Anisotropy, segmental dynamics and polymorphism of crystalline biogenic carboxylic acids

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61389013%3A_____%2F22%3A00563408" target="_blank" >RIV/61389013:_____/22:00563408 - isvavai.cz</a>

Alternative codes found

RIV/68378271:_____/22:00563408 RIV/60461373:22340/22:43924284

Result on the web

<a href="https://pubs.rsc.org/en/content/articlelanding/2022/CP/D2CP03698C" target="_blank" >https://pubs.rsc.org/en/content/articlelanding/2022/CP/D2CP03698C</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/D2CP03698C" target="_blank" >10.1039/D2CP03698C</a>

Result language

angličtina

Original language name

Anisotropy, segmental dynamics and polymorphism of crystalline biogenic carboxylic acids

Original language description

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.n

Czech name

—

Czech description

—

Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

—

OECD FORD branch

10403 - Physical chemistry

Project

<a href="/en/project/LTAUSA18011" target="_blank" >LTAUSA18011: Ab Initio Investigation of Polymorphism of Active Pharmaceutical Ingredients Supported by State of the Art NMR Crystallographic and Calorimetric Experiments.</a><br>

Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2022

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

Physical Chemistry Chemical Physics

ISSN

1463-9076

e-ISSN

1463-9084

Volume of the periodical

24

Issue of the periodical within the volume

42

Country of publishing house

GB - UNITED KINGDOM

Number of pages

14

Pages from-to

25904-25917

UT code for WoS article

000869849700001

EID of the result in the Scopus database

2-s2.0-85141553866