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J Am Oil Chem Soc DOI 10.

1007/s11746-011-1952-3

LETTER TO THE EDITOR

Triacylglycerol Polymorphism: What Can We Learn from Space Groups and Crystalline Tendency?
R. John Craven Robert W. Lencki

Received: 20 July 2011 / Revised: 16 September 2011 / Accepted: 6 October 2011 AOCS 2011

Polymorphism strongly affects the functionality of fat and fat-containing foods. For instance, margarine in the desirable b0 form is smooth and creamy, whereas, the more stable b polymorph is associated with a grainy texture. Similarly, cocoa butter in form V produces chocolate that is glossy, snaps nicely, and melts in your mouth, whereas, the more stable form VI is a dull white or grey lm that does not melt as readily [1]. Many organic compounds are polymorphic and this polymorphism occurs via numerous mechanismssome of which are ill-dened [2]. Similarly, the current understanding of triacylglycerol (TAG) polymorphism is, in many ways, incomplete. A number of factors are thought to contribute to TAG polymorphism. In the solid phase, TAG molecules adopt one of several possible chain-length (double or triple chain length aka 2L or 3L) and glycerol conformation (chair or tuning fork) structures. These structures are determined to a large part by the TAGs substituent fatty acids and their relative afnity for each other, with acyl chains congregating due to similarities in length and degree of saturation [3, 4]. In addition, variations in acyl-chain tilt as well as acyl-chainand methyl-end-packing are also thought to contribute to, or be indicative of, polymorphic behavior [5, 6]. While this descriptive mechanism has been useful, particularly for molecules with minimal stereochemistry (i.e. n-parafns and waxes) [7] it is incapable of predicting or explaining some common polymorphic behavior of TAG. For example the current model cannot explain why, while simple (monoacid)
R. J. Craven R. W. Lencki (&) Department of Food Science, University of Guelph, Guelph, ON N1G 2W1, Canada e-mail: rlencki@uoguelph.ca R. J. Craven e-mail: craven@uoguelph.ca

TAG are b-tending, enantiopure mixed (di- and triacid) TAG (e.g. milk fat, sn-10:0-10:0-16:0 and sn-16:0-16:0-14:0) are b0 -stable [810]. Moreover, it does not explain why enantiopure TAG (sn-10:0-10:0-16:0 and sn-16:0-16:0-14:0) are b0 -stable while the corresponding racemic mixtures (rac-10:0-10:0-16:0 and rac-16:0-16:0-14:0) are b-stable [9, 10]. Perhaps the current descriptive mechanism for TAG polymorphism could be improved by including some consideration for the stereochemical conformation of constituent molecules.

Crystalline Tendency The relative stereochemistry of molecules within the unit cell can be determined by spectroscopic means (single-crystaland powder diffraction X-ray) or from the phase behavior of enantiomeric mixtures (crystalline tendency) [1113]. In our lab we employed the latter technique to understand the relationship between polymorphism and stereochemistry for a chiral TAG system (sn-10:0-10:0-16:0 and sn-16:0-10:0-10:0). Samples of enantiopure 1,2-bisdecanoyl-3-palmitoyl-sn-glycerol (sn-10:0-10:0-16:0; E-TAG) and racemic bisdecanoyl-1(3)-palmitoyl-rac-glycerol (rac-10:0-10:0-16:0 : 50% sn-10:0-10:0-16:0 ? 50% sn-16:0-10:0-10:0; R-TAG) were prepared in [99% purity (by GC) [9]. While their melting points were similar (sn-10:0-10:0-16:0: Tp = 32.9 C; rac-10:0-10:0-16:0: Tp = 33.38 C) their polymorphism (b0 -tending E-TAG vs b-tending R-TAG) and consequently their crystallization and melting behavior was remarkably different [9]. A similar polymorphic tendency has been reported for sn-16:0-16:0-14:0 (b0 -tending) and rac-16:0-16:0-14:0 (b-tending) [10]. Liquidus data was used to construct a phase diagram for enantiomeric mixtures of sn-10:0-10:0-16:0 and

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J Am Oil Chem Soc

sn-16:0-10:0-10:0 (cf. Fig. 12 in Reference 9). One half of the phase diagram was derived with the understanding that the other half of the diagram is an identical mirror image. Analysis of this data revealed that blends of sn-10:0-10:0-16:0 and sn-16:0-10:0-10:0 form a meta-stable eutectic (i.e. conglomerate in the b0 polymorph) and a stable 1:1 molecular compound (i.e. racemic compound in the b polymorph). In addition, the most thermodynamically-stable polymorph for enantiopure sn-10:0-10:0-16:0 and by analogy sn-16:0-10:0-10:0 is b0 . Thus, for the subject compounds, molecules of opposite enantiomers occupy separate unit cells in the b0 -form and are matched in the unit cell of the b-form [9]. These results are summarized under the heading crystalline tendency in Tables 1, 2.

Table 2 Unit cell stereochemistry for b0 -form triacylglycerols One stereoisomer in the unit cell Crystalline tendency [9] Pure enantiomer (sn-10:0-10:0-16:0) is b-tending Racemic mixture (sn-10:0-10:0-16:0 and sn-16:0-10:0-10:0) forms a metastable conglomerate (eutectic) Single-crystal X-ray 12:0-14:0-12:0 C2 [28], sn-16:0-16:0-14:0 C2 [10 ] X-ray powder diffraction 12:0-14:0-12:0, 14:0-16:0-14:0 (at 250 K) I2 [29] 16:0-18:1t-16:0, 16:0-18:0-16:0, 16:0-16:0-18:1t, 16:0-16:018:0 I2 [6] Both stereoisomers in the unit cell Single-crystal X-ray

Stereochemistry of the Unit Cell for b- and b0 -Form Triacylglycerols As mentioned above, the relative stereochemistry of molecules within the unit cell can also be determined by X-ray spectroscopy (single-crystal and powder diffraction). This information is expressed by the crystallographic space group determined for the crystal structure [11, 12]. Crystallographic space groups have been assigned for many b- and b0 -form TAG and as a result the relative stereochemistry of their unit cells can be determined (Tables 1, 2).

11:0-11:0-11:0 P21/c [30]twinning observed but not taken into account X-ray powder diffraction 10:0-12:0-10:0, 14:0-16:0-14:0 (at 298 K), 16:0-18:0-16:0 Iba2 [29], 16:0-18:0-18:0 C2/c [6]difculties reported but twinning not considered

Table 1 Unit cell stereochemistry for b-form triacylglycerols Both stereoisomers in the unit cell Crystalline tendency [9] sn-10:0-10:0-16:0 and sn-16:0-10:0-10:0 (racemic mixture) form a stable 1:1 molecular compound (racemic compound) Single-crystal X-ray " 10:0-10:0-10:0 P1 [18], 12:0-12:0-12:0 P" [19], 18:0-18:0-18:0 1 [20], 10:0-C11Br:0-10:0 P" [21], 16:0-16:0-16:0 P" [22], 1 1 18:1t-18:1t-18:1t P" [23] 1 X-ray powder diffraction 14:0-14:0-14:0, 18:0-18:0-18:0 P" [24], 13:0-13:0-13:0, 1 15:0-15:0-15:0, 17:0-17:0-17:0, 19:0-19:0-19:0 P" [25], 1 18:0-18:1-18:0 P" [1], 14:0-18:1-14:0, 16:0-18:1-16:0, 1 18:0-18:1-18:0, 16:0-18:1-18:0, 18:0-18:1-20:0 P21/n [26], 16:0-18:1-16:0, 18:0-18:1-18:0, 16:0-18:1-18:0, 18:0-18:1-20:0 Cc [27], 18:0-18:0-18:1t, 16:0-18:0-18:0, 16:0-16:0-18:0, 16:0-16:0-18:1t, 14:0-14:0-16:0, 12:0-14:0-14:0, 12:0-12:0-14:0, 18:0-18:1t-18:0, 16:0-18:1t-16:0, 16:0-18:0-16:0 P" [5] 1 One stereoisomer in the unit cell Single-crystal X-ray sn-16:0-16:0-2:0 P21 [14]exceptional polymorphic behavior common for acetoyl acylglycerols

Based on crystalline tendency and crystallographic space group assignments (P" for the most part) the unit cell 1 of b-form TAG generally contains both stereoisomers (Table 1). Not surprisingly, 1,2-dipalmitoyl-3-acetoyl-snglycerol (sn-16:0-16:0-2:0) [14] is an exception as are many acetoyl acylglycerols [15]. While the stereochemical composition of the unit cell for b-form TAG is clear-cut, the situation appears more complex for b0 -form TAG (Table 2). However, if the role of crystal twinning in TAG b0 forms is taken into account the matter is simplied. For b0 forms of TAG, the determination of crystal structure by X-ray (single-crystal and powder) is frequently confounded by the growth of crystal twins [4]; thus, variations in crystal growth conditions coupled with crystal twinning effects are a probable cause for the multitude of b0 forms reported for numerous TAG including tristearin (18:0-18:0-18:0) and tripalmitin (16:0-16:0-16:0). [Crystal twinning is] the growth of two or more differently oriented domains of a single structure into a twinned crystal twinning can be described in terms of a symmetry element, the twin-element, which, unlike normal symmetry elements, does not occur in every unit cell but relatively few timesor even only onceon a macroscopic scale [16]. When results from X-ray studies where crystal twinning was negligible or was properly accounted for are included with the crystalline tendency results the unit cell for b0 form TAG contains only one stereoisomer (Table 2). It appears that the unit cell of all b-form TAG contains both stereoisomers (Table 1)the exceptional polymorphism of acetoyl acylglycerols notwithstanding (viz.

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J Am Oil Chem Soc Fig. 1 Schematic for a b and b b0 unit cells of achiral TAG and racemic mixtures of chiral TAG

sn-16:0-16:0-2:0). Pure enantiomers must therefore assume the b0 form because the unit cell for these compounds can only contain one stereoisomer. Moreover, when the effects of twinning are taken into account the current data indicates that the unit cell for b0 forms of chiral and achiral TAG (e.g. the CnCn?2Cn series) contain only one stereoisomer (Table 2). This preliminary analysis demonstrates the key role unit cell stereochemistry plays in TAG polymorphism (Fig. 1). At present, crystallographic space group assignments, drawn from X-ray data, are available for many b- and b0 -form TAG (Tables 1, 2). However, only one study to determine the crystalline tendency of chiral TAG via the binary phase behavior of enantiomeric mixtures has been conducted (Tables 1, 2) [9]. Further work in this area will indicate whether the trends noted here are system-specic or whether they are the general rule. Given the role of crystalline tendency in the polymorphism of chiral systems [13] and new insights regarding conformational polymorphism [17] we hypothesize that these observations will apply to the general case.

References
1. Peschar R, Pop MM, De Ridder DJA, Van Mechelen JB, Driessen R, Schenk H (2004) Crystal structures of 1,3-distearoyl-2oleoylglycerol and cocoa butter in the beta(V) phase reveal the driving force behind the occurrence of fat bloom in chocolate. J Phys Chem B 108:1545015453 2. Bernstein J (2002) Polymorphism in molecular crystals. Oxford University Press, Oxford 3. Sato K, Ueno S (2001) Molecular interactions and phase behavior of polymorphic fats. In: Garti N, Sato K (eds) Crystallization Processes in Fats and Lipid Systems. Marcel Dekker, NY, pp 177288 4. Larsson K (1994) Lipids: molecular organization, physical functions and technical applications. The Oily Press, Dundee 5. Van Mechelen JB, Peschar R, Schenk H (2008) Structures of mono-unsaturated triacylglycerols. III. The beta-2 polymorphs of trans-mono-unsaturated triacylglycerols and related fully saturated triacylglycerols. Acta Cryst B64:240284

6. Van Mechelen JB, Peschar R, Schenk H (2008) Structures of mono-unsaturated triacylglycerols. IV. The highest melting betaprime-2 polymorphs of trans-mono-unsaturated triacylglycerols and related saturated TAGs and their polymorphic stability. Acta Cryst B64:249259 7. Dorset DL (2005) Crystallography of the polymethylene chain. Oxford University Press, Oxford 8. Gresti J, Bugaut C, Maniongui C, Bezard J (1993) Composition of molecular species of triacylglycerols in bovine milk fat. J Dairy Sci 76(7):18501869 9. Craven RJ, Lencki RW (2011) Crystallization, polymorphism, and binary phase behavior of model enantiopure and racemic triacylglycerols. Cryst Growth Des 11:17231732 10. Sato K, GotoM, Yano J, Honda K, Kodali DR, Small DM (2001) Atomic resolution structure analysis of b polymorph crystal of a triacylglycerol: 1,2-dipalmitoyl-3-myristoyl-sn-glycerol. J Lipid Res 42:338345 11. Hargittai M, Hargittai I (2009) Symmetry through the eyes of a chemist. Springer, Hungary 12. Tilley RJD (2006) Crystals and crystal structures. John Wiley, Chichester 13. Jacques J, Collet A, Wilen SH (1981) Enantiomers, racemates and resolutions. John Wiley, NY 14. Goto M, Kodali DR, Small DM, Honda K, Kozawa K, Uchida T (1992) Single crystal structure of a mixed-chain triacylglycerol: 1,2-Dipalmitoyl-3-acetoyl-sn-glycerol. Proc Nat Acad Sci 89:8083 8086 15. Craven RJ, Lencki RW (2011) Crystallization and polymorphism of 1,3-acyl-palmitoyl-rac-glycerols. J Am Oil Chem Soc 88:11131123 16. Massa W (2004) Crystal structure determination. Springer, Berlin 17. Nangia A (2008) Conformational polymorphism of organic crystals. Acc Chem Res 41:595604 18. Jensen LH, Mabis AJ (1963) Crystal structure of b-tricaprin. Nature 197:681682 19. Larsson K (1964) The crystal structure of the beta-form of trilaurin. Arkiv fur Kemi 23:115 20. Skoda W, Hoekstra LL, Van Soest TC, Bennema P, Van den Tempel M (1967) Structure and morphology of beta-crystals of glyceryl tristearate. Kolloid-Zeitschrift und Zeitschrift fur Polymere 219:149156 21. Doyne TH, Gordon JT (1968) The crystal structure of a diacid triglyceride. J Am Oil Chem Soc 45:333334 22. Van Langevelde A, Van Malssen KF, Hollander F, Peschar R, Schenk H (1999) Structure of mono-acid even-numbered b-triacylglycerols. Acta Cryst B55:114122 23. Culot C, Norberg B, Evrard G, Durant F (2000) Molecular analysis of the beta-polymorphic form of trielaidin: crystal structure at low temperature. Acta Cryst B56:317321

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J Am Oil Chem Soc 24. Van Langevelde A, Peschar R, Schenk H (2001) Structure of b-myrisitin and b-tristearin from high-resolution X-ray powder diffraction data. Acta Cryst B57:372377 25. Helmholdt RB, Peschar R, Schenk H (2002) Structure of C15-, C17-, and C19-mono acid beta-triacylglycerols. Acta Cryst B58:134139 26. van Mechelen JB, Peschar R, Schenk H (2006) Structures of mono-unsaturated triacylglycerols. I. The b1 polymorph. Acta Cryst B62:11211130 27. Van Mechelen JB, Peschar R, Schenk H (2006) Structures of mono-unsaturated triacylglycerols. II. The beta2 polymorph. Acta Cryst B62:11311138 28. Birker PJMWL, De Jong S, Roijers EC, Van Soest TC (1991) Structural investigations of beta-prime triacylglycerols: an X-ray diffraction and microscopic study of twinned beta-prime crystals. J Am Oil Chem Soc 68:895906 29. Van Langevelde A, Van Malssen KF, Driessen R, Goubitz K, Hollander F, Peschar R, Zwart P, Schenk H (2000) Structure of CnCn?2Cn-type (n = even) b-triacylglycerols. Acta Cryst B56:11031111 30. Hernqvist L, Larsson K (1982) On the crystal structure of the beta-prime-form of triglycerides and structural changes at the phase transitions LIQ-alpha-betaprime-beta. Fette Seifen Anstrichmittel 84:349354

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