[en] This paper deals with the formation of a series of antioxidant depsides obtained from flavonoid solutions irradiated with gamma rays. These reactions take place in radiolyzed alcohol solutions, a medium that is very rich in many different highly reactive species and that hosts specific reactions. We focus on the first step of those reactions, i.e., reactivity of the solute (flavonoid) with the alkoxy radicals CH(3)O(*) and CH(3)CH(2)O(*) formed in methanol and ethanol, respectively, and their carbon-centered isomers: the 1-hydroxy-methyl ((*)CH(2)OH) and the 1-hydroxy-ethyl (CH(3)(*)CHOH) radicals. Among the different flavonoid groups of molecules, only flavonols are transformed. To establish the structure-reactivity relationship that explains why the radiolytic transformation occurs only for those compounds, the process is rationalized theoretically, with Density Functional Theory calculations, taking into account the solvent effects by a Polarizable Continuum Model and a microhydrated environment (one or two water molecules surrounding the active center). The first redox reaction, occurring between the flavonol and the reactive species formed upon irradiation of the solvent, is studied in terms of (1) the O-H bond dissociation enthalpy of each OH group of the flavonoids and (2) electron abstraction from the molecule. We conclude that the reaction, initiated preferentially by the alkoxy radicals, first occurs at the 3-OH group of the flavonol. It is then followed by the formation of a peroxyl radical (after molecular oxygen or superoxide addition). The different cascades of reactions, which lead to the formation of depsides via C-ring opening, are discussed on the basis of the corresponding calculated energetic schemes.
Disciplines :
Chemistry Physics
Author, co-author :
Kozlowski, Dorothée ; Université de Mons > Faculté de Psychologie et des Sciences de l'Education > Méthodologie et formation
Marsal, Philippe
Steel, M.C.
Mokrini, R.
Duroux, J.L.
Lazzaroni, Roberto ; Université de Mons > Faculté des Sciences > Service de Chimie des matériaux nouveaux
Trouillas, P.
Language :
English
Title :
Theoretical Investigation of the Formation of a New Series of Antioxidant Depsides from the Radiolysis of Flavonoid Compounds
Publication date :
01 August 2007
Journal title :
Radiation Research
ISSN :
0033-7587
Publisher :
Radiation Research Society, Vatican City
Volume :
168
Issue :
2
Pages :
243-252
Peer reviewed :
Peer Reviewed verified by ORBi
Research unit :
S817 - Chimie des matériaux nouveaux
Research institute :
R400 - Institut de Recherche en Science et Ingénierie des Matériaux
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