We demonstrate on synthetic eumelanin that biomolecular conductivity models should account for temperature and hydration effects coherently.

Eumelanin is a widespread biomacromolecule pigment in the biosphere and has been widely investigated for 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 behavior is connected to a comproportionation reaction between oxidized and reduced monomer moieties and water. A hydration-dependent FTIR spectroscopic study on eumelanin is presented herein, which allows for the first time tracking the comproportionation reaction via the gradual increase of the overall aromaticity of melanin monomers in the course of hydration. We identified spectral features associated with the presence of specific “one and a half” C𝌁O bonds, typical for o-semiquinones. Signatures of semiquinone monomers with internal hydrogen bonds and that carboxylic groups, in contrast to semiquinones, begin to dissociate at the very beginning of melanin hydration were indicated. As such, we suggest a modification to the common hydration-dependent conductivity mechanism and propose that the conductivity at low hydration is dominated by carboxylic acid protons, whereas higher hydration levels manifest semiquinone protons.

The electrodynamics of metals is well understood within the Drude conductivity model; properties of insulators and semiconductors are governed by a gap in the electronic states. But there is a great variety of disordered materials that do not fall in these categories and still respond to external field in an amazingly uniform manner. At radiofrequencies delocalized charges yield a frequency-independent conductivity σ 1(ν) whose magnitude exponentially decreases while cooling. With increasing frequency, dispersionless conductivity starts to reveal a power-law dependence σ 1(ν)∝ν s with s < 1 caused by hopping charge carriers. At low temperatures, such Universal Dielectric Response can cross over to another universal regime with nearly constant loss ε″∝σ1/ν = const. The powerful research potential based on such universalities is widely used in condensed matter physics. Here we study the broad-band (1–1012 Hz) dielectric response of Shewanella oneidensis MR-1 extracellular matrix, cytochrome C and serum albumin. Applying concepts of condensed matter physics, we identify transport mechanisms and a number of energy, time, frequency, spatial and temperature scales in these biological objects, which can provide us with deeper insight into the protein dynamics.

We find that water morphology within melanin is purely interfacial in nature, even at high water contents. This morphology brings into question the proton conduction mechanism within melanin with implications or other conductive biomaterials.

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