Quantitative kinetic analysis of hydrogen transfer reactions from dietary polyphenols to the DPPH radical

被引:305
作者
Goupy, P [1 ]
Dufour, C [1 ]
Loonis, M [1 ]
Dangles, O [1 ]
机构
[1] Univ Agivnon, INRA, UMRA 408, F-84914 Avignon 9, France
关键词
polyphenol; flavonol; flavanol; procyanidin; caffeic acid ester; antioxidant; DPPH; kinetics;
D O I
10.1021/jf025938l
中图分类号
S [农业科学];
学科分类号
09 ;
摘要
Diphenylpicrylhydrazyl (DPPH) is widely used for quickly assessing the ability of polyphenols to transfer labile H atoms to radicals, a likely mechanism of antioxidant protection. This popular test generally pays no attention to the kinetics of H atom transfer, which however could be even more important than the total H-atom-donating capacities (stoichiometry, EC50) typically evaluated. In the present work, a series of dietary polyphenols belonging to the most representative families (flavonols from onion, flavanol monomers and oligomers from barley, and caffeic acid and caffeoyl esters from artichoke and endive) are characterized not only by their total stoichiometries (n(tot)) but also by their rate constants of first H atom abstraction by DPPH (k(1)), deduced from the kinetic analysis of the decay of the DPPH visible band following addition of the antioxidant. The mildly reactive DPPH radical allows a good discrimation between polyphenols, as demonstrated by the relatively large ranges of k(1) (ca. 400-5000 M-1 s(-1)) and n(tot) (ca. 1-5) values typically measured with antioxidants having a single polyphenolic nucleus. With antioxidants displaying more than one polyphenolic nucleus (procyanidin oligomers, dicaffeoyl esters), the kinetic analysis makes it possible to demonstrate significant differences in reactivity between the subunits (two distinct k(1) values whose ratio lies in the range 3-10) and nonadditive stoichiometries.
引用
收藏
页码:615 / 622
页数:8
相关论文
共 53 条
[1]  
Alluis B, 2001, HELV CHIM ACTA, V84, P1133, DOI 10.1002/1522-2675(20010516)84:5<1133::AID-HLCA1133>3.0.CO
[2]  
2-Z
[3]   Electron paramagnetic resonance studies of radical species of proanthocyanidins and gallate esters [J].
Bors, W ;
Michel, C ;
Stettmaier, K .
ARCHIVES OF BIOCHEMISTRY AND BIOPHYSICS, 2000, 374 (02) :347-355
[4]  
BORS W, 1990, METHOD ENZYMOL, V186, P343
[5]   Structure-activity relationship and classification of flavonoids as inhibitors of xanthine oxidase and superoxide scavengers [J].
Cos, P ;
Ying, L ;
Calomme, M ;
Hu, JP ;
Cimanga, K ;
Van Poel, B ;
Pieters, L ;
Vlietinck, AJ ;
Vanden Berghe, D .
JOURNAL OF NATURAL PRODUCTS, 1998, 61 (01) :71-76
[6]   Antioxidant properties of hydroxy-flavones [J].
Cotelle, N ;
Bernier, JL ;
Catteau, JP ;
Pommery, J ;
Wallet, JC ;
Gaydou, EM .
FREE RADICAL BIOLOGY AND MEDICINE, 1996, 20 (01) :35-43
[7]   Quercetin metabolites inhibit copper ion-induced lipid peroxidation in rat plasma [J].
da Silva, EL ;
Piskula, MK ;
Yamamoto, N ;
Moon, JH ;
Terao, J .
FEBS LETTERS, 1998, 430 (03) :405-408
[8]   Antioxidant properties of anthocyanins and tannins:: a mechanistic investigation with catechin and the 3′,4′,7-trihydroxyflavylium ion [J].
Dangles, O ;
Fargeix, G ;
Dufour, C .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 2000, (08) :1653-1663
[9]   One-electron oxidation of quercetin and quercetin derivatives in protic and non protic media [J].
Dangles, O ;
Fargeix, G ;
Dufour, C .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1999, (07) :1387-1395
[10]   Flavonol-serum albumin complexation. Two-electron oxidation of flavonols and their complexes with serum albumin [J].
Dangles, O ;
Dufour, C ;
Bret, S .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1999, (04) :737-744