Abstract
Incubation of [1-14C]linoleic acid with an enzyme preparation obtained from the red algaLithothamnion corallioides Crouan resulted in the formation of 11-hydroxy-9(Z),12(Z)-octadecadienoic acid as well as smaller amounts of 9-hydroxy-10(E),12(Z)-octadecadienoic acid, 13-hydroxy-9(Z),11(E)-octadecadienoic acid and 11-keto-9(Z),12(Z)-octadecadienoic acid. Steric analysis showed that the 11-hydroxyoctadecadienoic acid had the (R) configuration. The 9- and 13-hydroxyoctadecadienoic acids were not optically pure, but were due to mixtures of 75% (R) and 25% (S) enantiomers (9-hydroxyoctadecadienoate), and 24% (R) and 76% (S) enantiomers (13-hydroxy-octadecadienoate). 11-Hydroxyoctadecadienoic acid was unstable at acidic pH. In acidified water, equal parts of 9(R,S)-hydroxy-10(E),12(Z)-octadecadienoate and 13(R,S)-hydroxy-9(Z),11(E)-octadecadienoate, plus smaller amounts of the corresponding (E),(E) isomers were produced. In aprotic solvents, acid treatment resulted in dehydration and in the formation of equal amounts of 8,10,12- and 9,11,13-octadecatrienoates. The enzymatic conversion of linoleic acid into the hydroxyoctadecadienoic acids and the ketooctadecadienoic acid was oxygen-dependent; however, inhibitor experiments indicated that neither lipoxygenase nor cytochrome P-450 were involved in the conversion. This conclusion was supported by experiments with18O2 and H2 18O, which demonstrated that the hydroxyl oxygen of the hydroxy-octadecadienoic acids and the keto oxygen of the 11-ketooctadecadienoic acid were derived from water and not from molecular oxygen.
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Abbreviations
- ETYA:
-
5,8,11,14-eicosatetraynoic acid
- GC/MS:
-
gas chromatography/mass spectrometry
- GLC:
-
gas-liquid chromatography
- 12(R),13(S)-diHETE:
-
12(R),13(S)-dihydroxy-5(Z),8(Z)10(E),14(Z)-eicosatetraenoic acid
- 5-HETE:
-
5-hydroxy-6(E),8(Z),11(Z),14(Z)-eicosatetraenoic acid
- 11-HETE:
-
11-hydroxy-5(Z),8(Z),12(E),14(Z)-eicosatetraenoic acid
- 12-HETE:
-
12-hydroxy-5(Z),8(Z),10(E),14(Z)-eicosatetraenoic acid
- 15-HETE:
-
15-hydroxy-5(Z),8(Z),11(Z),13(E)-eicosatetraenoic acid
- 9-HOD:
-
9-hydroxy-10(E),12(Z)-octadecadienoic acid
- 13-HOD:
-
13-hydroxy-9(Z),11(E)-octadecadienoic acid
- 12(S)-HPETE:
-
12(S)-hydroperoxy-5(Z),8(Z),10(E),14(Z)-eicosatetraenoic acid
- MC, (−)-menthoxycarbonyl:
-
Me3Si, trimethylsilyl
- NDGA:
-
nordihydroguaiaretic acid
- TLC:
-
thin-layer chromatography
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The term “oxylipin” was introduced recently (ref. 1) as an encompassing term for oxygenated compounds which are formed from fatty acids by reaction(s) involving at least one step of mono- or dixoygenase-catalyzed oxygenation.
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Hámberg, M., Gerwick, W.H. & Åsen, P.A. Linoleic acid metabolism in the red algaLithothamnion corallioides: Biosynthesis of 11(R)-hydroxy-9(Z),12(Z)-octadecadienoic acid. Lipids 27, 487–493 (1992). https://doi.org/10.1007/BF02536128
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DOI: https://doi.org/10.1007/BF02536128