Spectral changes and reactivity of azacumarine homologes in supramolecular systems based on cyclodextrins and cucurbiturils

Cyclodextrins (CDs) and cucurbiturils (CBs) are host molecules, relatively soluble in water with cavities described as hydrophobic. Although the cavity polarity of CDs and CBs is similar, their structural and dimensional differences have produced variations in their functionality in terms of reactiv...

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Autor: Alcázar Jiménez, Jackson José
Tipo de recurso: tesis doctoral
Estado:Versión publicada
Fecha de publicación:2021
País:Chile
OAI Identifier:oai:repositorio.anid.cl:10533/42665
Acceso en línea:https://hdl.handle.net/10533/42665
Access Level:acceso abierto
Palabra clave:Ciencias Naturales
Ciencias Químicas
Otras Especialidades de la Química
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dc.title.en.fl_str_mv Spectral changes and reactivity of azacumarine homologes in supramolecular systems based on cyclodextrins and cucurbiturils
Cambios espectrales y reactividad de homologos de azacumarina en sistemas supramoleculares basados en ciclodextrinas y cucurbiturilos
title Spectral changes and reactivity of azacumarine homologes in supramolecular systems based on cyclodextrins and cucurbiturils
spellingShingle Spectral changes and reactivity of azacumarine homologes in supramolecular systems based on cyclodextrins and cucurbiturils
Alcázar Jiménez, Jackson José
Ciencias Naturales
Ciencias Químicas
Otras Especialidades de la Química
title_short Spectral changes and reactivity of azacumarine homologes in supramolecular systems based on cyclodextrins and cucurbiturils
title_full Spectral changes and reactivity of azacumarine homologes in supramolecular systems based on cyclodextrins and cucurbiturils
title_fullStr Spectral changes and reactivity of azacumarine homologes in supramolecular systems based on cyclodextrins and cucurbiturils
title_full_unstemmed Spectral changes and reactivity of azacumarine homologes in supramolecular systems based on cyclodextrins and cucurbiturils
title_sort Spectral changes and reactivity of azacumarine homologes in supramolecular systems based on cyclodextrins and cucurbiturils
dc.creator.en.fl_str_mv Alcázar Jiménez, Jackson José
author Alcázar Jiménez, Jackson José
author_facet Alcázar Jiménez, Jackson José
author_role author
dc.contributor.advisor.en.fl_str_mv Aliaga Miranda, Margarita Elly
dc.contributor.institution.en.fl_str_mv UNIVERSIDAD CATOLICA
dc.subject.oecd1n.en.fl_str_mv Ciencias Naturales
topic Ciencias Naturales
Ciencias Químicas
Otras Especialidades de la Química
dc.subject.oecd2n.en.fl_str_mv Ciencias Químicas
dc.subject.oecd3n.en.fl_str_mv Otras Especialidades de la Química
description Cyclodextrins (CDs) and cucurbiturils (CBs) are host molecules, relatively soluble in water with cavities described as hydrophobic. Although the cavity polarity of CDs and CBs is similar, their structural and dimensional differences have produced variations in their functionality in terms of reactivity and selectivity. In this context, this research work has as a general objective, to evaluate the spectral behaviors and the reactivity against the hydrolysis reaction for a series of substituted aza-coumarins in the presence and absence of CDs and CBs. For this, five homologues of 3-substituted 7-(dialkylamino)aza-coumarin (DAAS) were successfully synthesized and characterized by NMR, ESI-HRMS and IR. Then such substrates were studied spectroscopically in aqueous solution in the absence and presence of β-CD, DM-β-CD, γ-CD and CB7. The results showed that the spectral properties of the synthesized DAAS and their reactivities against the hydrolysis reaction can be affected depending on the nature of the macrocycle used, with CB7 and DM-β-CD being the most influential macrocycles in the kinetic results of DAAS. this work. Among the results, the following stand out: large bathochromic effects (4500cm-1) and total deactivation of the DAAS emission, attributed to the protonation of the heterocyclic nitrogen of the substrate after its inclusion in CB7. It also highlights an increase of up to 5.5 times in the quantum yield of DAAS in the presence of DM-β-CD. In terms of reactivity, DM-β-CD and CB7 produced significant inhibition effects against the hydrolysis reaction in acid medium for DAAS of the Schiff base type (DMSB), with different association constants 3x103 and 2x105 M-1, respectively. Finally, to elucidate the inhibition effect, a kinetic study on imino-coumarins (IC) was carried out, in such a way that a general kinetic model for the acid hydrolysis of imines, in the presence of CB7, was proposed.
publishDate 2021
dc.date.issued.en.fl_str_mv 2021
dc.date.accessioned.en.fl_str_mv 2022-04-06T21:44:42Z
dc.date.available.en.fl_str_mv 2022-04-06T21:44:42Z
dc.date.accessioned.none.fl_str_mv 2023-05-30T12:28:07Z
dc.date.available.none.fl_str_mv 2023-05-30T12:28:07Z
dc.type.driver.en.fl_str_mv info:eu-repo/semantics/doctoralThesis
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dc.type.tesis.en.fl_str_mv Tesis
format doctoralThesis
status_str publishedVersion
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spelling UNIVERSIDAD CATOLICAAlcázar Jiménez, Jackson José2021https://hdl.handle.net/10533/42665http://purl.org/coar/access_right/c_abf2Otras Especialidades de la QuímicaCiencias QuímicasCiencias NaturalesSpectral changes and reactivity of azacumarine homologes in supramolecular systems based on cyclodextrins and cucurbiturilsAliaga Miranda, Margarita EllyUNIVERSIDAD CATOLICAChileAlcázar Jiménez, Jackson José2022-04-06T21:44:42Z2023-05-30T12:28:07Z2022-04-06T21:44:42Z2023-05-30T12:28:07Z2021Cyclodextrins (CDs) and cucurbiturils (CBs) are host molecules, relatively soluble in water with cavities described as hydrophobic. Although the cavity polarity of CDs and CBs is similar, their structural and dimensional differences have produced variations in their functionality in terms of reactivity and selectivity. In this context, this research work has as a general objective, to evaluate the spectral behaviors and the reactivity against the hydrolysis reaction for a series of substituted aza-coumarins in the presence and absence of CDs and CBs. For this, five homologues of 3-substituted 7-(dialkylamino)aza-coumarin (DAAS) were successfully synthesized and characterized by NMR, ESI-HRMS and IR. Then such substrates were studied spectroscopically in aqueous solution in the absence and presence of β-CD, DM-β-CD, γ-CD and CB7. The results showed that the spectral properties of the synthesized DAAS and their reactivities against the hydrolysis reaction can be affected depending on the nature of the macrocycle used, with CB7 and DM-β-CD being the most influential macrocycles in the kinetic results of DAAS. this work. Among the results, the following stand out: large bathochromic effects (4500cm-1) and total deactivation of the DAAS emission, attributed to the protonation of the heterocyclic nitrogen of the substrate after its inclusion in CB7. It also highlights an increase of up to 5.5 times in the quantum yield of DAAS in the presence of DM-β-CD. In terms of reactivity, DM-β-CD and CB7 produced significant inhibition effects against the hydrolysis reaction in acid medium for DAAS of the Schiff base type (DMSB), with different association constants 3x103 and 2x105 M-1, respectively. Finally, to elucidate the inhibition effect, a kinetic study on imino-coumarins (IC) was carried out, in such a way that a general kinetic model for the acid hydrolysis of imines, in the presence of CB7, was proposed.Las ciclodextrinas (CDs) y cucurbiturilos (CBs) son moléculas anfitrionas, relativamente solubles en agua con cavidades descritas como hidrofóbicas. Aunque la polaridad en la cavidad de las CDs y CBs es similar, sus diferencias estructurales y dimensionales han producido variaciones en su funcionalidad en términos de reactividad y selectividad. En este contexto, este trabajo de investigación tiene como objetivo general, evaluar los comportamientos espectrales y la reactividad frente a la reacción de hidrólisis para una serie de aza-cumarinas sustituidas en presencia y ausencia de CDs y CBs. Para ello, cinco homólogos de 7-(dialquilamino)aza-cumarina 3-sustituidas (DAAS) fueron sintetizados y caracterizados satisfactoriamente por RMN, ESI-HRMS e IR. Luego tales sustratos fueron estudiados espectroscópicamente en solución acuosa en ausencia y presencia de β-CD, DM-β-CD, -CD y CB7. Los resultados mostraron, que las propiedades espectrales de las DAAS sintetizadas y sus reactividades frente a la reacción de hidrólisis pueden ser afectadas según la naturaleza del macrociclo empleado, siendo el CB7 y la DM-β-CD los macrociclos más influyentes en los resultados cinéticos de este trabajo. Entre los resultados destacan: grandes efectos batocrómicos (4500cm-1) y desactivación total de la emisión de las DAAS, atribuido a la protonación del nitrógeno heterocíclico del sustrato tras su inclusión en CB7. También destaca un aumento de hasta 5,5 veces en el rendimiento cuántico de las DAAS en presencia de DM-β-CD. En términos de reactividad, el DM-β-CD y el CB7 produjeron efectos de inhibición significativos frente a la reacción de hidrólisis en medio ácido para el DAAS de tipo base de Schiff (DMSB), con diferentes constantes de asociación 3x103 y 2x105 M-1, respectivamente. Finalmente, para dilucidar el efecto de inhibición, un estudio cinético en imino-cumarinas (IC) fue llevado a cabo, de tal manera que, un modelo cinético general para la hidrólisis ácida de iminas, en presencia de CB7, fue propuesto.211707931160271https://hdl.handle.net/10533/42665instname: Conicytreponame: Repositorio Digital RI2.0info:eu-repo/grantAgreement//21170793info:eu-repo/grantAgreement//1160271info:eu-repo/grantAgreement//1170753info:eu-repo/semantics/dataset/hdl.handle.net/10533/93488https://repositorio.uc.cl/handle/11534/61938info:eu-repo/semantics/openAccessAttribution-NonCommercial-NoDerivs 3.0 Chilehttp://creativecommons.org/licenses/by-nc-nd/3.0/cl/Ciencias NaturalesCiencias QuímicasOtras Especialidades de la QuímicaSpectral changes and reactivity of azacumarine homologes in supramolecular systems based on cyclodextrins and cucurbiturilsCambios espectrales y reactividad de homologos de azacumarina en sistemas supramoleculares basados en ciclodextrinas y cucurbiturilosinfo:eu-repo/semantics/doctoralThesisinfo:eu-repo/semantics/publishedVersionTesisTesishttps://hdl.handle.net/10533/4266528d82c6d-eb8a-49b4-8b1b-1010068a28fbvirtual::79893-128d82c6d-eb8a-49b4-8b1b-1010068a28fbvirtual::79893-1ORIGINALTesis_Jackson.pdfapplication/pdf4646819https://repositorio.anid.cl/bitstreams/c6e7bc86-645d-4fd0-8ad0-62f80fb1337e/download10d8a1b932dfd2f73251204c7f9c40e7MD5110533/42665oai:repositorio.anid.cl:10533/426652024-01-17 16:13:05.706http://creativecommons.org/licenses/by-nc-nd/3.0/cl/info:eu-repo/semantics/openAccesshttps://repositorio.anid.clRepositorio ANIDaletelier@anid.cl
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