The impact of chemical structure on the formation of the medium-range order and dynamical properties of selected antifungal APIs

Heczko, Dawid; Jurkiewicz, Karolina; Tarnacka, Magdalena; Grelska, Joanna; Wrzalik, R.; Kamiński, Kamil; Paluch, Marian; Kamińska, Ewa

doi:10.1039/d0cp02332a

Cited by 5 publications

(16 citation statements)

References 58 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Both processes shift toward lower frequency ( f ) with decreasing T /increasing p . Additionally, for POS, ITZ, and TER, like at ambient p , the presence of the SM at f preceding the main α-mode can be detected. It should be mentioned that this special kind of dielectric response occurring in ITZ is related to the rotation of a rod-like molecule (a characteristic feature of LC materials) around its short axisso-called flip-flop motions. , That is why we label it as δ-relaxation.…”

Section: Resultsmentioning

confidence: 91%

“…Additionally, for POS, ITZ, and TER, like at ambient p , the presence of the SM at f preceding the main α-mode can be detected. It should be mentioned that this special kind of dielectric response occurring in ITZ is related to the rotation of a rod-like molecule (a characteristic feature of LC materials) around its short axisso-called flip-flop motions. , That is why we label it as δ-relaxation. A similar origin of the slower relaxation (marked as α′) could be suggested for POS, since it has some tendency to form a nematic-like order .…”

Section: Resultsmentioning

confidence: 91%

“…It should be mentioned that this special kind of dielectric response occurring in ITZ is related to the rotation of a rod-like molecule (a characteristic feature of LC materials) around its short axisso-called flip-flop motions. , That is why we label it as δ-relaxation. A similar origin of the slower relaxation (marked as α′) could be suggested for POS, since it has some tendency to form a nematic-like order . However, since this kind of ordering is residual in this compound, it may not be the case.…”

Section: Resultsmentioning

confidence: 99%

“…Dielectric permittivity values ( ε *(ω) = ε ′(ω) – i ε ″(ω)) at ambient pressure were taken using the Novo-Control Alpha dielectric spectrometer (Novocontrol Technologies GmbH & Co. KG, Hundsangen, Germany) over a frequency range from 10 –2 to 10 6 Hz. , The samples were placed between two stainless-steel electrodes (diameter, 20 mm; gap, 0.078 mm) and mounted on a cryostat. During the experiments, each sample was maintained under dry nitrogen gas flow.…”

Section: Experimental Sectionmentioning

confidence: 99%

“…In this context, it should be mentioned that one of the most useful tools dedicated to studying this phenomenon is X-ray diffraction (XRD). In the diffractograms collected for the systems creating supramolecular structures partially ordered on the nanoscale, except for the main diffraction peak connected to the short-range molecular order, also a “pre-peak” originating from the medium-range intermolecular correlations can be detected. ,,,,− From the analysis of the position, width, shape, and intensity of this peak, together with the Fourier analysis of the total diffraction data in the form of the atomic pair distribution function, researchers may deliver important information about the size, range of order, geometry, and concentration of formed supramolecular associates/aggregates . Nevertheless, extensive studies on monohydroxy alcohols indicated that the analysis of the diffractograms even supported by the results of theoretical calculations (e.g., molecular dynamics and reverse Monte Carlo simulations) may lead to divergent conclusions and provide inconsistent information about the size of the supramolecular associates, their morphology, architecture, etc., even for the same compound. − Therefore, to facilitate the diffraction data analysis, it is crucial to combine different information sources from various experimental and theoretical tools.…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

Influence of High Pressure on the Local Order and Dynamical Properties of the Selected Azole Antifungals

et al. 2020

Self Cite

View full text Add to dashboard Cite

Dielectric studies under various temperature (T) and pressure (p) conditions on five active pharmaceutical ingredients (APIs) with antifungal propertiesitraconazole (ITZ), posaconazole (POS), terconazole (TER), ketoconazole (KET), and fluconazole (FLU)were carried out. We have thoroughly studied the connection between the pressure coefficient of the glass transition temperature (dT g /dp) and the activation volume of both relaxation modes (ΔV α , ΔV δ/α′ ) with respect to the molecular weight (M w ) or molar volume (V m ) in these systems. Besides, high pressure data revealed that the time scale separation between αand δor α′-processes increases with pressure in ITZ and TER. What is more, the activation entropy, which is a measure of cooperativity, calculated from the Eyring model for the secondary (β)-relaxation in ITZ and POS, increased and decreased, respectively, in the compressed samples. To understand these peculiar results, we have carried out X-ray diffraction (XRD) measurements on the pressure-densified glasses and found that pressure may induce frustration in molecular organization and destroy the medium-range order while enhancing the short-range correlations between molecules. This finding allowed us to conclude that varying molecular spatial arrangement is responsible for the extraordinary dynamical behavior of ITZ, POS, and TER at high pressure.

show abstract

Section: Resultsmentioning

confidence: 91%