Mechanism of radiation-induced reactions in aqueous solution of coumarin-3-carboxylic acid: effects of concentration, gas and additive on fluorescent product yield.

Abstract:

:The radiation-induced reactions of a water-soluble coumarin derivative, coumarin-3-carboxyl acid (C3CA), have been investigated in aqueous solutions by pulse radiolysis with a 35 MeV electron beam, final product analysis following (60)Co γ-irradiations and deterministic model simulations. Pulse radiolysis revealed that C3CA reacted with both hydroxyl radicals ((•)OH) and hydrated electrons (e(-) (aq)) with near diffusion-controlled rate constants of 6.8 × 10(9) and 2.1 × 10(10) M(-1) s(-1), respectively. The reactivity of C3CA towards O(2)(• -) was not confirmed by pulse radiolysis. Production of the fluorescent molecule, 7-hydroxy-coumarin-3-carboxylic acid (7OH-C3CA), was confirmed by final product analysis with a fluorescence spectrometer coupled to a high performance liquid chromatography (HPLC) system. Production yields of 7OH-C3CA following (60)Co γ-irradiations depended on the irradiation conditions and ranged from 0.025 to 0.18 (100 eV) (-1). Yield varied with saturating gas, additive and C3CA concentration, implying the presence of at least two pathways capable of providing 7OH-C3CA as a stable product following the scavenging reaction of C3CA with (•)OH, including a peroxidation/elimination sequence and a disproportionation pathway. A reaction mechanism for the two pathways was proposed and incorporated into a deterministic simulation, showing that the mechanism can explain experimentally measured 7OH-C3CA yields with a constant conversion factor of 4.7% from (•)OH scavenging to 7OH-C3CA production, unless t-BuOH was added.

journal_name

Free Radic Res

journal_title

Free radical research

authors

Yamashita S,Baldacchino G,Maeyama T,Taguchi M,Muroya Y,Lin M,Kimura A,Murakami T,Katsumura Y

doi

10.3109/10715762.2012.684879

subject

Has Abstract

pub_date

2012-07-01 00:00:00

pages

861-71

issue

7

eissn

1071-5762

issn

1029-2470

journal_volume

46

pub_type

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