Antioxidant behaviour of caffeine: Efficient scavenging of hydroxyl radicals

doi:10.1016/0278-6915(91)90056-D

Food and Chemical Toxicology

Volume 29, Issue 1, 1991, Pages 1-6

https://doi.org/10.1016/0278-6915(91)90056-D Get rights and content

Abstract

Considerable controversy exists in the literature regarding the toxicity of coffee, including its possible carcinogenic and anticarcinogenic properties. This study reports on the reaction of 1,3,7-trimethylxanthine (caffeine) with the hydroxyl radical (·OH), as investigated by electron spin resonance (ESR) spin trapping. The ·OH was generated by the Fenton reaction (Fe²⁺ + H₂O₂) as well as by the reaction of chromium(V) with H₂O₂. The results show that caffeine effectively scavenges ·OH with a reaction rate constant of ∼ 5.9 × 10⁹m⁻¹ sec⁻¹ that is comparable with those of other efficient ·OH radical scavengers. ESR measurements provide evidence that a caffeine-derived oxygen-centred radical is formed in the reaction of caffeine with ·OH and suggest a biochemical basis for the understanding of the reported anticarcinogenic properties of caffeine and related methylxanthine compounds.

References (41)

E. Alejandre-Duran et al.
Implication of active oxygen species in the direct-acting mutagenicity of tea
Mutation Research
(1987)
B.N. Ames
Endogenous DNA damage as related to cancer and aging
Mutation Research
(1989)
R.R. Ariza et al.
Study of the causes of direct-acting mutagenicity in coffee and tea using the Ara test in Salmonella typhimurium
Mutation Research
(1988)
J. Booth et al.
The reaction of the carcinogenic dibenzcarbazoles and dibenzacridines with purines and nucleic acid
Biochimica et Biophysica Acta
(1953)
G.R. Buettner
Spin trapping: ESR parameters of spin adducts
Free Radical Biology and Medicine
(1987)
G.R. Buettner et al.
Considerations in the spin trapping of superoxide and hydroxyl radical in aqueous systems using 5,5-dimethylpyrroline-N-oxide
Biochemical and Biophysical Research Communications
(1978)
P. Cole
Coffee-drinking and cancer of the lower urinary tract
Lancet
(1971)
H.C. Grice
Genotoxicity and carcinogenicity assessments of caffeine and theobromine (Letter)
Food and Chemical Toxicology
(1987)
D. Jamieson
Oxygen toxicity and reactive oxygen metabolites in mammals
Free Radical Biology and Medicine
(1989)
M.B. Kadiiska et al.
A comparison of cobalt (II) and iron (II) hydroxyl and superoxide free radical formation
Archives of Biochemistry and Biophysics
(1989)

K.R. Maples et al.

Free radical metabolite of uric acid

Journal of Biological Chemistry

(1988)

U. Mohr et al.

The influence of caffeine on tumour incidence in Sprague-Dawley rats

Food and Chemical Toxicology

(1984)

L.W. Oberley et al.

Cell differentiation, aging and cancer: the possible roles of superoxide and superoxide dismutases

Medical Hypotheses

(1980)

H.S. Rosenkranz et al.

Genotoxicity and carcinogenicity assessments of caffeine and theobromine (Letter)

Food and Chemical Toxicology

(1987)

A. Sevanian et al.

Conservation of vitamin C by uric acid in blood

Journal of Free Radical Biology and Medicine

(1985)

X. Shi et al.

Chromium (V) and hydroxyl radical formation during the glutathione reductase-catalyzed reduction of chromium (VI)

Biochemical and Biophysical Research Communications

(1989)

X. Shi et al.

On the hydroxyl radical formation in the reaction between hydrogen peroxide and biologically generated chromium (V) species

Archives of Biochemistry and Biophysics

(1990)

M.G. Simic

Mechanism of inhibition of free-radical processes in mutagenesis and carcinogenesis

Mutation Research

(1988)

M.G. Simic et al.

Generation of oxy radicals in biosystems

Mutation Research

(1989)

H.-P. Würzner et al.

A 2-year feeding study of instant coffees in rats

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Research sectionAntioxidant behaviour of caffeine: Efficient scavenging of hydroxyl radicals

Abstract

Mutation Research

Mutation Research

Mutation Research

Biochimica et Biophysica Acta

Free Radical Biology and Medicine

Biochemical and Biophysical Research Communications

Lancet

Food and Chemical Toxicology

Free Radical Biology and Medicine

Archives of Biochemistry and Biophysics

Journal of Biological Chemistry

Food and Chemical Toxicology

Medical Hypotheses

Food and Chemical Toxicology

Journal of Free Radical Biology and Medicine

Biochemical and Biophysical Research Communications

Archives of Biochemistry and Biophysics

Mutation Research

Mutation Research

Research section
Antioxidant behaviour of caffeine: Efficient scavenging of hydroxyl radicals