Abstract
Furan fatty acids (F-acids) are a class of natural antioxidants with a furan moiety in the acyl chain. These minor fatty acids have been reported to occur with high proportions in the cholesteryl ester fraction of fish livers. Here we present a method for the direct analysis of intact cholesteryl esters with F-acids and other fatty acids in cod liver lipids. For this purpose, the cholesteryl ester fraction was isolated by solid phase extraction (SPE) and subsequently analyzed by gas chromatography with mass spectrometry (GC/MS) using a cool-on-column inlet. Pentadecanoic acid esterified with cholesterol was used as an internal standard. GC/MS spectra of F-acid cholesteryl esters featured the molecular ion along with characteristic fragment ions for both the cholesterol and the F-acid moiety. All investigated cod liver samples (n = 8) showed cholesteryl esters of F-acids and, to a lower degree, of conventional fatty acids. By means of GC/MS-SIM up to ten F-acid cholesteryl esters could be determined in the samples. The concentrations of cholesteryl esters with conventional fatty acids amounted to 78–140 mg/100 g lipids (mean 97 mg/100 g lipids), while F-acid cholesteryl esters were present at 47–270 mg/100 g lipids (mean 130 mg/100 g lipids).
Similar content being viewed by others
Abbreviations
- 7D5:
-
7-(3,4-Dimethyl-5-pentylfuran-2-yl)-heptanoic acid
- 9D3:
-
9-(3,4-Dimethyl-5-propylfuran-2-yl)-nonanoic acid
- 9D5:
-
9-(3,4-Dimethyl-5-pentylfuran-2-yl)-nonanoic acid
- 9M5:
-
9-(3-Methyl-5-pentylfuran-2-yl)-nonanoic acid
- 11D3:
-
11-(3,4-Dimethyl-5-propylfuran-2-yl)-undecanoic acid
- 11D5:
-
11-(3,4-Dimethyl-5-pentylfuran-2-yl)-undecanoic acid
- 11M3:
-
11-(3-Methyl-5-propylfuran-2-yl)-undecanoic acid
- 11M5:
-
11-(3-Methyl-5-pentylfuran-2-yl)-undecanoic acid
- 13D3:
-
13-(3,4-Dimethyl-5-propylfuran-2-yl)-tridecanoic acid
- 13D5:
-
13-(3,4-Dimethyl-5-pentylfuran-2-yl)-tridecanoic acid
- CE:
-
Cholesteryl ester
- DHA:
-
Docosahexaenoic acid (22:6n-3)
- EPA:
-
Eicosapentaenoic acid (20:5n-3)
- F-acid:
-
Furan fatty acid
- F-CE:
-
Furan fatty acid cholesteryl ester
- FAME:
-
Fatty acid methyl ester
- GC/MS:
-
Gas chromatography with mass spectrometry
- HPLC:
-
High performance liquid chromatography
- NMR:
-
Nuclear magnetic resonance
- PUFA:
-
Polyunsaturated fatty acid
- SIM:
-
Selected ion monitoring
- SPE:
-
Solid phase extraction
- TIC:
-
Total ion current
References
Spiteller G (2005) Furan fatty acids: occurrence, synthesis, and reactions. Are furan fatty acids responsible for the cardioprotective effects of a fish diet? Lipids 40(8):755–771
Vetter W, Laure S, Wendlinger C, Mattes A, Smith AWT, Knight DW (2012) Determination of furan fatty acids in food samples. J Am Oil Chem Soc 89(8):1501–1508
Pacetti D, Mozzon M, Lucci P, Frega NG (2013) Bioactive fish fatty acids: Health effects and their use as functional food ingredients. Curr Nutr Food Sci 9(4):283–297
Vetter W, Wendlinger C (2013) Furan fatty acids—valuable minor fatty acids in food. Lipid Technol 25(1):7–10
Glass RL, Krick TP, Eckhardt AE (1974) New series of fatty acids in northern pike (Esox lucius). Lipids 9(12):1004–1008
Gunstone FD, Wijesundera RC (1978) The component acids of the lipids in four commercial fish meals. J Sci Food Agric 29(1):28–32
Hannemann K, Puchta V, Simon E, Ziegler H, Ziegler G, Spiteller G (1989) The common occurrence of furan fatty acids in plants. Lipids 24(4):296–298
Guth H, Grosch W (1992) Furan fatty acids in butter and butter oil. Z Lebensm Unters Forsch 194(4):360–362
Pacetti D, Alberti F, Boselli E, Frega NG (2010) Characterisation of furan fatty acids in Adriatic fish. Food Chem 122(1):209–215
Boselli E, Grob K, Lercker G (2000) Determination of furan fatty acids in extra virgin olive oil. J Agric Food Chem 48(7):2868–2873
Glass RL, Krick TP, Olson DL, Thorson RL (1977) The occurrence and distribution of furan fatty acids in spawning male freshwater fish. Lipids 12(10):828–836
Schoedel R, Spiteller G (1987) On the occurrence of F-acids in cattle liver and their enzymic degradation during tissue damage. Liebigs Ann Chem 5:459–462
Kamm W, Dionisi F, Fay L, Hischenhuber C, Schmarr H-G, Engel K-H (2001) Analysis of steryl esters in cocoa butter by on-line liquid chromatography–gas chromatography. J Chromatogr A 918(2):341–349
Evershed RP, Male VL, Goad LJ (1987) Strategy for the analysis of steryl esters from plant and animal tissues. J Chromatogr 400:187–205
Esche R, Barnsteiner A, Scholz B, Engel K-H (2012) Simultaneous analysis of free phytosterols/phytostanols and intact phytosteryl/phytostanyl fatty acid and phenolic acid esters in cereals. J Agric Food Chem 60(21):5330–5339
Verleyen T, Forcades M, Verhe R, Dewettinck K, Huyghebaert A, De Greyt W (2002) Analysis of free and esterified sterols in vegetable oils. J Am Oil Chem Soc 79(2):117–122
Esche R, Carcelli A, Barnsteiner A, Sforza S, Engel K-H (2013) Analysis of phytosteryl and phytostanyl fatty acid esters in enriched dairy foods: a combination of acid digestion, lipid extraction, and on-line LC-GC. Eur Food Res Technol 236(6):999–1007
Glass RL, Krick TP, Sand DM, Rahn CH, Schlenk H (1975) Furanoid fatty acids from fish lipids. Lipids 10(11):695–702
Rahn CH, Sand DM, Krick TP, Glass RL, Schlenk H (1981) Syntheses of radioactive furan fatty acids. Lipids 16(5):360–364
Lusby WR, Thompson MJ, Kochansky J (1984) Analysis of sterol esters by capillary gas chromatography-electron impact and chemical ionization-mass spectrometry. Lipids 19(11):888–901
Bauer ST (1946) The preparation of fatty acid chlorides. Oil Soap 23(1):1–5
Gunstone FD, Wijesundera RC, Scrimgeour CM (1978) The component acids of lipids from marine and freshwater species with special reference to furan-containing acids. J Sci Food Agric 29(6):539–550
Evershed RP, Prescott MC, Spooner N, Goad LJ (1989) Negative ion ammonia chemical ionization and electron impact ionization mass spectrometric analysis of steryl fatty acyl esters. Steroids 53(3–5):285–309
Brown AJ, Jessup W (1999) Oxysterols and atherosclerosis. Atherosclerosis 142(1):1–28
Brown AJ, Dean RT, Jessup W (1996) Free and esterified oxysterol: formation during copper-oxidation of low density lipoprotein and uptake by macrophages. J Lipid Res 37(2):320–335
Brown AJ, Leong SL, Dean RT, Jessup W (1997) 7-Hydroperoxycholesterol and its products in oxidized low density lipoprotein and human atherosclerotic plaque. J Lipid Res 38(9):1730–1745
Rezanka T (1992) Analysis of sterol esters from alga and yeast by high-performance liquid chromatography and capillary gas chromatography-mass spectrometry with chemical ionization. J Chromatogr 598(2):219–226
Kuksis A, Myher JJ, Marai L, Little JA, McArthur RG, Roncari DAK (1986) Fatty acid composition of individual plasma steryl esters in phytosterolemia and xanthomatosis. Lipids 21(6):371–377
Smith NB (1982) Hydrogenation of cholesteryl esters during gas chromatography on a polar fused-silica capillary column. J Chromatogr 249(1):57–63
The AOCS Lipid Library. http://lipidlibrary.aocs.org/
Acknowledgments
We gratefully acknowledge the financial support of the Fonds der Chemischen Industrie in the form of a stipend grant to S.H.
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Below is the link to the electronic supplementary material.
About this article
Cite this article
Hammann, S., Wendlinger, C. & Vetter, W. Analysis of Intact Cholesteryl Esters of Furan Fatty Acids in Cod Liver. Lipids 50, 611–620 (2015). https://doi.org/10.1007/s11745-015-4019-7
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11745-015-4019-7