| This thesis is an investigation of the oxidative properties of 8-(4"-hydroxyphenyl)-2'-deoxyguanosine (24) which is a potential biomarker for phenolic toxin exposure. Adduct 24 undergoes oxidation readily and in the presence of Na2IrCl6 forms polyphenolic compounds through ortho-ortho C-C bonds. This chemistry is due to the formation of a phenolic radical which affords the products observed and is in contrast to all other known C8-aryl deoxyguanosine (dG) oxidation mechanisms. Oxidation studies with horseradish peroxidase and 24 solidified the mechanism of phenolic radical formation. Replacement of OH with OCH3 in 8-(4"-methoxyphenyl)-2'-dG (54), restores the well-established oxidative chemistry for dG adducts that form spiroiminodihydantoin (Sp) lesions. The oxidized product of 24 also forms a cross-link with dG. These results show that the phenolic group can expand the redox properties of dG adducts to afford new reactive intermediates and may yield useful substrates for biomaterials.;The second part of this thesis examines the metal binding properties of the dimer (56) and trimer (57) compounds. Compounds 56, and 57 showed substantial metal binding affinity to divalent metal ions Zn(II), Ni(II), and Cu(II). These results highlight their potential use as metal ion sensors. |
