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Structures Controlled by Entropy: The Flexibility of Strychnine as Example

Sternberg, Ulrich 1; Witter, Raiker 2,3
1 Fakultät für Bauingenieur-, Geo- und Umweltwissenschaften (BGU), Karlsruher Institut für Technologie (KIT)
2 Institut für Nanotechnologie (INT), Karlsruher Institut für Technologie (KIT)
3 Center for Electrochemical Energy Storage Ulm & Karlsruhe (CELEST), Karlsruher Institut für Technologie (KIT)

Abstract:

To study the flexibility of strychnine, we performed molecular dynamics simulations with orientational tensorial constraints (MDOC). Tensorial constraints are derived from nuclear magnetic resonance (NMR) interaction tensors, for instance, from residual dipolar couplings (RDCs). Used as orientational constraints, they rotate the whole molecule and molecular parts with low rotational barriers. Since the NMR parameters are measured at ambient temperatures, orientational constraints generate conformers that populate the whole landscape of Gibbs free energy. In MDOC, structures are populated that are not only controlled by energy but by the entropy term TΔS of the Gibbs free energy. In the case of strychnine, it is shown that ring conformers are populated, which has not been discussed in former investigations. These conformer populations are not only in accordance with RDCs but fulfill nuclear Overhauser effect (NOE)-derived distance constraints and $^{3}J_{HH}$ couplings as well.


Verlagsausgabe §
DOI: 10.5445/IR/1000153595
Veröffentlicht am 04.01.2023
Originalveröffentlichung
DOI: 10.3390/molecules27227987
Scopus
Zitationen: 3
Web of Science
Zitationen: 3
Dimensions
Zitationen: 3
Cover der Publikation
Zugehörige Institution(en) am KIT Center for Electrochemical Energy Storage Ulm & Karlsruhe (CELEST)
Institut für Nanotechnologie (INT)
Publikationstyp Zeitschriftenaufsatz
Publikationsjahr 2022
Sprache Englisch
Identifikator ISSN: 1420-3049
KITopen-ID: 1000153595
HGF-Programm 43.31.01 (POF IV, LK 01) Multifunctionality Molecular Design & Material Architecture
Erschienen in Molecules
Verlag MDPI
Band 27
Heft 22
Seiten Art.Nr. 7987
Vorab online veröffentlicht am 17.11.2022
Nachgewiesen in Scopus
Web of Science
Dimensions
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