One-electron reduction of thionine has been studied by using the technique of nanosecond pulse radiolysis and kinetic spectrophotometry. H,eaq− as well as radicals derived from methanol, ethanol, isopropanol, THF, dioxane andt-butanol by H atom abstraction were used as reductants. The rate constants for the transfer of electrons from these radicalts to thionine were directly determined from the pseudo first-order formation rates of the product, semithionine and the one-electron reduction potential of thionine estimated. The absorption spectrum of semithionine in its different conjugate acid-base forms was found to be in agreement with previously reported spectra and the decay of the species was second order. By monitoring transient absorbance changes as a function of pH, twopKa values were observed and, based on the effect of ionic strength on the second-order decay constants of the species were assigned to the equilibria described.
Volume 135, 2023
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