S. Llesuy et al., KINETIC-ANALYSIS AND DOUBLE QUENCHING EXPERIMENTS AS TOOLS TO ELUCIDATE THE ACTION MECHANISM OF ANTIOXIDANTS, Boletin de la Sociedad Chilena de Quimica, 43(3), 1998, pp. 329-337
The dependence of the oxidation rate with the concentration of an addi
tive that reduces the rate of the process can be employed to determine
if its effect is due to trapping of active radicals (chain-breaking a
ntioxidant) or to its ability to chelate active metals (metal-chelatin
g antioxidant). Kinetic expressions are deduced for metal-chelating an
tioxidants of high or low efficiency and for chain-breaking antioxidan
ts. In particular, it is proposed that chain-breaking antioxidants mus
t provide lineal SternVolmer's like relationships, while efficient pri
mary antioxidants will give plots with a strong upward curvature. A se
cond procedure is proposed that could allow a determination of the mai
n mechanism of action of the additive based on double quenching experi
ments. The effect of the simultaneous addition of two antioxidant will
depend of their mechanism of action. Two strong metal-chelating antio
xidants will present a synergic behavior, while two chain-breaking ant
ioxidants acting on the same species will present antagonic behavior.
Antioxidants acting by different mechanisms will present an indifferen
t behavior, its efficiency being independent of the presence of the se
cond antioxidant. Several different situations are contrasted with dat
a obtained in the autoxidation of brain homogenates employing propyl g
allate, desferrioxamine and BHT as antioxidants.