Monitoring chemical and biological electron transfer reactions with a fluorogenic vitamin K analogue probe

Autores
Belzile, Mei-Ni; Godin, Robert; Durantini, Andres Matías; Cosa, Gonzalo
Año de publicación
2016
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
We report herein the design, synthesis, and characterization of a two-segment fluorogenic analogue of Vitamin K, B-VKQ, prepared by coupling Vitamin K3, also known as menadione (a quinone redox center), to a boron-dipyrromethene (BODIPY) fluorophore (a lipophilic reporter segment). Oxidation-reduction reactions, spectroelectrochemical studies, and enzymatic assays conducted in the presence of DT-diaphorase illustrate that the new probe shows reversible redox behavior on par with that of Vitamin K, provides a high-sensitivity fluorescence signal, and is compatible with biological conditions, opening the door to monitor remotely (i.e., via imaging) redox processes in real time. In its oxidized form, B-VKQ is non-emissive, while upon reduction to the hydroquinone form, B-VKQH2, BODIPY fluorescence is restored, with emission quantum yield values of ca. 0.54 in toluene. Density functional theory studies validate a photoinduced electron transfer intramolecular switching mechanism, active in the non-emissive quinone form and deactivated upon reduction to the emissive dihydroquinone form. Our results highlight the potential of B-VKQ as a fluorogenic probe to study electron transfer and transport in model systems and biological structures with optimal sensitivity and desirable chemical specificity. Use of such a probe may enable a better understanding of the role that Vitamin K plays in biological redox reactions ubiquitous in key cellular processes, and help elucidate the mechanism and pathological significance of these reactions in biological systems.
Fil: Belzile, Mei-Ni. Mcgill University; Canadá
Fil: Godin, Robert. Mcgill University; Canadá
Fil: Durantini, Andres Matías. Mcgill University; Canadá. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina
Fil: Cosa, Gonzalo. Mcgill University; Canadá
Materia
Electron Transfer
Vitamin K
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:11336/60942
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/60942
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Monitoring chemical and biological electron transfer reactions with a fluorogenic vitamin K analogue probeBelzile, Mei-NiGodin, RobertDurantini, Andres MatíasCosa, GonzaloElectron TransferVitamin Khttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1We report herein the design, synthesis, and characterization of a two-segment fluorogenic analogue of Vitamin K, B-VKQ, prepared by coupling Vitamin K3, also known as menadione (a quinone redox center), to a boron-dipyrromethene (BODIPY) fluorophore (a lipophilic reporter segment). Oxidation-reduction reactions, spectroelectrochemical studies, and enzymatic assays conducted in the presence of DT-diaphorase illustrate that the new probe shows reversible redox behavior on par with that of Vitamin K, provides a high-sensitivity fluorescence signal, and is compatible with biological conditions, opening the door to monitor remotely (i.e., via imaging) redox processes in real time. In its oxidized form, B-VKQ is non-emissive, while upon reduction to the hydroquinone form, B-VKQH2, BODIPY fluorescence is restored, with emission quantum yield values of ca. 0.54 in toluene. Density functional theory studies validate a photoinduced electron transfer intramolecular switching mechanism, active in the non-emissive quinone form and deactivated upon reduction to the emissive dihydroquinone form. Our results highlight the potential of B-VKQ as a fluorogenic probe to study electron transfer and transport in model systems and biological structures with optimal sensitivity and desirable chemical specificity. Use of such a probe may enable a better understanding of the role that Vitamin K plays in biological redox reactions ubiquitous in key cellular processes, and help elucidate the mechanism and pathological significance of these reactions in biological systems.Fil: Belzile, Mei-Ni. Mcgill University; CanadáFil: Godin, Robert. Mcgill University; CanadáFil: Durantini, Andres Matías. Mcgill University; Canadá. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; ArgentinaFil: Cosa, Gonzalo. Mcgill University; CanadáAmerican Chemical Society2016-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/60942Belzile, Mei-Ni; Godin, Robert; Durantini, Andres Matías; Cosa, Gonzalo; Monitoring chemical and biological electron transfer reactions with a fluorogenic vitamin K analogue probe; American Chemical Society; Journal of the American Chemical Society; 138; 50; 12-2016; 16388-163970002-78631520-5126CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/jacs.6b09735info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jacs.6b09735info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:15:57Zoai:ri.conicet.gov.ar:11336/60942instacron: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:34982025-09-29 10:15:57.793CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Monitoring chemical and biological electron transfer reactions with a fluorogenic vitamin K analogue probe
title Monitoring chemical and biological electron transfer reactions with a fluorogenic vitamin K analogue probe
spellingShingle Monitoring chemical and biological electron transfer reactions with a fluorogenic vitamin K analogue probe
Belzile, Mei-Ni
Electron Transfer
Vitamin K
title_short Monitoring chemical and biological electron transfer reactions with a fluorogenic vitamin K analogue probe
title_full Monitoring chemical and biological electron transfer reactions with a fluorogenic vitamin K analogue probe
title_fullStr Monitoring chemical and biological electron transfer reactions with a fluorogenic vitamin K analogue probe
title_full_unstemmed Monitoring chemical and biological electron transfer reactions with a fluorogenic vitamin K analogue probe
title_sort Monitoring chemical and biological electron transfer reactions with a fluorogenic vitamin K analogue probe
dc.creator.none.fl_str_mv Belzile, Mei-Ni
Godin, Robert
Durantini, Andres Matías
Cosa, Gonzalo
author Belzile, Mei-Ni
author_facet Belzile, Mei-Ni
Godin, Robert
Durantini, Andres Matías
Cosa, Gonzalo
author_role author
author2 Godin, Robert
Durantini, Andres Matías
Cosa, Gonzalo
author2_role author
author
author
dc.subject.none.fl_str_mv Electron Transfer
Vitamin K
topic Electron Transfer
Vitamin K
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv We report herein the design, synthesis, and characterization of a two-segment fluorogenic analogue of Vitamin K, B-VKQ, prepared by coupling Vitamin K3, also known as menadione (a quinone redox center), to a boron-dipyrromethene (BODIPY) fluorophore (a lipophilic reporter segment). Oxidation-reduction reactions, spectroelectrochemical studies, and enzymatic assays conducted in the presence of DT-diaphorase illustrate that the new probe shows reversible redox behavior on par with that of Vitamin K, provides a high-sensitivity fluorescence signal, and is compatible with biological conditions, opening the door to monitor remotely (i.e., via imaging) redox processes in real time. In its oxidized form, B-VKQ is non-emissive, while upon reduction to the hydroquinone form, B-VKQH2, BODIPY fluorescence is restored, with emission quantum yield values of ca. 0.54 in toluene. Density functional theory studies validate a photoinduced electron transfer intramolecular switching mechanism, active in the non-emissive quinone form and deactivated upon reduction to the emissive dihydroquinone form. Our results highlight the potential of B-VKQ as a fluorogenic probe to study electron transfer and transport in model systems and biological structures with optimal sensitivity and desirable chemical specificity. Use of such a probe may enable a better understanding of the role that Vitamin K plays in biological redox reactions ubiquitous in key cellular processes, and help elucidate the mechanism and pathological significance of these reactions in biological systems.
Fil: Belzile, Mei-Ni. Mcgill University; Canadá
Fil: Godin, Robert. Mcgill University; Canadá
Fil: Durantini, Andres Matías. Mcgill University; Canadá. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina
Fil: Cosa, Gonzalo. Mcgill University; Canadá
description We report herein the design, synthesis, and characterization of a two-segment fluorogenic analogue of Vitamin K, B-VKQ, prepared by coupling Vitamin K3, also known as menadione (a quinone redox center), to a boron-dipyrromethene (BODIPY) fluorophore (a lipophilic reporter segment). Oxidation-reduction reactions, spectroelectrochemical studies, and enzymatic assays conducted in the presence of DT-diaphorase illustrate that the new probe shows reversible redox behavior on par with that of Vitamin K, provides a high-sensitivity fluorescence signal, and is compatible with biological conditions, opening the door to monitor remotely (i.e., via imaging) redox processes in real time. In its oxidized form, B-VKQ is non-emissive, while upon reduction to the hydroquinone form, B-VKQH2, BODIPY fluorescence is restored, with emission quantum yield values of ca. 0.54 in toluene. Density functional theory studies validate a photoinduced electron transfer intramolecular switching mechanism, active in the non-emissive quinone form and deactivated upon reduction to the emissive dihydroquinone form. Our results highlight the potential of B-VKQ as a fluorogenic probe to study electron transfer and transport in model systems and biological structures with optimal sensitivity and desirable chemical specificity. Use of such a probe may enable a better understanding of the role that Vitamin K plays in biological redox reactions ubiquitous in key cellular processes, and help elucidate the mechanism and pathological significance of these reactions in biological systems.
publishDate 2016
dc.date.none.fl_str_mv 2016-12
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/11336/60942
Belzile, Mei-Ni; Godin, Robert; Durantini, Andres Matías; Cosa, Gonzalo; Monitoring chemical and biological electron transfer reactions with a fluorogenic vitamin K analogue probe; American Chemical Society; Journal of the American Chemical Society; 138; 50; 12-2016; 16388-16397
0002-7863
1520-5126
CONICET Digital
CONICET
url http://hdl.handle.net/11336/60942
identifier_str_mv Belzile, Mei-Ni; Godin, Robert; Durantini, Andres Matías; Cosa, Gonzalo; Monitoring chemical and biological electron transfer reactions with a fluorogenic vitamin K analogue probe; American Chemical Society; Journal of the American Chemical Society; 138; 50; 12-2016; 16388-16397
0002-7863
1520-5126
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/jacs.6b09735
info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jacs.6b09735
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
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
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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score 13.070432

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