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EN
Radiation-induced processes in ionic liquid (IL) methyltributylammonium bis[(trifl uoromethyl)sulfonyl] imide ([MeBu3N][NTf2]) solutions containing p-terphenyl (TP) and saturated with carbon dioxide (CO2) were studied using nanosecond pulse radiolysis technique with UV-vis detection. The transient absorption spectra generated in these solutions were assigned to TP radical anions (TP•–) and triplet excited states (3TP*). Saturation of [MeBu3N][NTf2] solutions with carbon dioxide efficiently takes out presolvated electrons (e–presolv) and solvated electrons (e–solv). On the other hand CO2 is not a scavenger of excited states of TP (1TP*, 3TP*), which in the reaction with triethylamine (TEA) leads to the formation of TP•-.
2
Content available Ionic processes in irradiated solid polymers
EN
The reactions of ionic species generated in irradiated polymers (polyethylene, poly(dimethylsiloxane), poly(methyl methacrylate), and poly(ethylene terephthalate)) doped with pyrene, Py, were observed by radiothermoluminescence and complementary absorption spectroscopic measurements. The charge stabilization in polymers and charge transfer to the solute depend on the chemical structure of polymer chains and physical state of the polymer matrix. The recombination of ionic species is stimulated by relaxation processes of polymers. Total neutralization of charges in irradiated polymers occurs at the glass transition temperature of polymers. Mutual recombination of Py radical ions generates singlet excited states of the solute followed by Py monomer and excimer (depending on the solute concentration) fluorescence. Recombination of Py radical cations and negative species from the polymer matrix leads to the formation of Py triplet excited states followed by Py phosphorescence.
EN
Reduction of the triplet state of 4-carboxybenzophenone (CB) by a series of five substituted methionines was monitored under laser flash photolysis conditions in aqueous solution. Spectral resolution techniques were employed to determine initial quantum yields of the photoproducts. Branching ratios were evaluated for the decay of the charge-transfer complex by the competing processes of back electron transfer, proton transfer, and escape of radical ions. The relative prominence of these processes was discussed in terms of the proton-transfer tendencies of the nominal sulfur-radical-cationic species. A scheme was proposed to account for the pH effects observed. The kinetic equations were solved with a minimum of assumptions, and simulations were performed that qualitatively support the proposed scheme.
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