Glassy Dynamics and Translational-Rotational Coupling of an Ionically Conducting Pharmaceutical Salt-Sodium Ibuprofen.

In this work, we study the structural dipolar relaxation and ionic conductivity relaxation in an ionized derived from a nonionized glass former. The latter is the salt form of a well-studied active pharmaceutical ingredient, sodium ibuprofen, and the former is ibuprofen. Quantum mechanical calculations were employed to study the variation in its molecular electrostatic potentials, and its spatial extent on its salt formation with Na+ ions. Measurements have been made using differential scanning calorimetry and broadband dielectric spectroscopy, and the characterization is assisted by density functional theory. The dielectric data contain information on both ionic and dipolar molecular mobility of NaIb and were extracted by representation in terms of the electric modulus and permittivity. A secondary ß-conductivity relaxation coexists with the primary α-conductivity relaxation. By use of the coupling model, we show that the ß-conductivity relaxation is connected to the α-conductivity relaxation and is the analogue of the relation of the Johari-Goldstein ß-relaxation to the structural α-relaxation, shown valid also in ibuprofen. This remarkable result has an impact on the fundamental understanding of the dynamics of ionic conductivity. By representing the data as permittivity, a dipolar ß-relaxation was found to have practically the same relaxation times as the ß-conductivity relaxation in the glassy state and translational-rotational coupling is valid at a more local secondary relaxation level. However, the α-conductivity relaxation decouples from structural α-relaxation because the structural glass transition temperature is lower than the conductivity counterpart by 29 K. These are novel findings. The study elucidates the effects on the dynamics by the change in the nature of bonding and in size on introducing sodium ions to ibuprofen in the glassy and supercooled liquid states.

The Interplay between Charge Transport and CO2 Capturing Mechanism in [EMIM][SCN] Ionic Liquid: A Broadband Dielectric Study.

The hoisted increment in the CO2 emission in the atmosphere is a noteworthy environmental problem. Gas-liquid absorption is a well-known strategy that can be used to control CO2 emissions from an increased rate of fossil fuel industrializations. In this work, a combination of broadband dielectric spectroscopy, Fourier infrared (FTIR) spectroscopy, and quantum chemical calculations were used to study the absorption, desorption and kinetic mechanism of a room temperature imidazolium ionic liquid (IL) with cyanide anion, 1-ethyl-3-methylimidazolium thiocyanate ([EMIM][SCN]) on CO2 exposure. Initially, the charge transport and glassy dynamics of [EMIM][SCN] is investigated in a wide frequency and temperature range using broadband dielectric spectroscopy and differential scanning calorimetry. The conductivity relaxation was well fitted with Havriliak-Negami function in the modulus formalism, while the dc conductivity correlated well with the Barton-Nakajima-Namikawa relation. Then, the conductometric approach was taken to monitor the interplay between the ionic conductivity of [EMIM][SCN] and diffusion of captured CO2 in it. The resistance of the IL increases upon CO2 exposure, indicating a chemical change at the molecular level of [EMIM][SCN]. The possible CO2 capturing mechanisms for [EMIM][SCN] were investigated with density functional theory calculations and FTIR spectroscopy. Thus, this work proposes a new strategy to explain the mechanism underlined in chemisorption of CO2 in the [EMIM][SCN]. This can be extended to more promising CO2 capturing materials including ionic liquids especially imidazolium-based ionic liquids with cyanide anions like dicyanimide, tricyanometanide, tetracyanoborate, etc.

Molecular dynamics, physical and thermal stability of neat amorphous amlodipine besylate and in binary mixture.

In this paper, a stable amorphous solid dispersion of an antihypertensive drug, amlodipine besylate (AMB) was prepared by entrapping it in a polymer matrix, polyvinyl pyrrollidone, in different weight ratios (AMB/PVP 05:95, 10:90, 20:80, 30:70). The glass forming ability of all binary dispersions were studied by means of differential scanning calorimetry and found good correlation between experimental Tg and Fox Flory's prediction. By considering the daily dosage limit of 5 mg, a weight ratio of 05:95 was further considered for the study. The structures of neat and binary of AMB were characterized by density functional theory, Fourier transform infrared spectroscopy, Fourier transform Raman spectroscopy and UV-visible spectroscopy. Further, detailed molecular dynamics of both pure and binary were investigated using broadband dielectric spectroscopy to judge the physical stability of the amorphous dispersions. Translation-rotation coupling of AMB possibly explains the dual conductivity and dipolar nature of the secondary relaxation in neat AMB. Thus, the binary dispersion of AMB with commercially acceptable weight ratio with strong glass forming behaviour and better shelf life was prepared and characterized for practical applications.

Molecular dynamics and the translational-rotational coupling of an ionically conducting glass-former: amlodipine besylate.

We studied the conductivity relaxation originating from a glass-former composed of cations and anions, and the relation to the structural α-relaxation at temperatures above and below the glass transition temperature. The material chosen was amorphous amlodipine besylate (AMB), which is also a pharmaceutical with a complex chemical structure. Measurements were made using differential scanning calorimetry (DSC), broadband dielectric spectroscopy (BDS) and X-ray diffraction, and the characterization was assisted using density functional theory (DFT). The X-ray diffraction pattern confirms the amorphous nature of vitrified AMB. Both the ionic and dipolar aspects of the dynamics of AMB were examined using these measurements and were used to probe the nature of the secondary conductivity and dipolar relaxations and their relation to the conductivity α-relaxation and the structural α-relaxation. The coupling model predictions and quantum mechanical simulations were used side by side to reveal the properties and nature of the secondary conductivity relaxation and the secondary dipolar relaxation. Remarkably, the two secondary relaxations have the same relaxation times, and are one and the same process performing dual roles in conductivity and dipolar relaxations. This is caused by the translation-rotation coupling of the AMB molecule. Thus, AMB has both conductivity α- and ß-relaxations, and application of the coupling model shows that these two relaxations are related in the same way as the structural α-relaxation and the Johari-Goldstein ß-relaxation are. This important result has an impact on the fundamental understanding of the dynamics of ionic conductivity.