Reactive Oxygen Species Mediated Activation of a Dormant Singlet Oxygen Photosensitizer: From Autocatalytic Singlet Oxygen Amplification to Chemicontrolled Photodynamic Therapy

Autores
Durantini, Andres Matías; Greene, Lana E.; Lincoln, Richard; Martínez, Sol R.; Cosa, Gonzalo
Año de publicación
2016
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Here we show the design, preparation, and characterization of a dormant singlet oxygen (1O2) photosensitizer that is activated upon its reaction with reactive oxygen species (ROS), including 1O2 itself, in what constitutes an autocatalytic process. The compound is based on a two segment photosensitizer–trap molecule where the photosensitizer segment consists of a Br-substituted boron-dipyrromethene (BODIPY) dye. The trap segment consists of the chromanol ring of α-tocopherol, the most potent naturally occurring lipid soluble antioxidant. Time-resolved absorption, fluorescence, and 1O2 phosphorescence studies together with fluorescence and 1O2 phosphorescence emission quantum yields collected on Br2B–PMHC and related bromo and iodo-substituted BODIPY dyes show that the trap segment provides a total of three layers of intramolecular suppression of 1O2 production. Oxidation of the trap segment with ROS restores the sensitizing properties of the photosensitizer segment resulting in ∼40-fold enhancement in 1O2 production. The juxtaposed antioxidant (chromanol) and prooxidant (Br-BODIPY) antagonistic chemical activities of the two-segment compound enable the autocatalytic, and in general ROS-mediated, activation of 1O2 sensitization providing a chemical cue for the spatiotemporal control of 1O2.The usefulness of this approach to selectively photoactivate the production of singlet oxygen in ROS stressed vs regular cells was successfully tested via the photodynamic inactivation of a ROS stressed Gram negative Escherichia coli strain.
Fil: Durantini, Andres Matías. McGill University; Canadá. Unversidad Nacional de Río Cuarto. Facultad de Ciencias Exactas, Fisicoquímicas y Naturales. Departamento de Química; Argentina
Fil: Greene, Lana E.. McGill University; Canadá
Fil: Lincoln, Richard. McGill University; Canadá
Fil: Martínez, Sol R.. McGill University; Canadá. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto Multidisciplinario de Biología Vegetal. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas Físicas y Naturales. Instituto Multidisciplinario de Biología Vegetal; Argentina
Fil: Cosa, Gonzalo. McGill University; Canadá
Materia
Photodynamic Therapy
Autocalysis
Reactive Oxygen Species
Singlet Oxygen
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:11336/23128
Acceder
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repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Reactive Oxygen Species Mediated Activation of a Dormant Singlet Oxygen Photosensitizer: From Autocatalytic Singlet Oxygen Amplification to Chemicontrolled Photodynamic TherapyDurantini, Andres MatíasGreene, Lana E.Lincoln, RichardMartínez, Sol R.Cosa, GonzaloPhotodynamic TherapyAutocalysisReactive Oxygen SpeciesSinglet Oxygenhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Here we show the design, preparation, and characterization of a dormant singlet oxygen (1O2) photosensitizer that is activated upon its reaction with reactive oxygen species (ROS), including 1O2 itself, in what constitutes an autocatalytic process. The compound is based on a two segment photosensitizer–trap molecule where the photosensitizer segment consists of a Br-substituted boron-dipyrromethene (BODIPY) dye. The trap segment consists of the chromanol ring of α-tocopherol, the most potent naturally occurring lipid soluble antioxidant. Time-resolved absorption, fluorescence, and 1O2 phosphorescence studies together with fluorescence and 1O2 phosphorescence emission quantum yields collected on Br2B–PMHC and related bromo and iodo-substituted BODIPY dyes show that the trap segment provides a total of three layers of intramolecular suppression of 1O2 production. Oxidation of the trap segment with ROS restores the sensitizing properties of the photosensitizer segment resulting in ∼40-fold enhancement in 1O2 production. The juxtaposed antioxidant (chromanol) and prooxidant (Br-BODIPY) antagonistic chemical activities of the two-segment compound enable the autocatalytic, and in general ROS-mediated, activation of 1O2 sensitization providing a chemical cue for the spatiotemporal control of 1O2.The usefulness of this approach to selectively photoactivate the production of singlet oxygen in ROS stressed vs regular cells was successfully tested via the photodynamic inactivation of a ROS stressed Gram negative Escherichia coli strain.Fil: Durantini, Andres Matías. McGill University; Canadá. Unversidad Nacional de Río Cuarto. Facultad de Ciencias Exactas, Fisicoquímicas y Naturales. Departamento de Química; ArgentinaFil: Greene, Lana E.. McGill University; CanadáFil: Lincoln, Richard. McGill University; CanadáFil: Martínez, Sol R.. McGill University; Canadá. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto Multidisciplinario de Biología Vegetal. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas Físicas y Naturales. Instituto Multidisciplinario de Biología Vegetal; ArgentinaFil: Cosa, Gonzalo. McGill University; CanadáAmerican Chemical Society2016-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/23128Durantini, Andres Matías; Greene, Lana E.; Lincoln, Richard; Martínez, Sol R.; Cosa, Gonzalo; Reactive Oxygen Species Mediated Activation of a Dormant Singlet Oxygen Photosensitizer: From Autocatalytic Singlet Oxygen Amplification to Chemicontrolled Photodynamic Therapy; American Chemical Society; Journal of the American Chemical Society; 138; 4; 1-2016; 1215-12250002-78631520-5126CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jacs.5b10288info:eu-repo/semantics/altIdentifier/doi/10.1021/jacs.5b10288info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T09:45:42Zoai:ri.conicet.gov.ar:11336/23128instacron: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:34982025-09-03 09:45:42.695CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Reactive Oxygen Species Mediated Activation of a Dormant Singlet Oxygen Photosensitizer: From Autocatalytic Singlet Oxygen Amplification to Chemicontrolled Photodynamic Therapy
title Reactive Oxygen Species Mediated Activation of a Dormant Singlet Oxygen Photosensitizer: From Autocatalytic Singlet Oxygen Amplification to Chemicontrolled Photodynamic Therapy
spellingShingle Reactive Oxygen Species Mediated Activation of a Dormant Singlet Oxygen Photosensitizer: From Autocatalytic Singlet Oxygen Amplification to Chemicontrolled Photodynamic Therapy
Durantini, Andres Matías
Photodynamic Therapy
Autocalysis
Reactive Oxygen Species
Singlet Oxygen
title_short Reactive Oxygen Species Mediated Activation of a Dormant Singlet Oxygen Photosensitizer: From Autocatalytic Singlet Oxygen Amplification to Chemicontrolled Photodynamic Therapy
title_full Reactive Oxygen Species Mediated Activation of a Dormant Singlet Oxygen Photosensitizer: From Autocatalytic Singlet Oxygen Amplification to Chemicontrolled Photodynamic Therapy
title_fullStr Reactive Oxygen Species Mediated Activation of a Dormant Singlet Oxygen Photosensitizer: From Autocatalytic Singlet Oxygen Amplification to Chemicontrolled Photodynamic Therapy
title_full_unstemmed Reactive Oxygen Species Mediated Activation of a Dormant Singlet Oxygen Photosensitizer: From Autocatalytic Singlet Oxygen Amplification to Chemicontrolled Photodynamic Therapy
title_sort Reactive Oxygen Species Mediated Activation of a Dormant Singlet Oxygen Photosensitizer: From Autocatalytic Singlet Oxygen Amplification to Chemicontrolled Photodynamic Therapy
dc.creator.none.fl_str_mv Durantini, Andres Matías
Greene, Lana E.
Lincoln, Richard
Martínez, Sol R.
Cosa, Gonzalo
author Durantini, Andres Matías
author_facet Durantini, Andres Matías
Greene, Lana E.
Lincoln, Richard
Martínez, Sol R.
Cosa, Gonzalo
author_role author
author2 Greene, Lana E.
Lincoln, Richard
Martínez, Sol R.
Cosa, Gonzalo
author2_role author
author
author
author
dc.subject.none.fl_str_mv Photodynamic Therapy
Autocalysis
Reactive Oxygen Species
Singlet Oxygen
topic Photodynamic Therapy
Autocalysis
Reactive Oxygen Species
Singlet Oxygen
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Here we show the design, preparation, and characterization of a dormant singlet oxygen (1O2) photosensitizer that is activated upon its reaction with reactive oxygen species (ROS), including 1O2 itself, in what constitutes an autocatalytic process. The compound is based on a two segment photosensitizer–trap molecule where the photosensitizer segment consists of a Br-substituted boron-dipyrromethene (BODIPY) dye. The trap segment consists of the chromanol ring of α-tocopherol, the most potent naturally occurring lipid soluble antioxidant. Time-resolved absorption, fluorescence, and 1O2 phosphorescence studies together with fluorescence and 1O2 phosphorescence emission quantum yields collected on Br2B–PMHC and related bromo and iodo-substituted BODIPY dyes show that the trap segment provides a total of three layers of intramolecular suppression of 1O2 production. Oxidation of the trap segment with ROS restores the sensitizing properties of the photosensitizer segment resulting in ∼40-fold enhancement in 1O2 production. The juxtaposed antioxidant (chromanol) and prooxidant (Br-BODIPY) antagonistic chemical activities of the two-segment compound enable the autocatalytic, and in general ROS-mediated, activation of 1O2 sensitization providing a chemical cue for the spatiotemporal control of 1O2.The usefulness of this approach to selectively photoactivate the production of singlet oxygen in ROS stressed vs regular cells was successfully tested via the photodynamic inactivation of a ROS stressed Gram negative Escherichia coli strain.
Fil: Durantini, Andres Matías. McGill University; Canadá. Unversidad Nacional de Río Cuarto. Facultad de Ciencias Exactas, Fisicoquímicas y Naturales. Departamento de Química; Argentina
Fil: Greene, Lana E.. McGill University; Canadá
Fil: Lincoln, Richard. McGill University; Canadá
Fil: Martínez, Sol R.. McGill University; Canadá. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto Multidisciplinario de Biología Vegetal. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas Físicas y Naturales. Instituto Multidisciplinario de Biología Vegetal; Argentina
Fil: Cosa, Gonzalo. McGill University; Canadá
description Here we show the design, preparation, and characterization of a dormant singlet oxygen (1O2) photosensitizer that is activated upon its reaction with reactive oxygen species (ROS), including 1O2 itself, in what constitutes an autocatalytic process. The compound is based on a two segment photosensitizer–trap molecule where the photosensitizer segment consists of a Br-substituted boron-dipyrromethene (BODIPY) dye. The trap segment consists of the chromanol ring of α-tocopherol, the most potent naturally occurring lipid soluble antioxidant. Time-resolved absorption, fluorescence, and 1O2 phosphorescence studies together with fluorescence and 1O2 phosphorescence emission quantum yields collected on Br2B–PMHC and related bromo and iodo-substituted BODIPY dyes show that the trap segment provides a total of three layers of intramolecular suppression of 1O2 production. Oxidation of the trap segment with ROS restores the sensitizing properties of the photosensitizer segment resulting in ∼40-fold enhancement in 1O2 production. The juxtaposed antioxidant (chromanol) and prooxidant (Br-BODIPY) antagonistic chemical activities of the two-segment compound enable the autocatalytic, and in general ROS-mediated, activation of 1O2 sensitization providing a chemical cue for the spatiotemporal control of 1O2.The usefulness of this approach to selectively photoactivate the production of singlet oxygen in ROS stressed vs regular cells was successfully tested via the photodynamic inactivation of a ROS stressed Gram negative Escherichia coli strain.
publishDate 2016
dc.date.none.fl_str_mv 2016-01
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/11336/23128
Durantini, Andres Matías; Greene, Lana E.; Lincoln, Richard; Martínez, Sol R.; Cosa, Gonzalo; Reactive Oxygen Species Mediated Activation of a Dormant Singlet Oxygen Photosensitizer: From Autocatalytic Singlet Oxygen Amplification to Chemicontrolled Photodynamic Therapy; American Chemical Society; Journal of the American Chemical Society; 138; 4; 1-2016; 1215-1225
0002-7863
1520-5126
CONICET Digital
CONICET
url http://hdl.handle.net/11336/23128
identifier_str_mv Durantini, Andres Matías; Greene, Lana E.; Lincoln, Richard; Martínez, Sol R.; Cosa, Gonzalo; Reactive Oxygen Species Mediated Activation of a Dormant Singlet Oxygen Photosensitizer: From Autocatalytic Singlet Oxygen Amplification to Chemicontrolled Photodynamic Therapy; American Chemical Society; Journal of the American Chemical Society; 138; 4; 1-2016; 1215-1225
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/url/http://pubs.acs.org/doi/abs/10.1021/jacs.5b10288
info:eu-repo/semantics/altIdentifier/doi/10.1021/jacs.5b10288
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
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 13.13397

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