  Eumelanin is a widespread biomacromolecule pigment in the biosphere and is
intensively tested in numerous bioelectronics and energetic applications. Many
of these applications depend on eumelanin's ability to conduct proton current
at various levels of hydration. The origin of this behaviour is connected with
a comproportionation reaction between oxidized and reduced monomer moieties and
water. However, neither this reaction nor the formation of the aqueous proton
species have ever been directly observed. Presented here is a hydration
dependent FTIR spectroscopic study on eumelanin, which allows for the first
time to track the comproportionation reaction via the gradual decrease of the
carbonyl group concentration (1725 $cm^{-1}$ band) versus hydration.
Furthermore, we detect two types of interfacial water (3253 $cm^{-1}$ and 3473
$cm^{-1}$ bands). Finally, the feature detected at the 3600 $cm^{-1}$ band is
assigned to the formation of the Zundel cation, $H_5O_2^+$, an observation and
suggestion not previously made. We suggests, due to the behaviour of the
hydration dependent feature at 3600 $cm^{-1}$ that the formation of the
$H_5O_2^+$ cation potentially functions as a trap for mobile proton species,
partially explaining the complex hydration dependent conductivity of eumelanin.
