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A pathway for biosynthesis of divinyl ether fatty acids in green leaves

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Lipids

Abstract

[1-14C]α-Linolenic acid was incubated with a particulate fraction of homogenate of leaves of the meadow buttercup (Ranunculus acris L.). The main product was a divinyl ether fatty acid, which was identified as 12-[1′(Z),3′(Z)-hexadienyloxy]-9(Z), 11(E)-dodecadienoic acid. Addition of glutathione peroxidase and reduced glutathione to incubations of α-linolenic acid almost completely suppressed formation of the divinyl ether acid and resulted in the appearance of 13(S)-hydroxy-9(Z), 11(E), 15(Z)-octadecatrienoic acid as the main product. This result, together with the finding that 13(S)-hydroperoxy-9(Z), 11(E), 15(Z)-octadecatrienoic acid served as an efficient precursor of the divinyl ether fatty acid, indicated that divinyl ether biosynthesis in leaves of R. acris occurred by a two-step pathway involving an ω6-lipoxygenase and a divinyl ether synthase. Incubations of isomeric hydroperoxides derived from α-linolenic and linoleic acids with the enzyme preparation from R. acris showed that 13(S)-hydroperoxy-9(Z), 11(E)-octadecadienoic acid was transformed into the divinyl ether 12-[1′(Z)-hexenyloxy]-9(Z), 11(E)-dodecadienoic acid. In contrast, neither the 9(S)-hydroperoxides of linoleic or α-linolenic acids nor the 13(R)-hydroperoxide of α-linolenic acid served as precursors of divinyl ethers.

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Abbreviations

9-H(P)OD:

9-hydro(pero)xy-10(E), 12(Z)-octadecadienoic acid

9-H(P)OT:

9-hydro(pero)xy-10(E), 12(Z), 15(Z)-octadecatrienoic acid

12-oxo-PDA:

12-oxo-10,15(Z)-phytodienoic acid

13-H(P)OD:

13-hydro(pero)xy-9(Z), 11(E)-octadecadienoic acid

13-H(P)OT:

13-hydro(pero)xy-9(Z), 11(E), 15(Z)-octadecatrienoic acid

colneleic acid:

9-[1′(E),3′(Z)-nonadienyloxy]-8(E)-nonenoic acid

colnelenic acid:

9-[1′(E),3′(Z),6′(Z)-nonatrienyloxy]-8(E)-nonenoic acid

etheroleic acid:

12-[1′(E)-hexenyloxy]-9(Z),11(E)-dodecadienoic acid

etherolenic acid:

12-[1′(E),3′(Z)-hexadienyloxy]-9(Z),11(E)-dodecadienoic acid

FT-IR:

Fourier transform infrared

GC-MS:

gas chromatography-mass spectrometry

GLC:

gas-liquid chromatography

GSH:

glutathione (reduced form)

GSH-px:

glutathione peroxidase

NMR:

nuclear magnetic resonance

RP-HPLC:

reversed-phase high-performance liquid chromatography

SP-HPLC:

straightphase high-performance liquid chromatography

SPE:

solid-phase extraction

UV:

ultraviolet

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  1. Department of Medical Biochemistry and Biophysics, Division of Physiological Chemistry II, Karolinska Institutet, S-171 77, Stockholm, Sweden

    Mats Hamberg

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  1. Mats Hamberg
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Hamberg, M. A pathway for biosynthesis of divinyl ether fatty acids in green leaves. Lipids 33, 1061–1071 (1998). https://doi.org/10.1007/s11745-998-0306-7

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  • DOI: https://doi.org/10.1007/s11745-998-0306-7

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