ABSTRACT
In this paper, the steric hindrance effect related to the presence of either a cyclic or aromatic ring on the self-association process in the series of monohydroxy alcohols (MAs), from cyclohexanemethanol to 4-cyclohexyl-1-butanol and from benzyl alcohol to 4-phenyl-1-butanol, was studied using X-Ray Diffraction (XRD), Differential Scanning Calorimetry (DSC), Fourier Transform Infrared (FTIR) spectroscopy, Broadband Dielectric Spectroscopy (BDS) and the Pendant Drop (PD) methods. Based on FTIR results, it was shown that phenyl alcohol (PhA) and cyclohexyl alcohol (CA) derivatives reveal substantial differences in the association degree, the activation energy of dissociation, and the homogeneity of supramolecular nanoassociates suggesting that the phenyl ring exerts a stronger steric impact on the self-assembling of molecules than cyclohexyl one. Additionally, XRD data revealed that phenyl moiety introduces more heterogeneity in the organization of molecules compared to the cyclic one. The changes in the self-association process of alcohols were also reflected in differences in the molecular dynamics of the H-bonded aggregates, as well as in the Kirkwood factor, defining the long-range correlation between dipoles, which were slightly higher for CAs with respect to those determined for PhAs. Unexpectedly it was also found that the surface layers of PhAs were more organized than those formed by CAs. Thus, these findings provided insight into the impact of aromaticity on the self-assembly process, H-bonding pattern, supramolecular structure, and intermolecular dynamics of the studied alcohols.
ABSTRACT
In this work, we examined the effect of the length of alkyl chain attached to the benzene ring on the self-assembling phenomena for a series of phenyl alcohol (PhA) derivatives, from phenylmethanol (benzyl alcohol) to 7-phenyl-1-heptanol, by means of X-Ray Diffraction (XRD), Differential Scanning Calorimetry (DSC), Fourier Transform Infrared (FTIR) spectroscopy, and Broadband Dielectric Spectroscopy (BDS) methods. XRD data in the reciprocal and real spaces showed a gradual increase in the local order with the elongation of the alkyl chain. However, the position and full width at half maximum of the main diffraction peak exhibited a non-systematic behavior. To better understand this fact, PhAs were subjected to FTIR spectroscopic studies. These investigations revealed that the association degree and the activation energy of dissociation increase as the alkyl chain length grows. On the other hand, BDS data showed a non-monotonic variation in the Kirkwood correlation factor with increasing length of the alkyl chain, indicating a competition between interactions of the non-polar and polar parts of the molecules in the studied PhAs. Finally, it was also found that the molar surface entropy for PhAs increases with the number of methylene groups, approaching values reported for alkanes, which indicates suppression of the surface order for PhAs with a long alkyl chain. This variability of the various parameters as a function of the length of the side chain shows that the interplay between soft interactions has a strong impact on the local structure and intra and intermolecular dynamics of the studied PhAs.
ABSTRACT
Itraconazole (ITZ) is a thermotropic liquid crystal that exhibits isotropic, nematic, and smectic phases on cooling towards the glass transition upon melting. Over the years, new aspects regarding the liquid-crystalline ordering of this antifungal drug were systematically revealed. It has been shown recently that the temperature range of individual mesophases in ITZ can be modified by adding a small amount of glycerol (GLY). Moreover, above the critical concentration of 5% w/w, a smectic to nematic transition can be avoided. Here we go one step further, and we used broadband dielectric spectroscopy to investigate the new phase behavior of the ITZ-GLY mixture (5% w/w). To confirm the phase transformations of the ITZ-GLY mixture, differential scanning calorimetry was also employed. The analysis of molecular dynamics of the ITZ-GLY mixture in the glassy and isotropic phases revealed features similar to those observed for neat ITZ. Two relaxation processes were identified in the smectic-A phase, with similar temperature dependence, most likely related to the fast rotations around the long axis of a molecule. Additionally, the derivative analysis revealed another low-frequency process hidden under DC conductivity ascribed to the slow rotations about a short axis. We will show that the differences in the molecular organization in the smectic-A and isotropic phases leave a clear fingerprint on the temperature behavior of relaxation times and other dielectric parameters, such as DC conductivity and dielectric strength, for which a pretransition effect has been detected.
ABSTRACT
Herein, we investigated the molecular dynamics as well as intramolecular interactions in two primary monohydroxy alcohols (MA), 2-ethyl-1-hexanol (2EHOH) and n-butanol (nBOH), by means of broad-band dielectric (BDS) and Fourier transform infrared (FTIR) spectroscopy. The modeling data obtained from dielectric studies within the Rubinstein approach [ Macromolecules 2013, 46, 7525-7541] originally developed to describe the dynamical properties of self-assembling macromolecules allowed us to calculate the energy barrier (Ea) of dissociation from the temperature dependences of relaxation times of Debye and structural processes. We found Ea â¼ 19.4 ± 0.8 and 5.3 ± 0.4 kJ/mol for the former and latter systems, respectively. On the other hand, FTIR data analyzed within the van't Hoff relationship yielded the energy barriers for dissociation Ea â¼ 20.3 ± 2.1 and 12.4 ± 1.6 kJ/mol for 2EHOH and nBOH, respectively. Hence, there was almost a perfect agreement between the values of Ea estimated from dielectric and FTIR studies for the 2EHOH, while some notable discrepancy was noted for the second alcohol. A quite significant difference in the activation barrier of dissociation indicates that there are probably supramolecular clusters of varying geometry or a ring-chain-like equilibrium is strongly affected in both alcohols. Nevertheless, our analysis showed that the association/dissociation processes undergoing within nanoassociates are one of the main factors underlying the molecular origin of the Debye process, supporting the transient chain model.
ABSTRACT
Broadband dielectric spectroscopy (BDS) has been used to study the molecular dynamics and aging process in neat probucol (PRO) as well as its binary mixtures with selected acetylated saccharides. In particular, we applied the Casalini and Roland approach to determine structural relaxation times in the glassy state of the examined systems (so-called isostructural times, τiso). Next, using the calculated τiso, primitive relaxation times of the coupling model were obtained and compared to the experimental secondary ß (Johari-Goldstein (JG) type) relaxation times. Interestingly, it turned out that there is a correlation between the ß-JG and the structural (α)-relaxation processes below the glass transition temperature (T < Tg) in each investigated sample. This is a new observation compared to previous studies demonstrating that such a relationship exists only in the supercooled liquid state of neat PRO. Moreover, it was revealed that the stretching parameters obtained from the aging procedure are very close to the ones determined by fitting the dielectric data above the Tg with the use of the Kohlrausch-Williams-Watts function, indicating that the aging process is governed by the α-relaxation. Complementary Fourier transform infrared and X-ray diffraction measurements allowed us to find a possible reason for these findings. It was demonstrated that although there are very weak intermolecular interactions between PRO and modified saccharides, the intra- and intermolecular structure of PRO is practically unaffected by the presence of modified saccharides.
