KINETICS OF THE COMPETITIVE DEGRADATION OF DEOXYRIBOSE AND OTHER MOLECULES BY HYDROXYL RADICALS PRODUCED BY THE FENTON REACTION IN THE PRESENCE OF ASCORBIC-ACID
Mj. Zhao et L. Jung, KINETICS OF THE COMPETITIVE DEGRADATION OF DEOXYRIBOSE AND OTHER MOLECULES BY HYDROXYL RADICALS PRODUCED BY THE FENTON REACTION IN THE PRESENCE OF ASCORBIC-ACID, Free radical research, 23(3), 1995, pp. 229-243
The competition method in which the Fenton reaction is employed as an
. OH radical generator and deoxyribose as a detecting molecule, has be
en used to determine the rate constants for reactions of the . OH radi
cal with its scavengers. Nonlinear competition plots were obtained for
those scavengers which reacted with the Fenton reagents (Fe2+ or H2O2
). Ascorbic acid is believed to overcome this problem. We have investi
gated the kinetics of deoxyribose degradation by . OH radicals generat
ed by the Fenton reaction in the presence of ascorbic acid, and observ
ed that the inclusion of ascorbic acid in the Fenton system greatly in
creased the rate of . OH radical generation. As a result, the interact
ion between some scavengers and the Fenton reagents became negligeable
and linear competition plots of A(0)/A vs scavenger concentrations we
re obtained. The effects of experimental conditions such as, the conce
ntrations of ascorbic acid, deoxyribose, H2O2 and Fe2+-EDTA, the EDTA/
Fe2+ ratio as well as the incubation time, on the deoxyribose degradat
ion and the determination of the rate constant for mercaptoethanol cho
sen as a reference compound were studied. The small standard error, (6
.76 +/- 0.21) x 10(9) M(-1)s(-1), observed for the rate constant value
s for mercaptoethanol determined under 13 different experimental condi
tions, indicates the latter did not influence the rate constant determ
ination. This is in fact assured by introducing a term, k(x), into the
kinetic equation. This term represents the rate of . OH reactions wit
h other reagents such as ascorbic acid, Fe2+-EDTA, H2O2 etc. The agree
ment of the rate constants obtained in this work with that determined
by pulse radiolysis techniques for cysteine, thiourea and many other s
cavengers, suggests that this simple competition method is applicable
to a wide range of compounds, including those which react with the Fen
ton reagents and those whose solubility in water is low.