Chapter 1

THE MECHANISM OF ANTIOXIDANT

ACTION IN VITRO
M. H. GORDON
Department of Food Science and Technology, University of Reading,
Whiteknights, Reading RG6 2AP; UK

INTRODUCTION
The spontaneous reaction of atmospheric oxygen with organic com-
pounds leads to a number of degradative changes that reduce the
lifetime of many products of interest to the chemical industry,
especially polymers, as well as causing the deterioration of lipids in
foods. The importance ofoxygen in the deterioration of rubber was
demonstrated over a century ago,l and this finding led chemists to
investigate the chemistry of oxidative deterioration and its inhibition.
Several observations including the detection of an induction period,
the pro- or antioxidant effects of small concentrations of impurities,
and the effect of UV light clearly led to the conclusion that the
reaction between lipids and oxygen, which is termed autoxidation, is a
free radical chain reaction. Like all chain reactions, the mechanism
can be discussed in terms of initiation reactions during which free
radicals are formed, propagation reactions during which free radicals
are converted into other radicals, and termination reactions which
involve the combination of two radicals with the formation of stable
products (Fig. 1).

Initiation of Autoxidation
The direct reaction of a lipid molecule, RH, with a molecule of oxygen
(1) would contravene the principle of conservation of spin angular
momentum, since the lipid molecule is in a singlet electronic state and
the oxygen molecule has a triplet ground state. As a consequence of
this principle, the initiation of autoxidation by the reaction of a lipid
1

B. J. F. Hudson (ed.), Food Antioxidants

© Elsevier Science Publishers Ltd 1990
2 M. H. GORDON

Initiation ROOH*::;;:= ROO' + H'

ROOH::;;:= RO' + 'OH
2 ROOH::;;:= RO' + H 2 0 + ROO'
Propagation R' + O 2 ::;;:= ROO'
ROO' + RIH::;;:=ROOH + R I .
Termination ROO' + RIOO' ::;;:=ROORI + O 2
RO' + R I . ::;;:=ROR'
* Formed by various pathways including reaction of 102 with unsaturated
lipids or lipoxygenase-catalysed oxidation of polyunsaturated fatty acids.

FIG. 1. Mechanism of autoxidation.

molecule with oxygen in its ground state (1) is highly improbable.

RH + 302~ ROOH (1)
The energy of activation for this reaction is very high, values in the
range of 146-272 kJ/mol being quoted?
There are two more probable processes to be considered in the
formation of free radicals. Chain initiation may occur by a direct
reaction between a metal catalyst and a lipid molecule (2). This
process has been shown to be exothermic for methyl linoleate
(!1H = -63 kJ/mol).3
(2)
However, the major initiation process is likely to involve the decom-
position of hydroperoxides. Hydroperoxides are formed during the
propagation reactions (12), but they may also be formed by the
reaction of a lipid molecule with an oxygen molecule in its singlet
excited state or by an enzyme-catalysed reaction. The conversion of
triplet oxygen to singlet oxygen may occur when a photosensitiser,
such as chlorophyll, haematoporphyrins or flavins, including ribofla-
vin, is present. 4 Photosensitisers absorb light in the visible or
near UV region, becoming electronically excited. They may then
transfer their excess energy to an oxygen molecule in an allowed
reaction (3).
Intersystem

) Sens (excited) ~ ISens + 102

1 1 • crossing 3 3°2
Sens~ Sens (excIted) (3)

The singlet oxygen thus formed may then react with a lipid molecule
to yield a hydroperoxide (4).
(4)