Lipid peroxidation, which plays a part in a wide variety of biological
processes, is an integral process in the oxidation of unsaturated fat
ty acids via a radical chain reaction. Among the various species which
may induce this reaction in vivo, reactive forms of oxygen such as pe
roxide anion, the hydroxyl radical and singlet oxygen are of cardinal
importance. These species may be generated enzymatically, chemically o
r by various radiochemical and photochemical reactions. We present her
e the advantages of photochemical induction of peroxidation, and we de
scribe the principles of the reactions, the photosensitizers that can
be employed to generate the various reactive species of oxygen, and th
e techniques, direct (ESR) or indirect (specific traps), used to detec
t the reactive species. Photosensitization can induce the formation of
a whole gamut of products of lipid peroxidation: conjugated dienes, a
ldehydes, hydroperoxides, etc. The relative proportions of the various
hydroperoxides of fatty acids or cholesterol depend on the nature of
the reactive species involved. Utilization of photochemical reactions
is an effective and clean way of inducing peroxidation, allowing fine
control of both initiation and orientation.