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dc.contributor.authorThakkar, Balmukund
dc.contributor.authorSvendsen, John Sigurd Mjøen
dc.contributor.authorEngh, Richard Alan
dc.date.accessioned2018-10-02T10:54:02Z
dc.date.available2018-10-02T10:54:02Z
dc.date.issued2018-09-25
dc.description.abstractCis/trans isomerization of amide bonds is a key step in a wide range of biological and synthetic processes. Occurring through C-N amide bond rotation, it also coincides with the activation of amides in enzymatic hydrolysis. In recently described QM studies of cis/trans isomerization in secondary amides using density functional methods, we highlighted that a peptidic prototype, such as glycylglycine methyl ester, can suitably represent the isomerization and complexities arising out of a larger molecular backbone, and can serve as the primary scaffold for model structures with different substitution patterns in order to assess and compare the steric effect of the substitution patterns. Here, we describe our theoretical assessment of such steric effects using <i>tert</i>-butyl as a representative bulky substitution. We analyze the geometries and relative stabilities of both trans and cis isomers, and effects on the cis/trans isomerization barrier. We also use the additivity principle to calculate absolute steric effects with a gradual increase in bulk. The study establishes that bulky substitutions significantly destabilize cis isomers and also increases the isomerization barrier, thereby synergistically hindering the cis/trans isomerization of secondary amides. These results provide a basis for the rationalization of kinetic and thermodynamic properties of peptides with potential applications in synthetic and medicinal chemistry.en_US
dc.description.sponsorshipUiT The Arctic University of Norwayen_US
dc.descriptionSource at <a href=https://doi.org/10.3390/molecules23102455> https://doi.org/10.3390/molecules23102455 </a>.en_US
dc.identifier.citationThakkar, B.S., Svendsen, J.S.M. & Engh, R.A. (2018). Density Functional Studies on Secondary Amides: Role of Steric Factors in Cis/Trans Isomerization. Molecules, 23(10). https://doi.org/10.3390/molecules23102455en_US
dc.identifier.cristinIDFRIDAID 1616950
dc.identifier.doi10.3390/molecules23102455
dc.identifier.issn1420-3049
dc.identifier.urihttps://hdl.handle.net/10037/13895
dc.language.isoengen_US
dc.publisherMDPIen_US
dc.relation.journalMolecules
dc.relation.urihttps://www.mdpi.com/1420-3049/23/10/2455/htm
dc.rights.accessRightsopenAccessen_US
dc.subjectVDP::Matematikk og naturvitenskap: 400::Kjemi: 440::Teoretisk kjemi, kvantekjemi: 444en_US
dc.subjectVDP::Mathematics and natural scienses: 400::Chemistry: 440::Theoretical chemistry, quantum chemistry: 444en_US
dc.subjectOrganisk kjemi / Organic chemistryen_US
dc.subjectdensity functional theoryen_US
dc.subjectcis/trans isomerizationen_US
dc.subjectsecondary amidesen_US
dc.subjectdipeptidesen_US
dc.subjectsteric effectsen_US
dc.subjecttert-butylen_US
dc.subjectadditivity principleen_US
dc.titleDensity Functional Studies on Secondary Amides: Role of Steric Factors in Cis/Trans Isomerizationen_US
dc.typeJournal articleen_US
dc.typeTidsskriftartikkelen_US
dc.typePeer revieweden_US


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