Kinetic and stoichiometric assessment of the antioxidant activity of flavonoids by electron spin resonance spectroscopy

D B McPhail, R C Hartley, P T Gardner, G G Duthie

Research output: Contribution to journalArticle

107 Citations (Scopus)

Abstract

dThere is current interest in the use of naturally occurring flavonoids as antioxidants for the preservation of foods and the prevention of diseases such as atherosclerosis and cancers. To establish the molecular characteristics required for maximum antioxidant activity, electron spin resonance (ESR) spectroscopy has been used to determine the stoichiometry and kinetics of the hydrogen-donating ability of 15 flavonoids and D-alpha-tocopherol to galvinoxyl, a resonance-stabilized, sterically protected aryloxyl radical. The second-order reaction rates, which will be governed by O-H bond dissociation energies, were myricetin > morin > quercetin > fisetin similar to catechin > kaempferol similar to luteolin > rutin > D-alpha-tocopherol > taxifolin > tamarixetin > myricetin 3',4',5'-trimethyl ether > datiscetin > galangin > hesperitin similar to apigenin. Reactivity is highly dependant on the configuration of OH groups on the flavonoid B and C rings, there being little contribution from the A ring to antioxidant effectiveness. Highest reaction rates and stoichiometries were observed with flavonols capable of being oxidized to orthoquinones or extended paraquinones. However, rates and stoichiometries did not always correlate and the data suggest that kinetic factors may be of greater importance within a biological context.

Original languageEnglish
Pages (from-to)1684-1690
Number of pages7
JournalJournal of Agricultural and Food Chemistry
Volume51
Issue number6
DOIs
Publication statusPublished - 12 Mar 2003

Keywords

  • ESR
  • flavonoids
  • antioxidant capacity
  • kinetics
  • stoichiometry
  • galvinoxyl radical
  • potentially anticarcinogenic flavonoids
  • bond-disociation entalpies
  • O-H
  • phenolic antioxidants
  • phenoxyl radicals
  • quercetin
  • media
  • polyphenols
  • beverages
  • energies

Cite this

Kinetic and stoichiometric assessment of the antioxidant activity of flavonoids by electron spin resonance spectroscopy. / McPhail, D B ; Hartley, R C ; Gardner, P T ; Duthie, G G.

In: Journal of Agricultural and Food Chemistry, Vol. 51, No. 6, 12.03.2003, p. 1684-1690.

Research output: Contribution to journalArticle

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AB - dThere is current interest in the use of naturally occurring flavonoids as antioxidants for the preservation of foods and the prevention of diseases such as atherosclerosis and cancers. To establish the molecular characteristics required for maximum antioxidant activity, electron spin resonance (ESR) spectroscopy has been used to determine the stoichiometry and kinetics of the hydrogen-donating ability of 15 flavonoids and D-alpha-tocopherol to galvinoxyl, a resonance-stabilized, sterically protected aryloxyl radical. The second-order reaction rates, which will be governed by O-H bond dissociation energies, were myricetin > morin > quercetin > fisetin similar to catechin > kaempferol similar to luteolin > rutin > D-alpha-tocopherol > taxifolin > tamarixetin > myricetin 3',4',5'-trimethyl ether > datiscetin > galangin > hesperitin similar to apigenin. Reactivity is highly dependant on the configuration of OH groups on the flavonoid B and C rings, there being little contribution from the A ring to antioxidant effectiveness. Highest reaction rates and stoichiometries were observed with flavonols capable of being oxidized to orthoquinones or extended paraquinones. However, rates and stoichiometries did not always correlate and the data suggest that kinetic factors may be of greater importance within a biological context.

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