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Anisotropy, segmental dynamics and polymorphism of crystalline biogenic carboxylic acids
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SYSNO ASEP 0563408 Document Type J - Journal Article R&D Document Type Journal Article Subsidiary J Článek ve WOS Title Anisotropy, segmental dynamics and polymorphism of crystalline biogenic carboxylic acids Author(s) Pokorný, Václav (UMCH-V) RID, ORCID
Touš, P. (CZ)
Štejfa, V. (CZ)
Růžička, K. (CZ)
Rohlíček, Jan (FZU-D) RID, ORCID
Czernek, Jiří (UMCH-V) RID
Brus, Jiří (UMCH-V) RID, ORCID
Červinka, D. (CZ)Source Title Physical Chemistry Chemical Physics. - : Royal Society of Chemistry - ISSN 1463-9076
Roč. 24, č. 42 (2022), s. 25904-25917Number of pages 14 s. Language eng - English Country GB - United Kingdom Keywords carboxylic acids ; anisotropy ; thermodynamic Subject RIV CF - Physical ; Theoretical Chemistry OECD category Physical chemistry Subject RIV - cooperation Institute of Physics - Solid Matter Physics ; Magnetism R&D Projects LTAUSA18011 GA MŠMT - Ministry of Education, Youth and Sports (MEYS) Research Infrastructure e-INFRA CZ - 90140 - CESNET, zájmové sdružení právnických osob Method of publishing Limited access Institutional support UMCH-V - RVO:61389013 ; FZU-D - RVO:68378271 UT WOS 000869849700001 EID SCOPUS 85141553866 DOI 10.1039/D2CP03698C Annotation Carboxylic acids of the Krebs cycle possess invaluable biochemical significance. Still, there are severe gaps in the availability of thermodynamic and crystallographic data, as well as ambiguities prevailing in the literature on the thermodynamic characterization and polymorph ranking. Providing an unambiguous description of the structure, thermodynamics and polymorphism of their neat crystalline phases requires a complex multidisciplinary approach. This work presents results of an extensive investigation of the structural anisotropy of the thermal expansion and local dynamics within these crystals, obtained from a beneficial cooperation of NMR crystallography and ab initio calculations of non-covalent interactions. The observed structural anisotropy and spin–lattice relaxation times are traced to large spatial variations in the strength of molecular interactions in the crystal lattice, especially in the orientation of the hydrogen bonds. A completely resolved crystal structure for oxaloacetic acid is reported for the first time. Thanks to multi-instrumental calorimetric effort, this work clarifies phase behavior, determines third-law entropies of the crystals, and states definitive polymorph ranking for succinic and fumaric acids. These thermodynamic observations are then interpreted in terms of first-principles quasi-harmonic calculations of cohesive properties. A sophisticated model capturing electronic, thermal, and configurational-entropic effects on the crystal structure approaches captures the subtle Gibbs energy differences governing polymorph ranking for succinic and fumaric acids, representing another success story of computational chemistry.
Workplace Institute of Macromolecular Chemistry Contact Eva Čechová, cechova@imc.cas.cz ; Tel.: 296 809 358 Year of Publishing 2023 Electronic address https://pubs.rsc.org/en/content/articlelanding/2022/CP/D2CP03698C
Number of the records: 1