Abstract
Triacylglycerols of the seed oils rich in α- and/or γ-linolenic acid moieties were separated by silver-ion high-performance liquid chromatography (HPLC) followed by on-line atmospheric pressure chemical ionization-mass spectrometric (APCI-MS) detection. Mass spectra of most triacylglycerols exhibited abundant [M + H]+ and [M − RCO2]+ ions, which defined the molecular weight and the molecular association of fatty acyl residues of a triacylglycerol, respectively. Silver ions formed weaker complexes with triacylglycerols containing γ-linolenic acid than with those containing α-linolenic acid, i.e., the elution order of molecules wasXYT γ>XYT α’,XT γ T α>XT α T α>, andT γ T γ T γ>T γ T γ T α>T γ T α T α>T α T α T α, whereT α=α-linolenic acid,T γ=γ-linolenic acid, andX, Y=fatty acids different from linolenic acid. Furthermore, silver-ion HPLC resulted in partial separation within equally unsaturated triacylglycerols according to differences in the combined number of acyl carbons. Regioisomeric forms of triacylglycerols were not determined from the seed oil samples, although differences were measured with reference compounds in the relative abundances of [M − RCO2]+ ions formed by a loss of a fatty acyl residue from thesn-2 position and thesn-1/3 positions. Silverion HPLC/APCI-MS provided valuable information for structure elucidation of seed oil triacylglycerols: 43 molecular species were identified from cloudberry seed oil, 39 from evening primrose oil, 79 from borage oil, 44 from alpine currant, and 56 from black currant seed oils. The quantitation requires to be studied further, especially in those cases where several molecular weight species of triacylglycerols eluted in a single chromatographic peak.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
Abbreviations
- APCI:
-
atmospheric pressure chemical ionization
- APCI-MS:
-
atmospheric pressure chemical ionization-mass spectrometry
- ELSD:
-
evaporative light-scattering detector
- FID:
-
flame-ionization detector
- HPLC:
-
high-performance liquid chromatography
- GC:
-
gas chromatography
- MS:
-
mass spectrometry
- TLC:
-
thin-layer chromatography
- RIC:
-
reconstructed ion chromatogram
References
Morris, L.J. (1966) Separations of Lipids by Silver-Ion Chromatography,J. Lipid Res. 7, 717–732.
Litchfield, C. (1972)Analysis of Triglycerides, pp. 50–66, Academic Press, London.
Nikolova-Damyanova, B. (1992) Silver-Ion Chromatography and Lipids, inAdvances in Lipid Methodology—One (Christie, W.W., ed.), pp. 181–237, The Oily Press, Ayr.
Dobson, G., Christie, W.W., and Nikolova-Damyanova, B. (1995) Silver-Ion Chromatography of Lipids and Fatty Acids,J. Chromatogr. B 671, 197–222.
Petersson, B., Podhala, O., and Jirskog-Hed, B. (1993) Triacylglycerol Analysis of Partially Hydrogenated Fats Using High-Performance Liquid Chromatography,J. Chromatogr. A 653, 25–35.
Christie, W.W. (1988) Separation of Molecular Species of Triacylglycerols by High-Performance Liquid Chromatography with a Silver-Ion Column,J. Chromatogr. 454, 273–284.
Jeffrey B.S.J. (1991) Silver-Complexation Liquid Chromatography for Fast, High-Resolution Separations of Triacylglycerols,J. Am. Oil Chem. Soc. 68, 289–293.
Christie, W.W. (1987) A Stable Silver-Loaded Column for the Separation of Lipids by High-Performance Liquid Chromatography,J. High Resolut. Chromatogr. Chromatogr. Commun. 10, 148–150.
Smith, K.W., Perkins, J.M., Jeffrey, B.S.J., and Phillips, D.L. (1994) Separation of Molecular Species ofcis- andtrans-Triacylglycerols intrans-Hardened Confectionery Fats by Silver-Ion High-Performance Liquid Chromatography,J. Am. Oil Chem Soc. 71, 1219–1222.
Neff, W.E., Adlof, R.O., and El-Agaimy, M. (1994) Silver-Ion High-Performance Liquid Chromatography of the Triacylglycerols ofCrepis alpina Seed Oil,J. Am. Oil Chem. Soc. 71, 853–855.
Joh, Y.-G., Kim, S.-J., and Christie, W.W. (1995) The Structure of the Triacylglycerols, Containing Punicic Acid, in the Seed Oil ofTrichosanthes kirilowii, J. Am. Oil Chem. Soc. 72, 1037–1042.
Laakso, P., and Kallio, H. (1993) Triacylglycerols of Winter Butterfat Containing Configurational Isomers of Monoenoic Fatty Acyl Residues. I. Disaturated Monoenoic Triacylglycerols,J. Am. Oil Chem. Soc. 70, 1161–1171.
Brühl, L., Schulte, E., and Thier, H.-P. (1993) Fraktionierung der Triglyceride von Muttermilch durch HPLC an einer Silberionensäule und and RP-18-Material mit dem Lichtstreudetektor,Fat Sci. Technol. 95, 370–376.
Winter, C.H., Hoving, E.B., and Muskiet, F.A.J. (1993) Fatty Acid Composition of Human Milk Triglyceride Species. Possible Consequences for Optimal Structures of Infant Formula Triglycerides,J. Chromatogr. 616, 9–24.
Laakso, P., Christie, W.W., and Pettersen, J. (1990) Analysis of North Atlantic and Baltic Fish Oil Triacylglycerols by High-Performance Liquid Chromatography with a Silver-Ion Column,Lipids 25, 284–291.
Laakso, P., and Christie, W.W. (1991) Combination of Silver Ion and Reversed-Phase High-Performance Liquid Chromatography in the Fractionation of Herring Oil Triacylglycerols,J. Am. Oil Chem. Soc. 68, 213–223.
McGill, A.S., and Moffat, C.F. (1992) A Study of the Composition of Fish Liver and Body Oil Triglycerides,Lipids 27, 360–370.
Nikolova-Damyanova, B., Herslof, B.G., and Christie, W.W. (1992) Silver-Ion High-Performance Liquid Chromatography of Derivatives of Isomeric Fatty Acids,J. Chromatogr. 609, 133–140.
Christie, W.W. (1991) Fractionation of the Triacylglycerols of Evening Primrose Oil by High-Performance Liquid Chromatography in the Silver-Ion Mode,Fat Sci. Technol. 93, 65–66.
Ratnayake, W.M.N., Matthews, D.G., and Ackman, R.G. (1989) Triacylglycerols of Evening Primrose (Oenothera biennis) Seed Oil,J. Am. Oil Chem. Soc. 66, 966–969.
Blomberg, L.G., Demirbüker, M., and Anderson, P.E. (1993) Argentation Supercritical Fluid Chromatography for Quantitative Analysis of Triacyglycerols,J. Am. Oil Chem. Soc. 70, 939–946.
Aitzetmüller, K., and Grönheim, M. (1992) Separation of Highly Unsaturated Triacylglycerols by Reversed-Phase HPLC with Short Wavelength UV Detection,J. High Resolut. Chromatogr. 15, 219–226.
Perrin, J.-L., Prevot, A., Traitler, H., and Bracco, U. (1987) Analysis of Triglyceride Species of Blackcurrant Seed Oil by HPLCvia a Laser Light-Scattering Detector,Rev. Fr. Corps Gras 34, 221–223.
Rezanka, T., and Mares, P. (1991) Determination of Plant Triacylglycerols Using Capillary Gas Chromatography, High-Performance Liquid Chromatography and Mass Spectrometry,J. Chromatogr. 542, 145–159.
Manninen, P., Laakso, P., and Kallio, H. (1995) Separation of γ- and α-Linolenic Acid Containing Triacylglycerols by Capillary Supercritical Fluid Chromatography,Lipids 30, 665–671.
Schuyl, P.J.W., de Joode, T., Duchateau, G.S.M.J.E., and Vasconcellos, M.A. (1995) HPLC-MS Analysis of Triacylglycerides, inProceedings of the 43rd ASMS Conference on Mass Spectrometry and Allied Topics, p. 1143, Atlanta, Georgia, May 21–26, 1995.
Byrdwell, W.C., and Emken, E.A. (1995) Analysis of Triglycerides Using Atmospheric Pressure Chemical Ionization Mass Spectrometry,Lipids 30,173–175.
Neff, W.E., and Byrdwell, W.C. (1995) Soybean Oil Triacylglycerol Analysis by Reversed-Phase High-Performance Liquid Chromatography Coupled with Atmospheric Pressure Chemical Ionization-Mass Spectrometry,J. Am. Oil Chem. Soc. 72, 1185–1191.
Christie, W.W. (1982) A Simple Procedure for Rapid Transmethylation of Glycerolipids and Cholesteryl Esters,J. Lipid Res. 23, 1072–1075.
Nikolova-Damyanova, B., Chobanov, D., and Dimov, S. (1993) Separation of Isomeric Triacylglycerols by Silver-Ion Thin-Layer Chromatography,J. Liq. Chromatogr. 16, 3997–4008.
Adlof, R.O. (1995) Analysis of Triacylglycerol Positional Isomers by Silver Ion High-Performance Liquid Chromatography,J. High Resol. Chromatogr. 18, 105–107.
Adlof, R.O. (1996) Analysis of Fatty Acid Mono- and Diacylglycerol Positional Isomers by Silver-Ion High-Performance Liquid Chromatography,J. Chromatogr. A. 741, 135–138.
Horrobin, D.F. (1992) Nutritional and Medical Importance of Gamma-Linolenic Acid,Prog. Lipid Res. 31, 163–194.
Author information
Authors and Affiliations
About this article
Cite this article
Laakso, P., Voutilainen, P. Analysis of triacylglycerols by silver-ion high-performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry. Lipids 31, 1311–1322 (1996). https://doi.org/10.1007/BF02587918
Received:
Revised:
Accepted:
Issue Date:
DOI: https://doi.org/10.1007/BF02587918