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Ascorbate oxidation by iron, copper and reactive oxygen species: review, model development, and derivation of key rate constants.

Published version
Peer-reviewed

Type

Article

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Authors

Shen, Jiaqi 
Griffiths, Paul T 
Campbell, Steven J 
Utinger, Battist 
Kalberer, Markus 

Abstract

Ascorbic acid is among the most abundant antioxidants in the lung, where it likely plays a key role in the mechanism by which particulate air pollution initiates a biological response. Because ascorbic acid is a highly redox active species, it engages in a far more complex web of reactions than a typical organic molecule, reacting with oxidants such as the hydroxyl radical as well as redox-active transition metals such as iron and copper. The literature provides a solid outline for this chemistry, but there are large disagreements about mechanisms, stoichiometries and reaction rates, particularly for the transition metal reactions. Here we synthesize the literature, develop a chemical kinetics model, and use seven sets of laboratory measurements to constrain mechanisms for the iron and copper reactions and derive key rate constants. We find that micromolar concentrations of iron(III) and copper(II) are more important sinks for ascorbic acid (both AH2 and AH-) than reactive oxygen species. The iron and copper reactions are catalytic rather than redox reactions, and have unit stoichiometries: Fe(III)/Cu(II) + AH2/AH-  + O2 → Fe(III)/Cu(II) + H2O2 + products. Rate constants are 5.7 × 104 and 4.7 × 104 M-2 s-1 for Fe(III) + AH2/AH- and 7.7 × 104 and 2.8 × 106 M-2 s-1 for Cu(II) + AH2/AH-, respectively.

Description

Keywords

3402 Inorganic Chemistry, 34 Chemical Sciences

Journal Title

Sci Rep

Conference Name

Journal ISSN

2045-2322
2045-2322

Volume Title

11

Publisher

Springer Science and Business Media LLC