The influence of iron on selected properties of synthetic pheomelanin

It is believed that while eumelanin plays photoprotective and antioxidant role in pigmented tissues, pheomelanin being more photoreactive could behave as a phototoxic agent. Although the metal ion-sequestering ability of melanin might be protective, transition metal ions present in natural melanins could affect their physicochemical properties. The aim of this research was to study iron binding by pheomelanin and analyze how such a binding affects selected properties of the melanin. Synthetic pheomelanin (CDM), prepared by enzymatic oxidation of DOPA in the presence of cysteine was analyzed by electron paramagnetic resonance (EPR) spectroscopy, spectrophotometry, chemical analysis, and time-resolved measurements of singlet oxygen phosphorescence. Iron broadened EPR signal of melanin and increased its optical absorption. Iron bound to melanin exhibited EPR signal at g = 4.3, typical for high-spin iron (III). Iron bound to melanin significantly altered the kinetics of melanin photodegradation, which in turn modified the accessibility and stability of the melanin-iron complexes as indicated by the release of iron from melanin induced by diethylenetriaminepentaacetic acid and KCN. Although bound to melanin iron little affects initial stages of photodegradation of CDM, the effect of iron becomes more pronounced at later stages of melanin photolysis.