Infrared fingerprints of water collective dynamics indicate proton transport in biological systems

Recent publications on spectroscopy of water layers in water bridge structures revealed a significant enhancement of the proton mobility and the dielectric contribution of translational vibrations of water molecules in the interfacial layers compared to bulk water. Herewith, the results of long-term studies of proton dynamics in solid-state acids have shown that proton mobility increases significantly with the predominance of hydronium, but not Zundel, cations in the aqueous phase. In the present work, in the light of these data, we reanalyzed our previously published results on broadband dielectric spectroscopy of bovine heart cytochrome c, bovine serum albumin, and the extracellular matrix and filaments of Shewanella oneidensis MR-1. We revealed that, just as in water bridges, an increase in electrical conductivity in these systems correlates with an increase in the dielectric contribution of water molecular translational vibrations. In addition, the appearance of spectral signatures of the hydronium cations was observed only in those cases when the system revealed noticeable electrical conductivity due to delocalized charge carriers.