Ferrous ion formation by ferrioxamine prepared from aged desferrioxamine: a potential prooxidant property

The siderophore desferrioxamine (DEFOM) binds ferric ions in a 1:1 ratio resulting in a ferrioxamine (FOM) complex. When DEFOM is stored or heat degraded, the resulting FOMD undergoes an autoreduction with the transfer of electrons to the bound ferric ions forming ferrous ions which react with Ferrozine to yield a pink-coloured complex absorbing at 562 nm. Heat-aged DEFOM forms a FOMD complex with an absorption maxima changing from 432 nm to 441 nm. When the autoreduced FOMD complex is placed in a phosphate buffer at pH 7.4, ferrous ions autoxidise transferring electrons to molecular oxygen to form superoxide and hydrogen peroxide. Fenton chemistry leading to the formation of hydroxyl radicals can then occur. Studies with a variety of reactive oxygen scavengers support a role for the hydroxyl radical in damage to the detector molecule deoxyribose. However, when EDTA is present, damage to deoxyribose is decreased and the radicals causing deoxyribose degradation no longer appear to be characteristic of the hydroxyl radical.