Investigation of biosynthetic pathways to hydroxycoumarins during post-harvest physiological deterioration in cassava roots by using stable isotope labelling

S A L Bayoumi, Michael G Rowan, J R Beeching, I S Blagbrough

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13 Citations (Scopus)

Abstract

Cassava (Manihot esculenta Crantz) is an important starch-rich crop, but the storage roots only have a short shelf-life due to post-harvest physiological deterioration (PPD) which includes the over-production and polymerisation of hydroxycoumarins. Key aspects of coumarin secondary metabolite biosynthesis remain unresolved. Here we exploit this accumulation of hydroxycoumarins to test alternative pathways for their biosynthesis. Using isotopically labelled intermediates (p-coumarate-2-13C, caffeate-2-13C, ferulate-2-13C, umbelliferone-2-18O and esculetin-2-18O), we show that the major biosynthetic pathway to scopoletin and its glucoside scopolin in cassava roots during PPD is through p-coumaric, caffeic and then ferulic acids. An alternate pathway through 2',4'-dihydroxycinnamate and umbelliferone leads to esculetin and esculin. We have used C18O2-carboxylate labelled cinnamic and ferulic acids, and feeding experiments in an atmosphere of 18O2, to investigate the o-hydroxylation and cyclisation steps. We demonstrate that the major pathway is through o-hydroxylation and not via a proposed spirolactone-dienone intermediate.
Original languageEnglish
Pages (from-to)3013-3022
Number of pages10
JournalChemBiochem
Volume9
Issue number18
Early online date26 Nov 2008
DOIs
Publication statusPublished - 15 Dec 2008

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ferulic acid
7-hydroxycoumarin
Isotope Labeling
Manihot
Hydroxylation
Biosynthesis
Biosynthetic Pathways
Isotopes
Labeling
Deterioration
Esculin
Scopoletin
Spironolactone
Cyclization
Glucosides
Metabolites
Starch
Crops
Polymerization
Atmosphere

Cite this

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abstract = "Cassava (Manihot esculenta Crantz) is an important starch-rich crop, but the storage roots only have a short shelf-life due to post-harvest physiological deterioration (PPD) which includes the over-production and polymerisation of hydroxycoumarins. Key aspects of coumarin secondary metabolite biosynthesis remain unresolved. Here we exploit this accumulation of hydroxycoumarins to test alternative pathways for their biosynthesis. Using isotopically labelled intermediates (p-coumarate-2-13C, caffeate-2-13C, ferulate-2-13C, umbelliferone-2-18O and esculetin-2-18O), we show that the major biosynthetic pathway to scopoletin and its glucoside scopolin in cassava roots during PPD is through p-coumaric, caffeic and then ferulic acids. An alternate pathway through 2',4'-dihydroxycinnamate and umbelliferone leads to esculetin and esculin. We have used C18O2-carboxylate labelled cinnamic and ferulic acids, and feeding experiments in an atmosphere of 18O2, to investigate the o-hydroxylation and cyclisation steps. We demonstrate that the major pathway is through o-hydroxylation and not via a proposed spirolactone-dienone intermediate.",
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T1 - Investigation of biosynthetic pathways to hydroxycoumarins during post-harvest physiological deterioration in cassava roots by using stable isotope labelling

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AU - Rowan, Michael G

AU - Beeching, J R

AU - Blagbrough, I S

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AB - Cassava (Manihot esculenta Crantz) is an important starch-rich crop, but the storage roots only have a short shelf-life due to post-harvest physiological deterioration (PPD) which includes the over-production and polymerisation of hydroxycoumarins. Key aspects of coumarin secondary metabolite biosynthesis remain unresolved. Here we exploit this accumulation of hydroxycoumarins to test alternative pathways for their biosynthesis. Using isotopically labelled intermediates (p-coumarate-2-13C, caffeate-2-13C, ferulate-2-13C, umbelliferone-2-18O and esculetin-2-18O), we show that the major biosynthetic pathway to scopoletin and its glucoside scopolin in cassava roots during PPD is through p-coumaric, caffeic and then ferulic acids. An alternate pathway through 2',4'-dihydroxycinnamate and umbelliferone leads to esculetin and esculin. We have used C18O2-carboxylate labelled cinnamic and ferulic acids, and feeding experiments in an atmosphere of 18O2, to investigate the o-hydroxylation and cyclisation steps. We demonstrate that the major pathway is through o-hydroxylation and not via a proposed spirolactone-dienone intermediate.

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