Infrared spectroscopy of hydration-controlled eumelanin films suggests the presence of the Zundel cation

Abstract

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.