Alternative pathways of dehydroascorbic acid degradation in vitro and in plant cell cultures: novel insights into vitamin C catabolism

Harriet T. Parsons, Tayyaba Yasmin, Stephen C. Fry

Research output: Contribution to journalArticlepeer-review

Abstract / Description of output

L-Ascorbate catabolism involves reversible oxidation to DHA (dehydroascorbic acid), then irreversible oxidation or hydrolysis. The precursor-product relationships and the identity of several major DHA breakdown products remained unclear. In the presence of added H2O2, DHA underwent little hydrolysis to DKG (2,3-dioxo-L-gulonate). Instead, it yielded OxT (oxalyl L-threonate), cOxT (cyclic oxalyl L-threonate) and free oxalate (similar to 6:1:1), essentially simultaneously, suggesting that all three product classes independently arose from ode reactive intermediate, proposed to be cyclic-2,3-O-oxalyl-L-threonolactone. Only with plant apoplastic esterases present were the esters significant precursors of free oxalate. Without added H2O2, DHA was slowly hydrolysed to DKG. Downstream of DKG was a singly ionized dicarboxy compound (suggested to be 2-carboxy-L-xylonolactone plus 2-carboxy-L-lyxonolactone), which reversibly de-lactonized to a dianionic carboxypentonate. Formation of these lactones and acid was minimized by the presence of residual unreacted ascorbate. In vivo, the putative 2-carboxy-L-pentonolactones were relatively stable. We propose that DHA is a branch-point in ascorbate catabolism, being either oxidized to oxalate and its esters or hydrolysed to DKG and downstream carboxypentonates. The oxidation/hydrolysis ratio is governed by reactive oxygen species status. In vivo, oxalyl esters are enzymatically hydrolysed, but the carboxypentonates are stable. The biological roles of these ascorbate metabolites invite future exploration.

Original languageEnglish
Pages (from-to)375-383
Number of pages9
JournalBiochemical Journal
Volume440
Issue number3
DOIs
Publication statusPublished - 15 Dec 2011

Keywords / Materials (for Non-textual outputs)

  • ascorbic acid
  • carboxy-L-xylonic acid
  • dioxogulonic acid
  • hydrogen peroxide (H2O2)
  • oxalyl esterase
  • oxalyl threonate

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