Tuning proton conductivity and energy barriers for proton transfer.

Proton transport is critical for many technologies and for a variety of biochemical and biophysical processes. Proton transfer between molecules (via structural diffusion) is considered to be an efficient mechanism in highly proton conducting materials. Yet, the mechanism and what controls energy barriers for this process remain poorly understood. It was shown that mixing phosphoric acid (PA) with lidocaine leads to an increase in proton conductivity at the same liquid viscosity. However, recent simulations of mixtures of PA with various bases, including lidocaine, suggested no decrease in the proton transfer energy barrier. To elucidate this surprising result, we have performed broadband dielectric spectroscopy to verify the predictions of the simulations for mixtures of PA with several bases. Our results reveal that adding bases to PA increases the energy barriers for proton transfer, and the observed increase in proton conductivity at a similar viscosity appears to be related to the increase in the glass transition temperature (Tg) of the mixture. Moreover, the energy barrier seems to increase with Tg of the mixtures, emphasizing the importance of molecular mobility or interactions in the proton transfer mechanism.