Biosynthesis of Mono- and Sesquiterpenes in Strawberry Fruits and Foliage: 2H Labeling Studies
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- 作者：Daniela Hampel ; Armin Mosandl ; and Matthias Wü ; st
- 刊名：Journal of Agricultural and Food Chemistry
- 出版年：2006
- 出版时间：February 22, 2006
- 年：2006
- 卷：54
- 期：4
- 页码：1473 - 1478
- 全文大小：83K
- 年卷期：v.54,no.4(February 22, 2006)
- ISSN：1520-5118
文摘
The biosynthesis of the monoterpene (S)-linalool and the sesquiterpene trans-(S)-nerolidol in fruitsof Fragaria × ananassa Duch. cv. Eros and Florence and of the monoterpene (-)-
-pinene in Fragariavesca was investigated by in vivo feeding experiments with [5,5-2H2]mevalonic acid lactone (d2-MVL)and [5,5-2H2]-1-deoxy-D-xylulose (d2-DOX). The feeding experiments indicate that (S)-linalool andtrans-(S)-nerolidol in Fragaria × ananassa Duch. and (-)--pinene in F. vesca are exclusivelysynthesized via the cytosolic mevalonic acid pathway without any contribution from the plastidial1-deoxy-D-xylulose/2-C-methyl-D-erythritol 4-phosphate (DOXP/MEP) route. Inhibition experimentsrevealed that even the presence of mevastatin, an export of plastid-derived isopentyl diphosphate/dimethylallyl diphosphate, cannot be induced. However, the enantioselective analysis shows that inFragaria × ananassa Duch. cv. Eros and Florence both linalool enantiomers are present and thatonly (S)-linalool is labeled after administration of d2-MVL. Therefore, the origin of (R)-linalool in thesefruits remains unknown. Contrarily, in Fragaria × ananassa Duch. foliage (R)-linalool is the dominantenantiomer. Feeding experiments revealed an incorporation of d2-MVL and d2-DOX at equal ratesexclusively into (S)-linalool. Only in F. vesca foliage, where (R)-linalool is present at high enantiomericpurity (ee > 90%), is a de novo biosynthesis of the (R)-enantiomer via the DOXP/MEP pathwaydetectable. These results demonstrate a complex intraplant variation of (R)- and (S)-linaloolbiosynthesis via the cytosolic and plastidial route.Keywords: Rosaceae; fruit flavor; terpenes; non-mevalonate pathway; stir bar sorptive extraction(SBSE); thermal desorption-enantioselective multidimensional gas chromatography-mass spectrometry(TD-enantio-MDGC-MS)
-pinene in Fragariavesca was investigated by in vivo feeding experiments with [5,5-2H2]mevalonic acid lactone (d2-MVL)and [5,5-2H2]-1-deoxy-D-xylulose (d2-DOX). The feeding experiments indicate that (S)-linalool andtrans-(S)-nerolidol in Fragaria × ananassa Duch. and (-)--pinene in F. vesca are exclusivelysynthesized via the cytosolic mevalonic acid pathway without any contribution from the plastidial1-deoxy-D-xylulose/2-C-methyl-D-erythritol 4-phosphate (DOXP/MEP) route. Inhibition experimentsrevealed that even the presence of mevastatin, an export of plastid-derived isopentyl diphosphate/dimethylallyl diphosphate, cannot be induced. However, the enantioselective analysis shows that inFragaria × ananassa Duch. cv. Eros and Florence both linalool enantiomers are present and thatonly (S)-linalool is labeled after administration of d2-MVL. Therefore, the origin of (R)-linalool in thesefruits remains unknown. Contrarily, in Fragaria × ananassa Duch. foliage (R)-linalool is the dominantenantiomer. Feeding experiments revealed an incorporation of d2-MVL and d2-DOX at equal ratesexclusively into (S)-linalool. Only in F. vesca foliage, where (R)-linalool is present at high enantiomericpurity (ee > 90%), is a de novo biosynthesis of the (R)-enantiomer via the DOXP/MEP pathwaydetectable. These results demonstrate a complex intraplant variation of (R)- and (S)-linaloolbiosynthesis via the cytosolic and plastidial route.Keywords: Rosaceae; fruit flavor; terpenes; non-mevalonate pathway; stir bar sorptive extraction(SBSE); thermal desorption-enantioselective multidimensional gas chromatography-mass spectrometry(TD-enantio-MDGC-MS)