Oxygen-Insensitive Aggregates of Pt(II) Complexes as Phosphorescent Labels of Proteins with Luminescence Lifetime-Based Readouts

Autores
Delcanale, Pietro; Galstyan, Anzhela; Daniliuc, Constantin G.; Grecco, Hernan Edgardo; Abbruzzetti, Stefania; Faust, Andreas; Viappiani, Cristiano; Strassert, Cristian A.
Año de publicación
2018
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The synthesis and photophysical properties of a tailored Pt(II) complex are presented. The phosphorescence of its monomeric species in homogeneous solutions is quenched by interaction with the solvent and therefore absent even upon deoxygenation. However, aggregation-induced shielding from the environment and suppression of rotovibrational degrees of freedom trigger a phosphorescence turn-on that is not suppressed by molecular oxygen, despite possessing an excited-state lifetime ranging in the microsecond scale. Thus, the photoinduced production of reactive oxygen species is avoided by the suppression of diffusion-controlled Dexter-type energy transfer to triplet molecular oxygen. These aggregates emit with the characteristic green luminescence profile of monomeric complexes, indicating that Pt-Pt or excimeric interactions are negligible. Herein, we show that these aggregates can be used to label a model biomolecule (bovine serum albumin) with a microsecond-range luminescence. The protein stabilizes the aggregates, acting as a carrier in aqueous environments. Despite spectral overlaps, the green phosphorescence can be separated by time-gated detection from the dominant autofluorescence of the protein arising from a covalently bound green fluorophore that emits in the nanosecond range. Interestingly, the aggregates also acted as energy donors able to sensitize the emission of a fraction of the fluorophores bound to the protein. This resulted in a microsecond-range luminescence of the fluorescent acceptors and a shortening of the excited-state lifetime of the phosphorescent aggregates. The process that can be traced by a 1000-fold increase in the acceptor's lifetime mirrors the donor's triplet character. The implications for phosphorescence lifetime imaging are discussed.
Fil: Delcanale, Pietro. Università di Parma; Italia
Fil: Galstyan, Anzhela. Westfalische Wilhelms Universitat; Alemania
Fil: Daniliuc, Constantin G.. Westfalische Wilhelms Universitat; Alemania
Fil: Grecco, Hernan Edgardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Física de Buenos Aires. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Física de Buenos Aires; Argentina
Fil: Abbruzzetti, Stefania. Università di Parma; Italia
Fil: Faust, Andreas. Westfalische Wilhelms Universitat; Alemania
Fil: Viappiani, Cristiano. Università di Parma; Italia
Fil: Strassert, Cristian A.. Westfalische Wilhelms Universitat; Alemania
Materia
DONOR-ACCEPTOR
ENERGY TRANSFER
LABELING
PHOTOPHYSICS
PLIM
PT(II) COMPLEX
SPECTROSCOPY
TIME-GATED SPECTROSCOPY
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:11336/96757
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/96757
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Oxygen-Insensitive Aggregates of Pt(II) Complexes as Phosphorescent Labels of Proteins with Luminescence Lifetime-Based ReadoutsDelcanale, PietroGalstyan, AnzhelaDaniliuc, Constantin G.Grecco, Hernan EdgardoAbbruzzetti, StefaniaFaust, AndreasViappiani, CristianoStrassert, Cristian A.DONOR-ACCEPTORENERGY TRANSFERLABELINGPHOTOPHYSICSPLIMPT(II) COMPLEXSPECTROSCOPYTIME-GATED SPECTROSCOPYhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The synthesis and photophysical properties of a tailored Pt(II) complex are presented. The phosphorescence of its monomeric species in homogeneous solutions is quenched by interaction with the solvent and therefore absent even upon deoxygenation. However, aggregation-induced shielding from the environment and suppression of rotovibrational degrees of freedom trigger a phosphorescence turn-on that is not suppressed by molecular oxygen, despite possessing an excited-state lifetime ranging in the microsecond scale. Thus, the photoinduced production of reactive oxygen species is avoided by the suppression of diffusion-controlled Dexter-type energy transfer to triplet molecular oxygen. These aggregates emit with the characteristic green luminescence profile of monomeric complexes, indicating that Pt-Pt or excimeric interactions are negligible. Herein, we show that these aggregates can be used to label a model biomolecule (bovine serum albumin) with a microsecond-range luminescence. The protein stabilizes the aggregates, acting as a carrier in aqueous environments. Despite spectral overlaps, the green phosphorescence can be separated by time-gated detection from the dominant autofluorescence of the protein arising from a covalently bound green fluorophore that emits in the nanosecond range. Interestingly, the aggregates also acted as energy donors able to sensitize the emission of a fraction of the fluorophores bound to the protein. This resulted in a microsecond-range luminescence of the fluorescent acceptors and a shortening of the excited-state lifetime of the phosphorescent aggregates. The process that can be traced by a 1000-fold increase in the acceptor's lifetime mirrors the donor's triplet character. The implications for phosphorescence lifetime imaging are discussed.Fil: Delcanale, Pietro. Università di Parma; ItaliaFil: Galstyan, Anzhela. Westfalische Wilhelms Universitat; AlemaniaFil: Daniliuc, Constantin G.. Westfalische Wilhelms Universitat; AlemaniaFil: Grecco, Hernan Edgardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Física de Buenos Aires. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Física de Buenos Aires; ArgentinaFil: Abbruzzetti, Stefania. Università di Parma; ItaliaFil: Faust, Andreas. Westfalische Wilhelms Universitat; AlemaniaFil: Viappiani, Cristiano. Università di Parma; ItaliaFil: Strassert, Cristian A.. Westfalische Wilhelms Universitat; AlemaniaAmerican Chemical Society2018-07info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/96757Delcanale, Pietro; Galstyan, Anzhela; Daniliuc, Constantin G.; Grecco, Hernan Edgardo; Abbruzzetti, Stefania; et al.; Oxygen-Insensitive Aggregates of Pt(II) Complexes as Phosphorescent Labels of Proteins with Luminescence Lifetime-Based Readouts; American Chemical Society; ACS Applied Materials & Interfaces; 10; 29; 7-2018; 24361-243691944-8244CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/acsami.8b02709info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acsami.8b02709info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:14:11Zoai:ri.conicet.gov.ar:11336/96757instacron: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 10:14:11.741CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Oxygen-Insensitive Aggregates of Pt(II) Complexes as Phosphorescent Labels of Proteins with Luminescence Lifetime-Based Readouts
title Oxygen-Insensitive Aggregates of Pt(II) Complexes as Phosphorescent Labels of Proteins with Luminescence Lifetime-Based Readouts
spellingShingle Oxygen-Insensitive Aggregates of Pt(II) Complexes as Phosphorescent Labels of Proteins with Luminescence Lifetime-Based Readouts
Delcanale, Pietro
DONOR-ACCEPTOR
ENERGY TRANSFER
LABELING
PHOTOPHYSICS
PLIM
PT(II) COMPLEX
SPECTROSCOPY
TIME-GATED SPECTROSCOPY
title_short Oxygen-Insensitive Aggregates of Pt(II) Complexes as Phosphorescent Labels of Proteins with Luminescence Lifetime-Based Readouts
title_full Oxygen-Insensitive Aggregates of Pt(II) Complexes as Phosphorescent Labels of Proteins with Luminescence Lifetime-Based Readouts
title_fullStr Oxygen-Insensitive Aggregates of Pt(II) Complexes as Phosphorescent Labels of Proteins with Luminescence Lifetime-Based Readouts
title_full_unstemmed Oxygen-Insensitive Aggregates of Pt(II) Complexes as Phosphorescent Labels of Proteins with Luminescence Lifetime-Based Readouts
title_sort Oxygen-Insensitive Aggregates of Pt(II) Complexes as Phosphorescent Labels of Proteins with Luminescence Lifetime-Based Readouts
dc.creator.none.fl_str_mv Delcanale, Pietro
Galstyan, Anzhela
Daniliuc, Constantin G.
Grecco, Hernan Edgardo
Abbruzzetti, Stefania
Faust, Andreas
Viappiani, Cristiano
Strassert, Cristian A.
author Delcanale, Pietro
author_facet Delcanale, Pietro
Galstyan, Anzhela
Daniliuc, Constantin G.
Grecco, Hernan Edgardo
Abbruzzetti, Stefania
Faust, Andreas
Viappiani, Cristiano
Strassert, Cristian A.
author_role author
author2 Galstyan, Anzhela
Daniliuc, Constantin G.
Grecco, Hernan Edgardo
Abbruzzetti, Stefania
Faust, Andreas
Viappiani, Cristiano
Strassert, Cristian A.
author2_role author
author
author
author
author
author
author
dc.subject.none.fl_str_mv DONOR-ACCEPTOR
ENERGY TRANSFER
LABELING
PHOTOPHYSICS
PLIM
PT(II) COMPLEX
SPECTROSCOPY
TIME-GATED SPECTROSCOPY
topic DONOR-ACCEPTOR
ENERGY TRANSFER
LABELING
PHOTOPHYSICS
PLIM
PT(II) COMPLEX
SPECTROSCOPY
TIME-GATED SPECTROSCOPY
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 synthesis and photophysical properties of a tailored Pt(II) complex are presented. The phosphorescence of its monomeric species in homogeneous solutions is quenched by interaction with the solvent and therefore absent even upon deoxygenation. However, aggregation-induced shielding from the environment and suppression of rotovibrational degrees of freedom trigger a phosphorescence turn-on that is not suppressed by molecular oxygen, despite possessing an excited-state lifetime ranging in the microsecond scale. Thus, the photoinduced production of reactive oxygen species is avoided by the suppression of diffusion-controlled Dexter-type energy transfer to triplet molecular oxygen. These aggregates emit with the characteristic green luminescence profile of monomeric complexes, indicating that Pt-Pt or excimeric interactions are negligible. Herein, we show that these aggregates can be used to label a model biomolecule (bovine serum albumin) with a microsecond-range luminescence. The protein stabilizes the aggregates, acting as a carrier in aqueous environments. Despite spectral overlaps, the green phosphorescence can be separated by time-gated detection from the dominant autofluorescence of the protein arising from a covalently bound green fluorophore that emits in the nanosecond range. Interestingly, the aggregates also acted as energy donors able to sensitize the emission of a fraction of the fluorophores bound to the protein. This resulted in a microsecond-range luminescence of the fluorescent acceptors and a shortening of the excited-state lifetime of the phosphorescent aggregates. The process that can be traced by a 1000-fold increase in the acceptor's lifetime mirrors the donor's triplet character. The implications for phosphorescence lifetime imaging are discussed.
Fil: Delcanale, Pietro. Università di Parma; Italia
Fil: Galstyan, Anzhela. Westfalische Wilhelms Universitat; Alemania
Fil: Daniliuc, Constantin G.. Westfalische Wilhelms Universitat; Alemania
Fil: Grecco, Hernan Edgardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Física de Buenos Aires. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Física de Buenos Aires; Argentina
Fil: Abbruzzetti, Stefania. Università di Parma; Italia
Fil: Faust, Andreas. Westfalische Wilhelms Universitat; Alemania
Fil: Viappiani, Cristiano. Università di Parma; Italia
Fil: Strassert, Cristian A.. Westfalische Wilhelms Universitat; Alemania
description The synthesis and photophysical properties of a tailored Pt(II) complex are presented. The phosphorescence of its monomeric species in homogeneous solutions is quenched by interaction with the solvent and therefore absent even upon deoxygenation. However, aggregation-induced shielding from the environment and suppression of rotovibrational degrees of freedom trigger a phosphorescence turn-on that is not suppressed by molecular oxygen, despite possessing an excited-state lifetime ranging in the microsecond scale. Thus, the photoinduced production of reactive oxygen species is avoided by the suppression of diffusion-controlled Dexter-type energy transfer to triplet molecular oxygen. These aggregates emit with the characteristic green luminescence profile of monomeric complexes, indicating that Pt-Pt or excimeric interactions are negligible. Herein, we show that these aggregates can be used to label a model biomolecule (bovine serum albumin) with a microsecond-range luminescence. The protein stabilizes the aggregates, acting as a carrier in aqueous environments. Despite spectral overlaps, the green phosphorescence can be separated by time-gated detection from the dominant autofluorescence of the protein arising from a covalently bound green fluorophore that emits in the nanosecond range. Interestingly, the aggregates also acted as energy donors able to sensitize the emission of a fraction of the fluorophores bound to the protein. This resulted in a microsecond-range luminescence of the fluorescent acceptors and a shortening of the excited-state lifetime of the phosphorescent aggregates. The process that can be traced by a 1000-fold increase in the acceptor's lifetime mirrors the donor's triplet character. The implications for phosphorescence lifetime imaging are discussed.
publishDate 2018
dc.date.none.fl_str_mv 2018-07
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/11336/96757
Delcanale, Pietro; Galstyan, Anzhela; Daniliuc, Constantin G.; Grecco, Hernan Edgardo; Abbruzzetti, Stefania; et al.; Oxygen-Insensitive Aggregates of Pt(II) Complexes as Phosphorescent Labels of Proteins with Luminescence Lifetime-Based Readouts; American Chemical Society; ACS Applied Materials & Interfaces; 10; 29; 7-2018; 24361-24369
1944-8244
CONICET Digital
CONICET
url http://hdl.handle.net/11336/96757
identifier_str_mv Delcanale, Pietro; Galstyan, Anzhela; Daniliuc, Constantin G.; Grecco, Hernan Edgardo; Abbruzzetti, Stefania; et al.; Oxygen-Insensitive Aggregates of Pt(II) Complexes as Phosphorescent Labels of Proteins with Luminescence Lifetime-Based Readouts; American Chemical Society; ACS Applied Materials & Interfaces; 10; 29; 7-2018; 24361-24369
1944-8244
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/acsami.8b02709
info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acsami.8b02709
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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