The dose rate effects on the in vitro radiolysis products of magnesium-guanosine-5'-monophosphate complexes in aqueous solutions.

This study examined the effects on the radiolysis of magnesium-guanosine-5'-monophosphate complexes in deaerated aqueous solutions, investigated by Fourier transform infrared (FT-IR) spectroscopy. It was found that when the system was irradiated with a dose rate of 500 rad/min (low dose rate), the OH radicals, H atoms and hydrated electrons (eaq-) produced from radiolysis of water reacted mainly by addition to the double bonds C4 = C5 and N7 = C8 of guanine. When the dose rate was 23,800 rad/min (high dose rate) the electrons reacted further with the complex by addition to the carbonyl group, C6 = O, of guanine.

Radiolysis of 4-benzylideneamino-2,2,6,6-tetramethylpiperidine-1-oxyl (BAPO) in aqueous didodecyldimethyl-ammonium bromide (DDAB) membrane mimetic systems.

The influence of solubilisation upon the reactivity of the nitroxyl BAPO with the free radicals produced in irradiated vesicle systems was investigated. The decomposition yield G(-BAPO) determined in didodecyldimethyl-ammonium bromide (DDAB) vesicle systems was found to be only 0.04, while in homogeneous aqueous solutions a value of 1.50 was observed. These results, as well as the EPR spectra of irradiated and nonirradiated samples, lead to the conclusion that BAPO is localized in the interior of the bilayer. This behavior is consistent with the hydrophobic character of the nitroxyl molecule due to its benzylidene group.

Radiolysis of 4-benzylideneamino-2,2,6,6-tetramethylpiperidine-1-oxyl (BAPO) and 3-carboxamido-2,2,5,5-tetramethyl-pyrrolidine-1-oxyl (CATPO) in aqueous solutions.

The mechanism of the gamma-radiolysis of the free nitroxyl radicals BAPO and CATPO in neutral deaerated as well as in N2O-saturated aqueous solutions was investigated. The decomposition of BAPO and CATPO was followed spectrophotometrically by measuring the absorbance at 249 and 233 nm, respectively. The yields G(-BAPO) and G(-CATPO) observed under several conditions are reported and discussed in relation to the yield of OH radicals, H atoms and e-aq, produced in irradiated aqueous solutions. It was found, on the analogy of other nitroxyls, that the corresponding hydroxylamines were formed when BAPO and CATPO react with H atoms, e-aq and hydroxyalkyl radicals. The H atoms and e-aq also react partly with BAPO and CATPO by addition to the aromatic nucleus and by elimination of NH3, respectively. The OH radicals react with BAPO by addition to the aromatic nucleus and by abstraction of H atoms from the 3 or 5 positions or from the methyl groups of the 2 or 6 positions. The reaction of OH radicals with CATPO consists in the abstraction of H atoms from the 3 or 4 positions or from the methyl groups of the 2 or 5 positions. The EPR spectra suggest that in both nitroxyls the final radiolysis products are stable biradicals and other paramagnetic compounds.