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A role for ascorbate conjugates of (+)-catechin in proanthocyanidin polymerization

Keji Yu, Richard A. Dixon and Changqing Duan ()
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Keji Yu: China Agricultural University
Richard A. Dixon: University of North Texas
Changqing Duan: China Agricultural University

Nature Communications, 2022, vol. 13, issue 1, 1-17

Abstract: Abstract Proanthocyanidins (PAs) are natural polymers of flavan-3-ols, commonly (+)-catechin and (−)-epicatechin. However, exactly how PA oligomerization proceeds is poorly understood. Here we show, both biochemically and genetically, that ascorbate (AsA) is an alternative “starter unit” to flavan-3-ol monomers for leucocyanidin-derived (+)-catechin subunit extension in the Arabidopsis thaliana anthocyanidin synthase (ans) mutant. These (catechin)n:ascorbate conjugates (AsA-[C]n) also accumulate throughout the phase of active PA biosynthesis in wild-type grape flowers, berry skins and seeds. In the presence of (−)-epicatechin, AsA-[C]n can further provide monomeric or oligomeric PA extension units for non-enzymatic polymerization in vitro, and their role in vivo is inferred from analysis of relative metabolite levels in both Arabidopsis and grape. Our findings advance the knowledge of (+)-catechin-type PA extension and indicate that PA oligomerization does not necessarily proceed by sequential addition of a single extension unit. AsA-[C]n defines a new type of PA intermediate which we term “sub-PAs”.

Date: 2022
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DOI: 10.1038/s41467-022-31153-2

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