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Numerous transition metal ions and their complexes in their lower oxidation states (LmMn+) were found to have the oxidative features of the Fenton reagent, and, therefore, the mixtures of these metal compounds with H2O2 were named "Fenton-like" reagents. Using the Marcus theory and the experimental data in the literature, it is shown that in most cases the(More)
In this study we calculate the half-life of .NO in its reactions with superoxide and with oxygen under various conditions using the known rate constants for these reactions. The measured half-life of .NO in biological systems is 3-5 s, which agrees well with the calculated value for intracellular .NO, but not for extracellular .NO under normal physiological(More)
The reactions of NO. with O2.- and with HO2. were studied using the pulse radiolysis technique under pseudo first order conditions where ([O2.-]o + [HO2.]o) > [NO.]o at pH 3.3-10.0. The rate constant of the reaction of NO. with O2.- was determined both by monitoring the decay of O2.- at 250 nm and the formation of ONOO- at 302 nm to be (4.3 +/- 0.5) x 10(9)(More)
Radiation chemical experiments demonstrate that the reaction of tyrosyl radical (TyrO(.)) with (.)NO(2) yields 45 +/- 3% 3-nitrotyrosine and that a major product of the reaction of TyrO(.) with (.)NO is 3,3'-dityrosine. Radiolysis was used to generate (.)NO and O-(2) in the presence of tyrosine and bicarbonate at pH 7.5 +/- 0.1. The nitration yield was(More)
We have studied the reaction kinetics of ten manganese porphyrins, differing in their meso substituents, with peroxynitrite (ONOO-) and carbonate radical anion (CO3.) using stopped-flow and pulse radiolysis, respectively. Rate constants for the reactions of Mn(III) porphyrins with ONOO- ranged from 1 x 10(5) to 3.4 x 10(7) m(-1) s(-1) and correlated well(More)
The method of determination of Redox potentials of radicals, using the pulse radiolysis technique, is outlined. The method is based on the determination of equilibrium constants of electron transfer reactions between the radicals and appropriate acceptors. The limitations of this technique are discussed. The redox potentials of several quinones-semiquinones(More)
The reaction of ONOO(-) with CO(2) at alkaline pH was recently reported to form a transient absorption with a maximum at 640 nm and a half-life of ca. 4 ms at 10 degrees C [Meli et al. (1999) Helv. Chim. Acta 82, 722-725]. This transient absorption was hardly affected by the presence of *NO, and therefore was attributed to the adduct ONOOC(O)O(-). This(More)
Using the pulse radiolysis technique it was shown that copper(II) complexes of kinetin and 6-benzylaminopurine (6-BAP) catalyze O2- dismutation very efficiently at physiological pH. The 'turnover' rate constants at pH 7 were determined to be (1.5 +/- 0.3) x 10(9) and (2.2 +/- 0.4) x 10(9) M-1s-1 for 6-BAP and kinetin, respectively. The system was studied at(More)
Copper complexes of 1,10-phenanthroline and some substituted 1,10-phenanthroline cleave DNA in the presence of a reducing agent and molecular oxygen. Generally, the damage is attributed to hydroxyl radicals which are formed through the Haber-Weiss reaction. It is assumed that this reaction occurs with the ternary metal complexes with the biological target(More)