    Google Scholar 

  2. Bernstein J (2002) Polymorphism in molecular crystals. Clarendon Press, Oxford

    Google Scholar 

  3. Widlak N, Hartel R, Narine SS (2001) Crystallization and Solidification properties of lipids. AOCS Press, Champaign

    Google Scholar 

  4. Ghotra BS, Dyal SD, Narine SS (2002) Lipid shortenings: a review. Food Res Int 35:1015–1048

    Article  CAS  Google Scholar 

  5. Humphrey KL, Narine SS (2007) Diminishing marginal utility of cooling rate increase on the crystallization behavior and physical properties of a lipid sample. J Am Oil Chem Soc 84:709–716

    Article  CAS  Google Scholar 

  6. Bouzidi L, Narine SS (2009) Evidence of critical cooling rates in the nonisothermal crystallization of triacylglycerols: a case for the existence and selection of growth modes of a lipid crystal network. Langmuir 26:4311–4319

    Article  CAS  Google Scholar 

  7. Narine SS, Humphrey KL, Bouzidi L (2006) Modification of the Avrami model for application to the kinetics of the melt crystallization of lipids. J Am Oil Chem Soc 83:913–921

    Article  CAS  Google Scholar 

  8. Rozendaal A, Macrae AR (1997) Interesterification of oils and fats. In: Gunstone FD, Padley FB (eds) Lipid technologies and applications. Marcel Dekker, New York, pp 223–264

    Google Scholar 

  9. Garcia-Macias P, Gordon MH, Frazier RA, Smith K, Gambelli L (2012) Effect of TAG composition on performance of low saturate shortenings in puff pastry. Eur J Lipid Sci Technol 114:741–747

    Article  CAS  Google Scholar 

  10. Lipp M, Anklam E (1998) Review of cocoa butter and alternative fats for use in chocolate—part A. Compositional data. Food Chem 62:73–97

    Article  CAS  Google Scholar 

  11. Wainwright RE (1996) Oils and fats in confections. In: Hui YH (ed) Bailey’s industrial oil and fat products. Wiley, New York, pp 353–408

    Google Scholar 

  12. Ueno S, Minato A, Yano J, Sato K (1999) Synchrotron radiation X-ray diffraction study of polymorphic crystallization of SOS from liquid phase. J Cryst Growth 198–199 Part2:1326–1329

    Article  Google Scholar 

  13. Yano J, Sato K, Kaneko F, Small DM, Kodali DR (1999) Structural analyses of polymorphic transitions of sn-1,3-distearoyl-2-oleoylglycerol (SOS) and sn-1,3-dioleoyl-2-stearoylglycerol (OSO): assessment on steric hindrance of unsaturated and saturated acyl chain interactions. J Lipid Res 40:140–151

    CAS  Google Scholar 

  14. Yano J, Ueno S, Sato K, Arishima T, Sagi N, Kaneko F, Kobayashi M (1993) FT-IR study of polymorphic transformations in SOS, POP, and POS. J Phys Chem 97:12967–12973

    Article  CAS  Google Scholar 

  15. Sato K, Arishima T, Wang Z, Ojima K, Sagi N, Mori H (1989) Polymorphism of POP and SOS. I. Occurrence and polymorphic transformation. J Am Oil Chem Soc 66:664–674

    Article  CAS  Google Scholar 

  16. Rousser P, Rappaz M (1996) Crystallization kinetics of the pure triacylglycerols glycerol-1,3-dipalmitate-2-oleate, glycerol-1-palmitate-2-oleate-3-stearate, and glycerol-1,3-distearate-2-oleate. J Am Oil Chem Soc 73:1051–1057

    Article  Google Scholar 

  17. Koyano T, Hachiya I, Arishimo T, Sato K, Sagi N (1989) Polymorphism of POP and SOS. II. Kinetics of melt crystallization. J Am Oil Chem Soc 66:675–679

    Article  CAS  Google Scholar 

  18. Ueno S, Minato A, Seto H, Amemiya Y, Sato K (1997) Synchrotron radiation X-ray diffraction study of liquid crystal formation and polymorphic crystallization of SOS (sn-1,3-distearoyl-2-oleoyl glycerol). J Phys Chem B 101:6847–6854

    Article  CAS  Google Scholar 

  19. Mykhaylyk OO, Hamley IW (2004) The packing of triacylglycerols from SAXS measurements: application to the structure of 1,3-distearoyl-2-oleoyl-sn-glycerol crystal phases. J Phys Chem B 108:8069–8083

    Article  CAS  Google Scholar 

  20. Peschar R, Pop MM, De Ridder DJA, van Mechelen JB, Driessen RAJ, Schenk H (2004) Crystal structures of 1,3-distearoyl-2-oleoylglycerol and cocoa butter in the β(V) phase reveal the driving force behind the occurrence of fat bloom on chocolate. J Phys Chem B 108:15450–15453

    Article  CAS  Google Scholar 

  21. van Mechelen JB, Peschar R, Schenk H (2006) Structures of mono-unsaturated triacylglycerols. I. The β1 polymorph. Acta Crystallog. B 62:1121–1130

    Article  CAS  Google Scholar 

  22. Takeuchi M, Ueno S, Floter E, Sato K (2002) Binary phase behavior of 1,3-distearoyl-2-oleoyl-sn-glycerol (SOS) and 1,3-distearoyl-2-linoleoyl-sn-glycerol (SLS). J Am Oil Chem Soc 79:627–632

    Article  CAS  Google Scholar 

  23. Koyano T, Hachiya I, Sato K (1992) Phase behavior of mixed systems of SOS and OSO. J Phys Chem 96:10514–10520

    Article  CAS  Google Scholar 

  24. Lavery H (1958) Differential thermal analysis of fats. II. Melting behavior of some pure glycerides. J Am Oil Chem Soc 35:418–422

    Article  CAS  Google Scholar 

  25. Engström L (1992) Triglyceride systems forming molecular compounds. Eur J Lipid Sci Technol 94:173–181

    Google Scholar 

  26. Takeuchi M, Ueno S, Sato K (2002) Crystallization kinetics of polymorphic forms of a molecular compound constructed by SOS (1,3-distearoyl-2-oleoyl-sn-glycerol) and SSO (1,2-distearoyl-3-oleoyl-rac-glycerol). Food Res Int 35:919–926

    Article  CAS  Google Scholar 

  27. Bentley PH, McCrae W (1970) Efficient synthesis of symmetrical 1,3-diglycerides. J Org Chem 35:2082–2083

    Article  CAS  Google Scholar 

  28. Bresson S, Rousseau D, Ghosh S, Marssi ME, Faivre V (2011) Raman spectroscopy of the polymorphic forms and liquid state of cocoa butter. Eur J Lipid Sci Technol 113:992–1004

    Article  CAS  Google Scholar 

  29. Larsson K (1966) Classification of glyceride crystal forms. Acta Chem Scand 20:2255–2260

    Article  CAS  Google Scholar 

  30. Mykhaylyk OO, Martin CM (2009) Effect of unsaturated acyl chains on structural transformations in triacylglycerols. Eur J Lipid Sci Technol 111:227–235

    Article  CAS  Google Scholar 

Download references

Acknowledgments

We would like to thank the Grain Farmers of Ontario, Elevance Renewable Sciences, Trent University, the GPA-EDC, Ontario Ministry of Agriculture, Food and Rural Affairs, Industry Canada and NSERC for financial support.

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Correspondence to Suresh S. Narine.

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Baker, M., Bouzidi, L., Garti, N. et al. Multi-length-Scale Elucidation of Kinetic and Symmetry Effects on the Behavior of Stearic and Oleic TAG. I. SOS and SSO. J Am Oil Chem Soc 91, 559–570 (2014). https://doi.org/10.1007/s11746-013-2404-z

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  • DOI: https://doi.org/10.1007/s11746-013-2404-z

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