Search

Different experimental techniques were applied to study thermal and structural properties, strength of H-bonds, possible keto - enol tautomerism and molecular dynamics at various thermodynamic conditions in the H-bonded active substance, curcumin (CRM). Dielectric measurements revealed dynamical features of examined compound that are uncharacteristic for the associated systems. This includes enormously large pressure coefficient of the glass transition temperature and prominent drop of the fragility with compression. Simultaneously, the shape of α -process slightly broadened at elevated pressures. Infrared investigations demonstrated that this effect is related to the variation in the population of H-bonds. Moreover, we studied the changes in the structural and dynamical properties of the glasses prepared upon cooling of the melt (ordinary glass, OG) and the one obtained after compression of CRM in the liquid phase and decompression at T = 293 K (dense glass, DG). Interestingly, during the aging of the latter sample, a clear shift of the β -relaxation towards higher frequencies was noted. This unexpected result indicated that the density of DG is probably getting smaller with time. Complementary X-ray diffraction experiments confirmed this supposition. Additionally, they showed that in DG there are traces of polymorph II of CRM that has a higher density than initial crystals (polymorph I). Finally, infrared studies demonstrated that H-bond pattern in DG is slightly different with respect to OG. Furthermore, Raman investigations suggested that probably keto - enol tautomerism might be shifted towards diketo form in the glass obtained at high compression. Our investigations are very interesting in the context of better understanding of the behavior of associated systems at high compression as well as provide a better insight into dynamics of higher density glasses produced at elevated pressures. Unlabelled Image [ABSTRACT FROM AUTHOR]

In this paper, the molecular dynamics as well as inter- and intramolecular interactions in the homogenous solid dispersions (SDs) of active pharmaceutical ingredient - probucol (PRO) with acetylated glucose (acGLU), acetylated sucrose (acSUC), and sucrose acetoisobutyrate (aibSUC), prepared in 5:1 molar ratio, have been investigated using broadband dielectric (BD) and Fourier transform infrared (FTIR) spectroscopy. Importantly, high pressure dielectric measurements revealed that as for neat PRO, a breakdown of the isochronal structural (α) and JG- β exact superpositioning, due to increasing separation between both processes under compression, can also be detected in its mixtures with acetylated saccharides (acSACCHs). Furthermore, the analysis of temperature dependences of JG- β -relaxation times for PRO and PRO-acSACCH SDs at selected isobaric conditions indicated the increase in the cooperativity of the secondary process (reflected in the value of the activation entropy, Δ S β) at elevated pressure in all systems. The mere addition of the small amount of excipient to neat PRO (p = 0.1 MPa) resulted in a greater value of Δ S β (it was the most noticeable in the case of aibSUC). Further FTIR studies carried out on the pressure densified glasses of PRO, and binary mixtures suggested that the observed changes in the cooperativity of the JG- β -process, as well as the failure of the exact isochronal superpositioning of α - and JG- β relaxation times, are due to varying H-bond pattern in the examined single- and two-component systems at high compression/in the presence of saccharide. [Display omitted] [ABSTRACT FROM AUTHOR]

In this paper, we studied the impact of saccharides having a similar backbone but differing in the degree of freedom, local molecular mobility, flexibility of the ring and intermolecular interactions on the glass-forming ability (GFA) of naproxen (NAP) in binary mixtures. For this purpose, a series of methyl and acetyl derivatives of glucose (GLS) and anhydroglucose (anhGLS), as well as neat anhGLS have been used to produce homogeneous solid dispersions (SDs) of varying molar concentration of examined active pharmaceutical ingredient (API). Systematic measurements with the use of Differential Scanning Calorimetry (DSC) and Broadband Dielectric Spectroscopy (BDS) enabled us to determine the phase transitions, homogeneity and molecular mobility of the investigated binary mixtures as well as the impact of excipient on the crystallization tendency of NAP. It turned out that acetylated glucose (acGLS), one of the most mobile and flexible saccharides of all examined herein materials, is the best excipient enhancing the GFA of studied API. Although, it should be noted that upon storage at room temperature, we observed the recrystallization of NAP from binary mixtures. Interestingly, API always crystallized to the initial polymorphic form, as shown by X-ray diffraction (XRD) investigations. Finally, since additional measurements with the use of Fourier Transform Infrared (FTIR) Spectroscopy clearly indicated that there are no significant differences in the intermolecular interactions in the systems composed of NAP and all examined saccharides, one can postulate that the mobility and ring flexibility of the matrix have, , the most important impact on the crystallization tendency of NAP upon cooling. Consequently, it seems that in some cases, more mobile/flexible matrices can be a much better choice to enhance the glass-forming ability of studied pharmaceutical. Image, graphical abstract [ABSTRACT FROM AUTHOR]

Highlights • There are marked differences in dynamics of modified linear and cyclic carbohydrates. • A variation in the distribution of τ α between linear and cyclic compounds is observed. • The evolutions of the T g and m versus M w in both groups of materials are different. • The shape of the α -process in saccharides of the same topology doesn't change with M w. Abstract In this paper, the molecular dynamics and thermal properties of representative acetylated linear and cyclic oligosaccharides: acTRE, acRAF, acSTA, ac-α-CD, ac-β-CD, ac-γ-CD, have been investigated by using broadband dielectric spectroscopy and differential scanning calorimetry. We found that there are marked differences in the dynamics of the structural and secondary relaxation processes in both groups of materials. Just to mention a variation in the distribution of the structural relaxation times as well as different evolutions of the glass transition temperature (T g) and fragility (m) versus molecular weight (M w), which seem to be affected by the shape of the molecule, strain in the carbohydrate ring and mobility of side acetyl moieties. [ABSTRACT FROM AUTHOR]