Spectral analysis and quantum chemical studies of chair and twist-boat conformers of cycloheximide in gas and solution phases

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dc.contributor.authorTokatli, A.
dc.contributor.authorUcun, F.
dc.contributor.authorSutcu, K.
dc.contributor.authorOsmanoglu, Y. E.
dc.contributor.authorOsmanoglu, S.
dc.date.accessioned2024-04-24T16:15:36Z
dc.date.available2024-04-24T16:15:36Z
dc.date.issued2018
dc.departmentDicle Üniversitesien_US
dc.description.abstractIn this study the conformational behavior of cycloheximide in the gas and solution (CHCl3) phases has theoretically been investigated by spectroscopic and quantum chemical properties using density functional theory (wB97X-D) method with 6-31++G(d,p) basis set, for the first time. The calculated IR results reveal that in the ground state the molecule exits as a mixture of the chair and twist-boat conformers in the gas phase, while the calculated NMR results reveal that it only exits as the chair conformer in the solution phase. In order to obtain the contributions coming from intramolecular interactions to the stability of the conformers in the gas and solution phases, the quantum theory of atoms in molecules (QTAIM), noncovalent interactions (NCI) method, and natural bond orbital analysis (NBO) have been employed. The QTAIM and NCI methods indicated that by intramolecular interactions with bond critical point (BCP) the twist-boat conformer is more stabilized than the chair conformer, while by steric interactions it is more destabilized. Considering that these interactions balance each other, the stabilities of the conformers are understood to be dictated by the van der Waals interactions. The NBO analyses show that the hyperconjugative and steric effects play an important role in the stabilization in the gas and solution phases. Furthermore, to get a better understanding of the chemical behavior of this important antibiotic drug we have evaluated and, commented the global and local reactivity descriptors of the both conformers. Finally, the EPR analysis of gamma-irradiated cycloheximide has been done. The comparison of the experimental and calculated data have showed the inducement of a radical structure of (CH2)(2)CCH2 in the molecule. The experimental EPR spectrum has also confirmed that the molecule simultaneously exists in the chair and twist-boat conformers in the solid phase. (C) 2017 Elsevier B.V. All rights reserved.en_US
dc.identifier.doi10.1016/j.molstruc.2017.10.037
dc.identifier.endpage436en_US
dc.identifier.issn0022-2860
dc.identifier.issn1872-8014
dc.identifier.scopus2-s2.0-85032037945
dc.identifier.scopusqualityQ1
dc.identifier.startpage428en_US
dc.identifier.urihttps://doi.org/10.1016/j.molstruc.2017.10.037
dc.identifier.urihttps://hdl.handle.net/11468/15863
dc.identifier.volume1154en_US
dc.identifier.wosWOS:000418212000047
dc.identifier.wosqualityQ3
dc.indekslendigikaynakWeb of Science
dc.indekslendigikaynakScopus
dc.language.isoenen_US
dc.publisherElsevieren_US
dc.relation.ispartofJournal of Molecular Structure
dc.relation.publicationcategoryMakale - Uluslararası Hakemli Dergi - Kurum Öğretim Elemanıen_US
dc.rightsinfo:eu-repo/semantics/closedAccessen_US
dc.subjectCycloheximideen_US
dc.subjectVibrational Spectraen_US
dc.subjectNmren_US
dc.subjectEpren_US
dc.subjectNcien_US
dc.subjectQtaimen_US
dc.titleSpectral analysis and quantum chemical studies of chair and twist-boat conformers of cycloheximide in gas and solution phasesen_US
dc.titleSpectral analysis and quantum chemical studies of chair and twist-boat conformers of cycloheximide in gas and solution phases
dc.typeArticleen_US

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