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excess of ONOO- at the highly alkaline conditions needed to
stabilize ONOO-. In other respects, additional information about
this reaction-diffusion system will surely benefit from ap-
propriate experiments under irreversible conditions with
femto-picosecond UV and IR pulse pump-probe spectroscopy
techniques.72,73 Other likely informative experiments can result
if chemically induced dynamic nuclear spin polarization
(CIDNP) and photo-CIDNP methods74,75 could be applied to
the study of in-cage geminate radicals versus bulk radicals
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The reaction type under study (A + B ) C, with [A] ) [B]
and kf diffusion controlled) has been extensively studied from
the theoretical point of view. Overall, the uncovering of a
•-
distance-dependent reaction rate constant between •NO or O2
to form ONOO- at chemical equilibrium is to the best of our
knowledge an unprecedented result in the experimental field of
reversible diffusion-controlled reactions, which confirms some
previous theoretical predictions for the behavior of reactions
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assumed the validity of the law of mass action, should be revised
and their distance/concentration dependence acknowledged.
Regarding kinetic data, our results (Figure 4C, eq 21C) support
diffusion-controlled distance-dependent forward rate constant
•-
for ONOO- formation kf310K g 7.5 × 109 M-1 s-1 from O2
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Acknowledgment. We thank Gerardo Ferrer-Sueta for critical
comments and discussions. H.B. acknowledges PEDECIBA and
ANII for support in the form of a Ph.D. fellowship and a
research grant (FCE 485). R.R. is a Howard Hughes Interna-
tional Research Scholar.
Supporting Information Available: Data on the rate
constant of peroxynitrite decay at pH >12, raw data on the
effects of 50% glycerol on the concentration of •NO in alkaline
ONOO- solutions, and ONOO- formation time courses after
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