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Metabolic profile of linoleic acid in stored apples: Formation of 13(R)-hydroxy-9(Z),11(E)-octadecadienoic acid

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Lipids

Abstract

During our ongoing project on the biosynthesis of R-(+)-octane-1,3-diol the metabolism of linoleic acid was investigated in stored apples after injection of [1-14C]-, [9,10,12,13-3H]-, 13C18- and unlabeled substrates. After different incubation periods the products were analyzed by gas chromatography-mass spectroscopy (MS), high-performance liquid chromatography-MS/MS, and HPLC-radiodetection. Water-soluble compounds and CO2 were the major products whereas 13(R)-hydroxy- and 13-keto-9(Z),11(E)-octadecadienoic acid, 9(S)-hydroxy-and 9-keto-10(E),12(Z)-octadecadienoic acid, and the stereoisomers of the 9,10,13- and 9,12,13-trihydroxyoctadecenoic acids were identified as the major metabolites found in the diethyl ether extracts. Hydroperoxides were not detected. The ratio of 9/13-hydroxy- and 9/13-keto-octadecadienoic acid was 1∶4 and 1∶10, respectively. Chiral phase HPLC of the methyl ester derivatives showed enantiomeric excesses of 75% (R) and 65% (S) for 13-hydroxy-9(Z),11(E)-octadecadienoic acid and 9-hydroxy-10(E),12(Z)-octadecadienoic acid, respectively. Enzymatically active homogenates from apples were able to convert unlabeled linoleic acid into the metabolites. Radiotracer experiments showed that the transformation products of linoleic acid were converted into (R)-octane-1,3-diol. 13(R)-Hydroxy-9(Z), 11(E)-octadecadienoic acid is probably formed in stored apples from 13-hydroperoxy-9(Z),11(E)-octadecadienoic acid. It is possible that the S-enantiomer of the hydroperoxide is primarily degraded by enzymatic side reactions, resulting in an enrichment of the R-enantiomer and thus leading to the formation of 13(R)-hydroxy-9(Z),11(E)-octadecadienoic acid.

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Abbreviations

ELSD:

Evaporative light scattering detector

GC-MS:

capillary gas chromatography-mass spectrometry

HODE:

hydroxy-octadecadienoic acid

HILC:

high-performance liquid chromatography

HPLC-MS/MS:

HPLC-tandem mass spectrometry

HPOD:

hydroperoxyoctadecadienoic acid

KODE:

keto-octadecadienoic acid

LC:

liquid chromatography

LOX:

lipoxygenase

RP18:

octadecy reversed phase

TLC:

thin-layer chromatography

UV:

ultraviolet

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  1. Lehrstuhl für Lebensmittelchemie, Universität Würzburg, D-97074, Würzburg, Germany

    Till Beuerle & Wilfried Schwab

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  1. Till Beuerle
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  2. Wilfried Schwab
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Correspondence to Wilfried Schwab.

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Beuerle, T., Schwab, W. Metabolic profile of linoleic acid in stored apples: Formation of 13(R)-hydroxy-9(Z),11(E)-octadecadienoic acid. Lipids 34, 375–380 (1999). https://doi.org/10.1007/s11745-999-0375-7

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  • DOI: https://doi.org/10.1007/s11745-999-0375-7

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