Search

In this paper, we investigate the effect of pressure on the molecular dynamics of protic ionic liquid lidocaine hydrochloride, a commonly used pharmaceutical, by means of dielectric spectroscopy and pressure-temperature-volume methods. We observed that near T(g) the pressure dependence of conductivity relaxation times reveals a peculiar behavior, which can be treated as a manifestation of decoupling between ion migration and structural relaxation times. Moreover, we discuss the validity of thermodynamic scaling in lidocaine HCl. We also employed the temperature-volume Avramov model to determine the value of pressure coefficient of glass transition temperature, dT(g)/dP|(P = 0.1). Finally, we investigate the role of thermal and density fluctuations in controlling of molecular dynamics of the examined compound.

Dielectric spectroscopy (DS) was used to investigate the relaxation dynamics of supercooled and glassy ibuprofen at various isobaric and isothermal conditions (pressure up to 1750 MPa). The ambient pressure data are in good agreement with that reported previously in the literature. Our high pressure measurements revealed validity of temperature-pressure superpositioning (TPS) for the alpha-peak. We also found that the value of the fragility index decreases with compression from m = 87 +/- 2 at atmospheric pressure to m = 72.5 +/- 3.5 at high pressure (p = 920 MPa). The drop of fragility observed in our experiment was discussed in the framework of the two-order-parameter (TOP) model. In addition, we have also studied crystallization kinetics in a liquid state of examined drug at ambient and high pressure. We found out that, for the same structural relaxation time/same viscosities, the samples prepared by compression of liquid at high temperatures have significantly elongated induction times as well as overall crystallization times (sample 2: t(0) approximately = 4 h, t(1/2) approximately = 37.5 h; sample 3: t(0) approximately = 5.6 h, t(1/2) approximately = 49 h) compared to that held at lower temperature and ambient pressure (sample 1: t(0) approximately = 1.2 h, t(1/2) approximately = 12.2 h). A possible explanation of this finding is also given.

Dielectric relaxation spectra of two closely related glass formers, dipropylene glycol [H–(C3H6O)2–OH] and dipropylene glycol dimethyl ether [CH3–O–(C3H6O)2–CH3], were measured at ambient and elevated pressures in the supercooled and the glassy states are presented. Hydrogen bonds formed in dipropylene glycol are removed when its ends are replaced by two methyl groups to become dipropylene glycol dimethyl ether. In the process, the primary relaxation, the excess wing, and the resolved secondary relaxation of dipropylene glycol are all modified when the structure is transformed to become dipropylene glycol dimethyl ether. The modifications include the pressure and temperature dependences of these relaxation processes and their interrelations. Thus, by comparing the dielectric spectra of these two closely related glass formers at ambient and elevated pressures, the differences in the relaxation dynamics and properties in the presence and absence of hydrogen bonding are identified. [ABSTRACT FROM AUTHOR]

In some polymers, in addition to the usual structural α relaxation, a slower α′ relaxation is observed with a non-Arrhenius temperature dependence. In order to understand better the molecular origin of this α′ relaxation in poly(methylphenylsiloxane) (PMPS) we have studied, for the first time, the pressure dependence of its relaxation time, together with the usual temperature dependence, by means of dynamic light scattering (DLS). For the same material the α relaxation was also studied by means of DLS and dielectric spectroscopy (DS) in broad temperature and pressure ranges. We find that the temperature dependence of both α and α′ relaxation times, at all pressures studied, can be described by a double Vogel-Fulcher-Tammann (VFT) law. The pressure dependence of the characteristic temperatures Tg (glass transition temperature) and T0 (Vogel temperature) as well as the activation volumes for both α and α′ processes are very similar, indicating, that both relaxation processes originate from similar local molecular dynamics. Additionally, for both α and α′ relaxations the combined temperature and pressure dependences of the relaxation times can be described using a parameter Γ=ρn/T with the same value of the exponent n. [ABSTRACT FROM AUTHOR]

Broadband dielectric measurements were carried out at isobaric and isothermal conditions up to 1.75 GPa for reconsidering the relaxation dynamics of decahydroisoquinoline, previously investigated by Richert et al. [R. Richert, K. Duvvuri, and L.-T. Duong, J. Chem. Phys. 118, 1828 (2003)] at atmospheric pressure. The relaxation time of the intense secondary relaxation τβ seems to be insensitive to applied pressure, contrary to the α-relaxation times τα. Moreover, the separation of the α- and β-relaxation times lacks correlation between shapes of the α-process and β-relaxation times, predicted by the coupling model [see for example, K. L. Ngai, J. Phys.: Condens. Matter 15, S1107 (2003)], suggesting that the β process is not a true Johari–Goldstein (JG) relaxation. From the other side, by performing measurements under favorable conditions, we are able to reveal a new secondary relaxation process, otherwise suppressed by the intense β process, and to determine the temperature dependence of its relaxation times, which is in agreement with that of the JG relaxation. [ABSTRACT FROM AUTHOR]

We investigated dielectric relaxation of a tri-propylene glycol system under high compression. By increasing temperature and pressure we observed that a new relaxation process emerges from the low frequency tail of the structural peak. This new peak starts to be visible at about 0.5 GPa and becomes clearly evident at 1.7 GPa. However, this additional peak merges again with the structural one as the glass transition is approached, since it has a weaker temperature dependence. This finding enriches the relaxation scenario of molecular glass formers confirming that the application of very high hydrostatic pressure can favor the detection of new relaxation or otherwise unresolved processes in supercooled liquid systems. [ABSTRACT FROM AUTHOR]

Advance was made recently in identifying the nature of the Debye relaxation observed by dielectric spectroscopy in monohydroxy alcohols by other experimental techniques. Consistent with the experimental findings, the transient chain model give a good description of the origin of the Debye relaxation. Notwithstanding, a general property of the Debye relaxation remains not explained, and that is the weaker temperature and pressure dependences of its relaxation time τ D (T,P) compared to τ α (T,P) of the faster structural α-relaxation at temperatures approaching the glass transition temperature T g. Based on the transient chain model for the Debye relaxation, and the Coupling Model for the α-relaxation, we have explained the difference in the temperature and pressure dependences of τ D (T,P) compared to τ α (T,P) quantitatively. [ABSTRACT FROM AUTHOR]

Abstract Influence of different factors on nematic alignment and relaxation dynamics in supercooled mixture of liquid crystals E7 was investigated by means of dielectric and rheo-dielectric spectroscopy. Results show that elevated pressure or application of strong oscillatory shear aligned the nematic director parallel to the electrodes. On the other hand, if after the shear treatment a static electric field is applied an alignment of the nematic director perpendicular to the electrodes is even better than in the sample quenched and aligned by bias field without the shear treatment. Highlights • E7 mixture of nematic liquid crystals is investigated here using dielectric and rheo-dielectric spectroscopy. • At ambient pressure the nematic director is self-oriented perpendicularly to the electrodes of the capacitor. • Application of the bias field increases ordering of the mesophase. • Densification or oscillatory shear can be crucial for changing an ordering of the mesophase. • Application of high pressure or strong oscillatory shear aligned the nematic director parallel to the electrodes. [ABSTRACT FROM AUTHOR]