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dc.creatorAssaleh, Mohamed H.
dc.creatorBožić, Aleksandra R.
dc.creatorBjelogrlić, Snežana
dc.creatorMilošević, Milena D.
dc.creatorSimić, Milena R.
dc.creatorMarinković, Aleksandar D.
dc.creatorCvijetić, Ilija
dc.date.accessioned2019-07-17T09:58:59Z
dc.date.available2019-07-17T09:58:59Z
dc.date.issued2019
dc.identifier.issn1040-0400
dc.identifier.urihttps://cer.ihtm.bg.ac.rs/handle/123456789/3037
dc.description.abstractThiocarbohydrazones (TCHs) and structurally related molecules are versatile organic compounds which exert antioxidant, anticancer, and other beneficial health effects. The combination of UV/Vis, NMR spectroscopy, and quantum chemical calculations was used to rationalize the experimentally observed increase in the radical scavenging activity upon the addition of water in DMSO solution of TCHs. Mono- and bis(salicylaldehyde) TCHs (compounds 1 and 2) undergo water-induced E-to-Z isomerization which is followed by disruption of intramolecular hydrogen bond, ground state destabilization, and 11 kcal/mol decrease in the bond dissociation enthalpy (BDE). Electron spin delocalization is more pronounced in Z-isomers of 1 and 2. On the other hand, 2-acetylpyridine TCHs (compounds 3 and 4) undergo thione-to-thiol tautomerism which also decreases the BDE and facilitates the hydrogen atom transfer to 2,2-diphenyl-1-picrylhydrazyl radical (DPPH∙). The appearance of thiolic –SH group as another reactive site toward free radicals improves the antioxidant activity of 3 and 4. The spin density of 3- and 4-thiol radicals is delocalized over the entire thiocarbohydrazide moiety compared to more localized spin of thione radicals. Additional stabilization of thiol radicals corroborates with the increased antioxidant activity. This study provides the new insights on the solution structure of TCHs, and also highlights the importance of solution structure determination when studying the structure-antioxidant relationships of isomerizable compounds.en
dc.language.isoensr
dc.publisherSpringersr
dc.relationinfo:eu-repo/grantAgreement/MESTD/Basic Research (BR or ON)/172013/RS//sr
dc.relationinfo:eu-repo/grantAgreement/MESTD/Basic Research (BR or ON)/172035/RS//sr
dc.relationinfo:eu-repo/grantAgreement/MESTD/Basic Research (BR or ON)/172055/RS//sr
dc.rightsrestrictedAccesssr
dc.sourceStructural Chemistrysr
dc.subjectThiocarbohydrazonessr
dc.subjectE/Z isomerismsr
dc.subjectTautomerismsr
dc.subjectAntioxidantactivitysr
dc.subjectBonddissociationenthalpysr
dc.subjectSpindensity distributionsr
dc.titleWater-induced isomerism of salicylaldehyde and 2-acetylpyridine mono- and bis-(thiocarbohydrazones) improves the antioxidant activity: spectroscopic and DFT studyen
dc.typearticlesr
dc.rights.licenseARRsr
dcterms.abstractМаринковић, Aлександар Д.; Aссалех, Мохамед Х.; Божић, Aлександра Р.; Бјелогрлић, Снежана; Милошевић, Милена; Симић, Милена; Цвијетић, Илија Н.;
dc.rights.holderSpringersr
dc.citation.volume30
dc.citation.spage2447
dc.citation.epage2457
dc.citation.rankM22~
dc.identifier.doi10.1007/s11224-019-01371-4
dc.identifier.scopus2-s2.0-85068185532
dc.identifier.wos000494698700034
dc.type.versionpublishedVersionsr


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