A quantum chemical explanation of the antioxidant activity of flavonoids

被引:368
作者
vanAcker, SABE [1 ]
deGroot, MJ [1 ]
vandenBerg, DJ [1 ]
Tromp, MNJL [1 ]
DonneOpdenKelder, G [1 ]
vanderVijgh, WJF [1 ]
Bast, A [1 ]
机构
[1] FREE UNIV AMSTERDAM HOSP,DEPT MED ONCOL,NL-1081 HV AMSTERDAM,NETHERLANDS
关键词
D O I
10.1021/tx9600964
中图分类号
R914 [药物化学];
学科分类号
100701 ;
摘要
Flavonoids are a group of naturally occurring antioxidants, which over the past years have gained tremendous interest because of their possible therapeutic applicability. The mechanism of their antioxidant activity has been extensively studied over several decades. However, there is still much confusion about the molecular mechanism of radical scavenging and the relationship between structure and activity. Therefore, we have calculated the heat of formation and the geometry of both the parent compound and the corresponding radical using the ab initio program GAMESS. We have compared their differences in energy in order to gain insight into the stability of the radical and the ease with which it is formed. We have also investigated the spin density of the radical, to determine the delocalization possibilities. These calculated data were compared with experimental data from ESR (hyperfine coupling constants) and electrochemical oxidation (E(p/2)) and were found to be in good agreement. By comparing the geometries of several flavonoids, we were able to explain the structural dependency of the antioxidant action of these compounds. The extremely good antioxidant activity of the flavonols could be explained by the formation of an intramolecular hydrogen bond.
引用
收藏
页码:1305 / 1312
页数:8
相关论文
共 34 条
[1]  
ALLAN FH, 1993, CHEM DESIGN AUTOMATI, V8, P31
[2]   SELF-CONSISTENT MOLECULAR-ORBITAL METHODS .21. SMALL SPLIT-VALENCE BASIS-SETS FOR 1ST-ROW ELEMENTS [J].
BINKLEY, JS ;
POPLE, JA ;
HEHRE, WJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1980, 102 (03) :939-947
[3]  
Bors W, 1987, Free Radic Res Commun, V2, P289, DOI 10.3109/10715768709065294
[4]  
BORS W, 1990, METHOD ENZYMOL, V186, P343
[5]  
*CHEM DES LTD, 1993, CHEMX VERS JAN
[6]   CONFORMATIONAL-ANALYSIS OF FLAVONOIDS - CRYSTAL AND MOLECULAR-STRUCTURES OF MORIN HYDRATE AND MYRICETIN (1/2) TRIPHENYLPHOSPHINE OXIDE COMPLEX [J].
CODY, V ;
LUFT, JR .
JOURNAL OF MOLECULAR STRUCTURE, 1994, 317 (1-2) :89-97
[7]   SCAVENGER AND ANTIOXIDANT PROPERTIES OF 10 SYNTHETIC FLAVONES [J].
COTELLE, N ;
BERNIER, JL ;
HENICHART, JP ;
CATTEAU, JP ;
GAYDOU, E ;
WALLET, JC .
FREE RADICAL BIOLOGY AND MEDICINE, 1992, 13 (03) :211-219
[8]  
*DEP CHEM COL U, 1994, BATCHMIN VERS 4 0
[9]  
*DEP CHEM COL U, 1994, MACR VERS 4 5
[10]  
DUPUIS M, 1980, QG01 NRCC GAMESS