2009 **Abstract:** Oxygen and oxidants enhance the sensitivity of cells to radiation. To understand this effect at the mechanistic level, the redox dependences for the reactivity of weakly reducing alpha-monoalkoxyalkyl radicals of 1,4-dioxane and tetrahydrofuran with a series of oxidants, for example, quinones, viologens, and nitro-arenes, with one-electron reduction potentials E71 values ranging from -80 to -640 mV, have been determined using the technique of pulse radiolysis. The second-order rate constants for these reaction…

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“…In the case of 1(iPr) •+ , the 14 N hfcs of 0.74 (1 N) and 0.69 (1 N) mT, with an average value of 0.72 mT, together with the remaining 1 H hfcs reveal that the electron and the charge in the cyclophane are basically confined to one PD-type moiety. For 3(Me) •+ and 3(iPr) •+ , compatible data can also be established (e.g., 14 N hfcs of 0.69 and 0.70 mT, respectively, see Table 1).…”

confidence: 95%

“…In the case of 1(iPr) •+ , the 14 N hfcs of 0.74 (1 N) and 0.69 (1 N) mT, with an average value of 0.72 mT, together with the remaining 1 H hfcs reveal that the electron and the charge in the cyclophane are basically confined to one PD-type moiety. For 3(Me) •+ and 3(iPr) •+ , compatible data can also be established (e.g., 14 N hfcs of 0.69 and 0.70 mT, respectively, see Table 1).…”

confidence: 95%

“…The spectrum of 1(iPr) 2+ showed significantly less resolution in the mixed solvent (Figure a) than in the single solvent butyronitrile rigid-glass, apparently because the monoradical impurity was considerably more intense. Failure to oxidize more completely probably occurs because of the lower redox potential of the Ag + used for carrying out the oxidation in the mixed solvent compared to CH 2 Cl 2 …”

confidence: 99%

“…These showed slopes considerably lower (~3-4 V -1 ) than found for radiosensitization efficiency (~8 V -1 ). 81,82 Lower slopes of the 'electron affinity' plots for radiosensitization, ~6 or 7 V -1 , were found if concentrations to achieve enhancement ratios of 1.2 or 1.4, rather than 1.6 were analysed, 14,15 analysis of the smaller effects possibly closer to the 'true' redox relationship because of fewer artefacts from thiol depletion.…”

confidence: 99%

“…31 Only few examples of the a-hydroxyalkyl radical reactions in aqueous solutions, all with aromatic compounds, were argued to involve the inner-sphere ET, 32 with examples of the possible outer-sphere ET also given. 33 An unambiguous theoretical corroboration of either variant is still lacking to our knowledge. The typically large imaginary frequencies (2300-2400i cm À1 ) are found indicative of the light particle transfer.…”

confidence: 99%