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Authordc.contributor.authorCampodónico, Paola R.
Authordc.contributor.authorAlarcón Espósito, Jazmín
Authordc.contributor.authorOlivares, Belén
Admission datedc.date.accessioned2022-07-18T16:28:40Z
Available datedc.date.available2022-07-18T16:28:40Z
Publication datedc.date.issued2022
Cita de ítemdc.identifier.citationFrontiers in Chemistry Jun 2022 Volume 10 Article 854918es_ES
Identifierdc.identifier.other10.3389/fchem.2022.854918
Identifierdc.identifier.urihttps://repositorio.uchile.cl/handle/2250/186795
Abstractdc.description.abstractFew kinetic parameters, or reaction rates, are known up to date in detail about 1-chloro and 1-fluoro-2,4-dinitrobenzene (ClDNB and FDNB, respectively) with a series of biothiols in aqueous media. These biological nucleophiles with thiol groups have been widely used as a reference in nucleophile reactivity assays due to their prevalence and cellular abundance. The main aim of this study was to elucidate the reaction mechanism based on Bronsted-type plots and reactivity patterns of the electrophile/nucleophile pairs. A complete kinetic study was performed in terms of the comparison of Bronsted-type slope parameters (beta(nuc)) for the reactions and was used for assigning the mechanism and the rate-determining step associated with the reaction route. A mass spectrometry analysis demonstrated that the nucleophilic center of the biothiols is the -SH group and there is only one kinetic product. The kinetic study suggests that the reaction mechanism might be the borderline between concerted and stepwise pathways. An amine-enol equilibrium for the most reactive nucleophiles appears to be the main determining factor controlling the nucleophilic attack in the nucleophilic aromatic substitution reactions investigated, highlighting the anionic form for these nucleophiles. This amine-enol equilibrium involves a hydrogen bond which stabilizes the intermediate species in the reaction pathway. Thus, intramolecular bonds are formed and enhance the nucleophilic strength through the contribution of the solvent surrounding the electrophile/nucleophile pairs. Finally, we highlight the importance of the formation of electrophile/nucleophile adducts that could modify structures and/or functions of biological systems with potential toxic effects. Therefore, it is essential to know all these kinetic and reactivity patterns and their incidence on other studies.es_ES
Patrocinadordc.description.sponsorshipComision Nacional de Investigacion Cientifica y Tecnologica (CONICYT) CONICYT FONDECYT 1150759 Instituto de Ciencias e Innovacion en Medicina, Facultad de Medicina, Clinica Alemana Universidad del Desarrolloes_ES
Lenguagedc.language.isoenes_ES
Publisherdc.publisherFrontiers Mediaes_ES
Type of licensedc.rightsAttribution-NonCommercial-NoDerivs 3.0 United States*
Link to Licensedc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/3.0/us/*
Sourcedc.sourceFrontiers in Chemistryes_ES
Keywordsdc.subjectSNAr reactionses_ES
Keywordsdc.subjectReaction mechanismes_ES
Keywordsdc.subjectBorder mechanismses_ES
Keywordsdc.subjectBiothiolses_ES
Keywordsdc.subjectReactivity patternses_ES
Títulodc.titleKinetics and reaction mechanism of biothiols involved in SNAr reactions: an experimental studyes_ES
Document typedc.typeArtículo de revistaes_ES
dc.description.versiondc.description.versionVersión publicada - versión final del editores_ES
dcterms.accessRightsdcterms.accessRightsAcceso abiertoes_ES
Catalogueruchile.catalogadorapces_ES
Indexationuchile.indexArtículo de publícación WoSes_ES


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Attribution-NonCommercial-NoDerivs 3.0 United States
Except where otherwise noted, this item's license is described as Attribution-NonCommercial-NoDerivs 3.0 United States