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Electron spin resonance of spin-trapped radicals in. gamma. -irradiated aqueous uracil solutions. Chromatographic separation of radicals

Journal Article · · J. Phys. Chem.; (United States)
DOI:https://doi.org/10.1021/j100229a028· OSTI ID:6107485

Air-saturated aqueous uracil solutions were ..gamma.. irradiated at room temperature in the presence of 2-methyl-2-nitrosopropane (the spin trap) (MNP). The resulting radicals were separated subsequently by high-performance liquid chromatography and detected by ESR. With a phosphate buffer (pH 7.0), the spin adduct, NH-C(=O)-NH-C(=O)-CH(-OH)-CH-N(O.)-/sup t/Bu (A), was obtained while with a Na/sub 2/HPO/sub 4/-NaOH buffer (pH 11.0), the spin adduct (B) which has the same chemical structure as (A) but shows a different ESR spectrum from that of (A) was separated. The spin adducts, A and B, were found to be cis-trans isomers of each other. The assignments for these spin adducts were confirmed by studying the ESR spectra of the spin adducts in H/sub 2/O and D/sub 2/O at various pH and pD values and also by investigating the ESR spectra obtained from ..gamma..-irradiated aqueous solutions containing uracil-5-d. In addition to these spin adducts, NH-C(=O)-NH-C(=O)-CH-(-N(O.)-/sup t/Bu)-CH-OH (C) was obtained. The ESR spectra of A, B, and C were compared with those obtained from the uv-irradiated aqueous dihydrouracil solutions containing MNP and H/sub 2/O/sub 2/ at various pH values and were found not to be due to H-addition products at the C5 or C6 of uracil. The spin adducts, A, B, and C, are formed from the radicals generated by addition of hydroxyl radicals to the 5,6 double bond of uracil.

Research Organization:
National Inst. of Health, Bethesda, MD
OSTI ID:
6107485
Journal Information:
J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 87:6; ISSN JPCHA
Country of Publication:
United States
Language:
English