Predicting the activity of phenolic antioxidants: Theoretical method, analysis of substituent effects, and application to major families of antioxidants

被引:1391
作者
Wright, JS
Johnson, ER
DiLabio, GA
机构
[1] Carleton Univ, Dept Chem, Ottawa, ON K1S 5B6, Canada
[2] Carleton Univ, Ottawa Carleton Chem Inst, Ottawa, ON K1S 5B6, Canada
关键词
D O I
10.1021/ja002455u
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A procedure based on density functional theory is used for the calculation of the gas-phase bond dissociation enthalpy (BDE) and ionization potential fur molecules belonging to the class of phenolic antioxidants. We show that use of locally dense basis sets (LDBS) vs full basis sets gives very similar results for monosubstituted phenols, and that the: LDBS procedure gives good agreement with the change in experimental BDE values for highly substituted phenols in benzene solvent. Procedures for estimating the O-H BDE based on group additivity rules are given and tested. Several interesting classes of phenolic antioxidants are studied with these methods, including commercial antioxidants used as food additives, compounds related to Vitamin E, flavonoids in tea, aminophenols, stilbenes related to resveratrol, and sterically hindered phenols. On the basis of these results we are able to interpret relative rates for the reaction of antioxidants with free radicals, including a comparison of both H-atom-transfer and single-electron-transfer mechanisms, and conclude that in most cases H-atom transfer will be dominant.
引用
收藏
页码:1173 / 1183
页数:11
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