Evidence of Porphyrin-Like Structures in Natural Melanin Pigments Using Electrochemical Fingerprinting.

Eumelanins are extended heterogeneous biopolymers composed of molecular subunits with ambiguous macromolecular topology. Here, an electrochemical fingerprinting technique is described, which suggests that natural eumelanin pigments contain indole-based tetramers that are arranged into porphyrin-like domains. Spectroscopy and density functional theory calculations suggest that sodium ions undergo occupancy-dependent stepwise insertion into the core of porphyrin-like tetramers in natural eumelanins at discrete potentials.