Effect of electrostatic interactions on the relaxation dynamics of pharmaceutical eutectics.

In this paper, we investigate the temperature-dependent relaxation dynamics in the glassy and supercooled liquid state of dipolar and ionic eutectic mixtures made of two anesthetic agents (lidocaine and prilocaine) and their hydrochloride salts, respectively. In addition to eutectic phases containing 1:1 and 4:1 mol/mol of LD/PRL and LD-HCl/PRL-HCl, respectively, the relaxation properties of non-eutectic compositions and parent compounds are also studied. We found that electrostatic long-range forces determine strongly the dielectric and mechanical response of eutectic material. As a result of Coulomb interactions between ion pairs, an additional β-relaxation mode was found in the dielectric spectra of glassy LD-HCl/PRL-HCl mixtures. On the other hand, the studies of relaxation dynamics of ionic and non-ionic mixtures at T > Tg revealed a continuous decrease of both fragility mP and the length scale of dynamic heterogeneity NαB(Tg), with simultaneous growth of Tg, when the electrostatics forces appear. At the same time, we found the charge transport being decoupled from structural dynamics in all studied ionic binary mixtures that is due to the fast proton hopping. However, the efficiency of proton transport is dropping down with an increase of Tg.