Metabolites of 2,3-diketogulonate delay peroxidase action and induce non-enzymic H2O2 generation: Potential roles in the plant cell wall

Kärkönen, Anna; Dewhirst, Rebecca A.; Mackay, C. Logan; Fry, Stephen C.

doi:10.1016/j.abb.2017.03.006

Title: Metabolites of 2,3-diketogulonate delay peroxidase action and induce non-enzymic H₂O₂ generation: Potential roles in the plant cell wall

Journal Article · 14 March 2017 · Archives of Biochemistry and Biophysics

DOI: https://doi.org/10.1016/j.abb.2017.03.006 · OSTI ID:1567079

Kärkönen, Anna ^[1];

^[2]; Mackay, C. Logan ^[3]; Fry, Stephen C. ^[3]

Univ. of Helsinki (Finland); Univ. of Edinburgh (United Kingdom)
Univ. of Edinburgh (United Kingdom); Univ. of Exeter (United Kingdom)
Univ. of Edinburgh (United Kingdom)

A proportion of the plant's l-ascorbate (vitamin C) occurs in the apoplast, where it and its metabolites may act as pro-oxidants and anti-oxidants. One ascorbate metabolite is 2,3-diketogulonate (DKG), preparations of which can non-enzymically generate H₂O₂ and delay peroxidase action on aromatic substrates. As DKG itself generates several by-products, we characterised these and their ability to generate H₂O₂ and delay peroxidase action. DKG preparations rapidly produced a by-product, compound (1), with λ_max 271 and 251 nm at neutral and acidic pH respectively. On HPLC, (1) co-eluted with the major H₂O₂-generating and peroxidase-delaying principle. Compound (1) was slowly destroyed by ascorbate oxidase, and was less stable at pH 6 than at pH 1. Electrophoresis of an HPLC-enriched preparation of (1) suggested a strongly acidic (pK_a ≈ 2.3) compound. Mass spectrometry suggested that un-ionised (1) has the formula C₆H₆O₅, i.e. it is a reduction product of DKG (C₆H₈O₇). In conclusion, compound (1) is the major H₂O₂-generating, peroxidase-delaying principle formed non-enzymically from DKG in the pathway ascorbate → dehydroascorbic acid → DKG → (1). We hypothesise that (1) generates apoplastic H₂O₂ (and consequently hydroxyl radicals) and delays cell-wall crosslinking - both these effects favouring wall loosening, and possibly playing a role in pathogen defence.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1567079

Journal Information:: Archives of Biochemistry and Biophysics, Vol. 620, Issue C; ISSN 0003-9861

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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The oxidation of dehydroascorbic acid and 2,3-diketogulonate by distinct reactive oxygen species Dewhirst, Rebecca A.; Fry, Stephen C. Biochemical Journal, Vol. 475, Issue 21 https://doi.org/10.1042/bcj20180688	journal	November 2018
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Related Subjects

59 BASIC BIOLOGICAL SCIENCES
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Ascorbate
dehydroascorbic acid
diketogulonate
apoplast
peroxidase
hydrogen peroxide
hydroxyl radical
plant cell wall

Title: Metabolites of 2,3-diketogulonate delay peroxidase action and induce non-enzymic H2O2 generation: Potential roles in the plant cell wall

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Title: Metabolites of 2,3-diketogulonate delay peroxidase action and induce non-enzymic H₂O₂ generation: Potential roles in the plant cell wall