Anisotropy, segmental dynamics and polymorphism of crystalline biogenic carboxylic acids

0563408 - ÚMCH 2023 RIV GB eng J - Journal Article
Pokorný, Václav - Touš, P. - Štejfa, V. - Růžička, K. - Rohlíček, Jan - Czernek, Jiří - Brus, Jiří - Červinka, D.
Anisotropy, segmental dynamics and polymorphism of crystalline biogenic carboxylic acids.
Physical Chemistry Chemical Physics. Roč. 24, č. 42 (2022), s. 25904-25917. ISSN 1463-9076. E-ISSN 1463-9084
R&D Projects: GA MŠMT(CZ) LTAUSA18011
Research Infrastructure: e-INFRA CZ - 90140
Institutional support: RVO:61389013 ; RVO:68378271
Keywords : carboxylic acids * anisotropy * thermodynamic
OECD category: Physical chemistry; Condensed matter physics (including formerly solid state physics, supercond.) (FZU-D)
Impact factor: 3.3, year: 2022
Method of publishing: Limited access
https://pubs.rsc.org/en/content/articlelanding/2022/CP/D2CP03698C

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.

Permanent Link: https://hdl.handle.net/11104/0336167