Thiol oxidation by plant peroxidases is an oxygen consuming process in
dependent of hydrogen peroxide addition. The in vitro system consists
of two interdependent reactions, i.e. hydrogen peroxide mediated oxida
tion of thiols via the enzymatic intermediates compound I and II yield
ing thiyl radicals, and further the non-enzymatic reaction of thiyl ra
dicals to the corresponding disulphides or reaction with molecular oxy
gen yielding superoxide radicals and hydrogen peroxide. The thiyl radi
cal generation per time (regulated by enzyme, thiol, and phenol concen
tration) determines the amount of hydrogen peroxide generated and as a
consequence the amount of phenol which is oxidized by this plant enzy
me. In the presence of phenols and with increasing pH oxygen consumpti
on, thiol oxidation, and as a consequence the amount of hydrogen perox
ide generated, increases. Considering phenol oxidation the system appa
rently becomes biphasic with a slow phenol oxidation phase A followed
by a rapid phenol oxidation phase B. During phase A oxygen consumption
occurs and thiol is oxidized completely. We present reaction schemes
and discuss the biological relevance with regard to a possible biosynt
hetic route of hydrogen peroxide in plants.