An interesting case where water behaves as a unique solvent: 4-aminophthalimide emission profile to monitor aqueous environment

Autores
Durantini, Andres Matías; Falcone, Ruben Dario; Anunziata, Jorge Daniel; Abuin, Elsa B.; Lissi, Eduardo A.; Chessa, Juana Josefa; Correa, Nestor Mariano
Año de publicación
2013
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The behavior of 4-aminophthalimide (4-AP), a common molecular probe utilized in solvation dynamics experiments, was revisited in polar aprotic and protic solvents using absorption, steady-state, and timeresolved fluorescence (TRES) techniques. Also, the deuterium isotope effect was investigated using D2O as solvent. The absorption spectra of 4- AP consist of two absorption bands with maxima around 300 nm (B2 band) and 370 nm (B1 band) depending on the environment, while the emission feature consists of a single band. In all the solvents investigated (excluding water), the 4-AP photophysics is similar and the emission spectra are independent of the excitation wavelength used. In water the behavior is unique and the emission spectra maximum is different depending on the excitation wavelength used. The emission maximum is 561.7 nm using the excitation wavelength that correspond to the B2 absorption band maximum (λexcB2 = 303.4 nm) but is 545.7 nm when the excitation wavelength that correspond to the B1 absorption maximum (λexcB1 = 370.0 nm) is used. Moreover, while the fluorescence decays of 4-AP in water exhibit no emission wavelength dependence at λexcB2, the situation is quite different when λexcB1 is used. In this case, we found a time-dependent emission spectrum that shifts to the blue with time. Our results show that the solvent-mediated proton transfer process displays a fundamental role in the 4-AP emission profile and for the first time a mechanism was proposed that fully explains the 4-AP behavior in every solvent including water. The deuterium isotope effect confirms the assumption because the proton-transfer process is dramatically retarded in this solvent. Consequently, we were able to elucidate not only why in water the emission spectra depend on the excitation wavelength but also why the time-dependent emission spectra shift to the blue with time. Thus, our work reveals the importance that the medium has on the behavior of a widespread dye used as chromophore. This is significant since the use of chromophores without understanding its chemistry can induce artifacts into the interpretation of solvation dynamics in heterogeneous environments, in particular, those provided by aqueous biological systems.
Fil: Durantini, Andres Matías. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Falcone, Ruben Dario. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Anunziata, Jorge Daniel. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Abuin, Elsa B.. Universidad de Santiago de Chile; Chile
Fil: Lissi, Eduardo A.. Universidad de Santiago de Chile; Chile
Fil: Chessa, Juana Josefa. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Correa, Nestor Mariano. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Materia
4-Ap
Water
Photochemistry
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/23475
Acceder
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network_name_str CONICET Digital (CONICET)
spelling An interesting case where water behaves as a unique solvent: 4-aminophthalimide emission profile to monitor aqueous environmentDurantini, Andres MatíasFalcone, Ruben DarioAnunziata, Jorge DanielAbuin, Elsa B.Lissi, Eduardo A.Chessa, Juana JosefaCorrea, Nestor Mariano4-ApWaterPhotochemistryhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The behavior of 4-aminophthalimide (4-AP), a common molecular probe utilized in solvation dynamics experiments, was revisited in polar aprotic and protic solvents using absorption, steady-state, and timeresolved fluorescence (TRES) techniques. Also, the deuterium isotope effect was investigated using D2O as solvent. The absorption spectra of 4- AP consist of two absorption bands with maxima around 300 nm (B2 band) and 370 nm (B1 band) depending on the environment, while the emission feature consists of a single band. In all the solvents investigated (excluding water), the 4-AP photophysics is similar and the emission spectra are independent of the excitation wavelength used. In water the behavior is unique and the emission spectra maximum is different depending on the excitation wavelength used. The emission maximum is 561.7 nm using the excitation wavelength that correspond to the B2 absorption band maximum (λexcB2 = 303.4 nm) but is 545.7 nm when the excitation wavelength that correspond to the B1 absorption maximum (λexcB1 = 370.0 nm) is used. Moreover, while the fluorescence decays of 4-AP in water exhibit no emission wavelength dependence at λexcB2, the situation is quite different when λexcB1 is used. In this case, we found a time-dependent emission spectrum that shifts to the blue with time. Our results show that the solvent-mediated proton transfer process displays a fundamental role in the 4-AP emission profile and for the first time a mechanism was proposed that fully explains the 4-AP behavior in every solvent including water. The deuterium isotope effect confirms the assumption because the proton-transfer process is dramatically retarded in this solvent. Consequently, we were able to elucidate not only why in water the emission spectra depend on the excitation wavelength but also why the time-dependent emission spectra shift to the blue with time. Thus, our work reveals the importance that the medium has on the behavior of a widespread dye used as chromophore. This is significant since the use of chromophores without understanding its chemistry can induce artifacts into the interpretation of solvation dynamics in heterogeneous environments, in particular, those provided by aqueous biological systems.Fil: Durantini, Andres Matías. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Falcone, Ruben Dario. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Anunziata, Jorge Daniel. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Abuin, Elsa B.. Universidad de Santiago de Chile; ChileFil: Lissi, Eduardo A.. Universidad de Santiago de Chile; ChileFil: Chessa, Juana Josefa. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Correa, Nestor Mariano. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaAmerican Chemical Society2013-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/23475Durantini, Andres Matías; Falcone, Ruben Dario; Anunziata, Jorge Daniel; Abuin, Elsa B.; Lissi, Eduardo A.; et al.; An interesting case where water behaves as a unique solvent: 4-aminophthalimide emission profile to monitor aqueous environment; American Chemical Society; Journal of Physical Chemistry B; 117; 7; 1-2013; 2160-21681089-5647CONICET DigitalCONICETenghttp://dx.doi.org/10.1021/jp402647dinfo:eu-repo/semantics/altIdentifier/doi/10.1021/jp310854sinfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jp310854sinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:33:40Zoai:ri.conicet.gov.ar:11336/23475instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-10-22 11:33:40.287CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv An interesting case where water behaves as a unique solvent: 4-aminophthalimide emission profile to monitor aqueous environment
title An interesting case where water behaves as a unique solvent: 4-aminophthalimide emission profile to monitor aqueous environment
spellingShingle An interesting case where water behaves as a unique solvent: 4-aminophthalimide emission profile to monitor aqueous environment
Durantini, Andres Matías
4-Ap
Water
Photochemistry
title_short An interesting case where water behaves as a unique solvent: 4-aminophthalimide emission profile to monitor aqueous environment
title_full An interesting case where water behaves as a unique solvent: 4-aminophthalimide emission profile to monitor aqueous environment
title_fullStr An interesting case where water behaves as a unique solvent: 4-aminophthalimide emission profile to monitor aqueous environment
title_full_unstemmed An interesting case where water behaves as a unique solvent: 4-aminophthalimide emission profile to monitor aqueous environment
title_sort An interesting case where water behaves as a unique solvent: 4-aminophthalimide emission profile to monitor aqueous environment
dc.creator.none.fl_str_mv Durantini, Andres Matías
Falcone, Ruben Dario
Anunziata, Jorge Daniel
Abuin, Elsa B.
Lissi, Eduardo A.
Chessa, Juana Josefa
Correa, Nestor Mariano
author Durantini, Andres Matías
author_facet Durantini, Andres Matías
Falcone, Ruben Dario
Anunziata, Jorge Daniel
Abuin, Elsa B.
Lissi, Eduardo A.
Chessa, Juana Josefa
Correa, Nestor Mariano
author_role author
author2 Falcone, Ruben Dario
Anunziata, Jorge Daniel
Abuin, Elsa B.
Lissi, Eduardo A.
Chessa, Juana Josefa
Correa, Nestor Mariano
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv 4-Ap
Water
Photochemistry
topic 4-Ap
Water
Photochemistry
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The behavior of 4-aminophthalimide (4-AP), a common molecular probe utilized in solvation dynamics experiments, was revisited in polar aprotic and protic solvents using absorption, steady-state, and timeresolved fluorescence (TRES) techniques. Also, the deuterium isotope effect was investigated using D2O as solvent. The absorption spectra of 4- AP consist of two absorption bands with maxima around 300 nm (B2 band) and 370 nm (B1 band) depending on the environment, while the emission feature consists of a single band. In all the solvents investigated (excluding water), the 4-AP photophysics is similar and the emission spectra are independent of the excitation wavelength used. In water the behavior is unique and the emission spectra maximum is different depending on the excitation wavelength used. The emission maximum is 561.7 nm using the excitation wavelength that correspond to the B2 absorption band maximum (λexcB2 = 303.4 nm) but is 545.7 nm when the excitation wavelength that correspond to the B1 absorption maximum (λexcB1 = 370.0 nm) is used. Moreover, while the fluorescence decays of 4-AP in water exhibit no emission wavelength dependence at λexcB2, the situation is quite different when λexcB1 is used. In this case, we found a time-dependent emission spectrum that shifts to the blue with time. Our results show that the solvent-mediated proton transfer process displays a fundamental role in the 4-AP emission profile and for the first time a mechanism was proposed that fully explains the 4-AP behavior in every solvent including water. The deuterium isotope effect confirms the assumption because the proton-transfer process is dramatically retarded in this solvent. Consequently, we were able to elucidate not only why in water the emission spectra depend on the excitation wavelength but also why the time-dependent emission spectra shift to the blue with time. Thus, our work reveals the importance that the medium has on the behavior of a widespread dye used as chromophore. This is significant since the use of chromophores without understanding its chemistry can induce artifacts into the interpretation of solvation dynamics in heterogeneous environments, in particular, those provided by aqueous biological systems.
Fil: Durantini, Andres Matías. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Falcone, Ruben Dario. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Anunziata, Jorge Daniel. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Abuin, Elsa B.. Universidad de Santiago de Chile; Chile
Fil: Lissi, Eduardo A.. Universidad de Santiago de Chile; Chile
Fil: Chessa, Juana Josefa. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Correa, Nestor Mariano. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
description The behavior of 4-aminophthalimide (4-AP), a common molecular probe utilized in solvation dynamics experiments, was revisited in polar aprotic and protic solvents using absorption, steady-state, and timeresolved fluorescence (TRES) techniques. Also, the deuterium isotope effect was investigated using D2O as solvent. The absorption spectra of 4- AP consist of two absorption bands with maxima around 300 nm (B2 band) and 370 nm (B1 band) depending on the environment, while the emission feature consists of a single band. In all the solvents investigated (excluding water), the 4-AP photophysics is similar and the emission spectra are independent of the excitation wavelength used. In water the behavior is unique and the emission spectra maximum is different depending on the excitation wavelength used. The emission maximum is 561.7 nm using the excitation wavelength that correspond to the B2 absorption band maximum (λexcB2 = 303.4 nm) but is 545.7 nm when the excitation wavelength that correspond to the B1 absorption maximum (λexcB1 = 370.0 nm) is used. Moreover, while the fluorescence decays of 4-AP in water exhibit no emission wavelength dependence at λexcB2, the situation is quite different when λexcB1 is used. In this case, we found a time-dependent emission spectrum that shifts to the blue with time. Our results show that the solvent-mediated proton transfer process displays a fundamental role in the 4-AP emission profile and for the first time a mechanism was proposed that fully explains the 4-AP behavior in every solvent including water. The deuterium isotope effect confirms the assumption because the proton-transfer process is dramatically retarded in this solvent. Consequently, we were able to elucidate not only why in water the emission spectra depend on the excitation wavelength but also why the time-dependent emission spectra shift to the blue with time. Thus, our work reveals the importance that the medium has on the behavior of a widespread dye used as chromophore. This is significant since the use of chromophores without understanding its chemistry can induce artifacts into the interpretation of solvation dynamics in heterogeneous environments, in particular, those provided by aqueous biological systems.
publishDate 2013
dc.date.none.fl_str_mv 2013-01
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/23475
Durantini, Andres Matías; Falcone, Ruben Dario; Anunziata, Jorge Daniel; Abuin, Elsa B.; Lissi, Eduardo A.; et al.; An interesting case where water behaves as a unique solvent: 4-aminophthalimide emission profile to monitor aqueous environment; American Chemical Society; Journal of Physical Chemistry B; 117; 7; 1-2013; 2160-2168
1089-5647
CONICET Digital
CONICET
url http://hdl.handle.net/11336/23475
identifier_str_mv Durantini, Andres Matías; Falcone, Ruben Dario; Anunziata, Jorge Daniel; Abuin, Elsa B.; Lissi, Eduardo A.; et al.; An interesting case where water behaves as a unique solvent: 4-aminophthalimide emission profile to monitor aqueous environment; American Chemical Society; Journal of Physical Chemistry B; 117; 7; 1-2013; 2160-2168
1089-5647
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv http://dx.doi.org/10.1021/jp402647d
info:eu-repo/semantics/altIdentifier/doi/10.1021/jp310854s
info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jp310854s
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
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eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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