In this paper, we investigate the molecular dynamics and ions transport properties of polymerized imidazolium-based protic ionic liquid [HSO 3 −BVIm][OTf]a new material with potential applications in energy storage and electrochemical devices. The results of dielectric measurements, analyzed in modulus M*(f) and conductivity σ*(f) formalisms, combined with temperature-modulated differential scanning calorimetry experiments, have revealed a fundamental difference between the conducting properties of the examined polymer membrane and its low-molecular weight counterpart. Our findings indicated a strong decoupling between conductivity relaxation times τ σ (related to the ions migration through the polymer matrix) and segmental dynamics when the ionic transport is controlled by fast proton hopping through the dense hydrogen-bond network. Finally, we also discuss, for the first time, the effect of water content on the glass transition temperature value, relation between the charge and mass diffusion, reflected in the decoupling phenomenon, and the conductivity mechanism of examined poly[HSO 3 −BVIm][OTf].
From an exhaustive examination of the molecular dynamics in practically all van der Waals molecular glass formers ever probed by dielectric spectroscopy, we found that the width of the α-loss peak at or near the glass transition temperature T_{g} is strongly anticorrelated with the polarity of the molecule. The larger the dielectric relaxation strength Δε(T_{g}) of the system, the narrower is the α-loss peak. This remarkable property is explained by the contribution from the dipole-dipole interaction potential V_{dd}(r)=-Dr^{-6} to the attractive part of the intermolecular potential, making the resultant potential more harmonic, and the effect increases rapidly with the dipole moment μ and Δε(T_{g}) in view of the relation, D∝(μ^{4}/kT_{g})∝kT_{g}[Δε(T_{g})]^{2}. Since the novel correlation discovered encompasses practically all van der Waals molecular glass formers studied by dielectric spectroscopy, it impacts the large dielectric research community as well as those engaged in solving the glass transition problem.
The purpose of this paper is to examine the role of molecular mobility in the recrystallization process from the amorphous state of the anticholesterol drug ezetimibe. Both the molecular dynamics and crystallization kinetics have been studied using various experimental techniques, such as broadband dielectric spectroscopy (BDS), differential scanning calorimetry (DSC), and X-ray diffraction (XRD). Our investigations have shown that ezetimibe easily recrystallizes from the disordered state, both below and above its glass transition temperature (Tg = 336 K). Moreover, we found that an only slightly elevated pressure (5 MPa) significantly accelerates the recrystallization process at T > Tg. We predict that the structural relaxation time of amorphous ezetimibe at 293 K (storage temperature) and ambient pressure is only 22 days. This result corresponds to the characteristic time, determined from XRD measurements, for amorphous ezetimibe to recrystallize during storage at Troom = 298 K. It leads to the conclusion that the molecular mobility reflected in structural relaxation of ezetimibe is mainly responsible for devitrification of this drug. Finally, we determined a relatively easy way to improve the physical stability of the drug by preparing a binary amorphous ezetimibe-Soluplus mixture. Ezetimibe in an amorphous mixture with 20 wt % Soluplus has a much better (over six times) solubility than the pure crystalline material.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.