Binding of metal ions to melanin and their effects on the aerobic reactivity

The binding of Mg(II), Ca(II), Zn(II), Cu(II) and Fe(III) to ETDA-washed Sepia melanin is quantified by inductively coupled plasma mass spectrometry. By monitoring the solution pH change associated with metal uptake, it is concluded that Mg(II), Ca(II) and Zn(II) bind to carboxylic acid groups in melanin, Cu(II) binds to hydroxyl (OH) groups and Fe(III) binds to OH or amine groups. The aerobic reactivity of melanins with different metal contents is analyzed by examining their ability to cause strand breaks in supercoiled pUC18 DNA. Cu(II)- and Fe(III)-enriched melanins induce the most damage. Hydroxyl radical, *OH, is proposed to be one of the reactive oxygen species responsible.