Amplified singlet oxygen generation in metallated-porphyrin doped conjugated polymer nanoparticles
- Autores
- Spada, Ramiro Martín; Macor, Lorena Paola; Hernández, Laura; Ponzio, Rodrigo Andrés; Ibarra, Luis Exequiel; Lorente, Carolina; Chesta, Carlos Alberto; Palacios, Rodrigo Emiliano
- Año de publicación
- 2018
- Idioma
- inglés
- Tipo de recurso
- artículo
- Estado
- versión publicada
- Descripción
- We report on the mechanism and efficiencies of singlet oxygen O2(1Δg) generation of nanoparticles (NP) of the conjugated polymer (CP) poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT) doped with platinum octaethylporphyrin (PtOEP) suspended in water. A detailed study of the photophysics of these NP, using stationary and time-resolved absorption and emission techniques, indicates that O2(1Δg) is generated by the triplet excited state of F8BT and not by that of PtOEP, as previously observed for other porphyrin doped CP NP. O2(1Δg) quantum yields (ΦΔ) were measured by quantifying the characteristic phosphorescence of O2(1Δg) in the NIR region (∼1268 nm). It was found that incorporation of relatively small amounts of PtOEP to F8BT NP results in a significant increase of ΦΔ. NP containing 10% PtOEP (w/w) show a ΦΔ ∼ 0.24, which is 3 times larger than that observed for undoped F8BT NP, and larger than the reported for most water-soluble porphyrins. ΦΔ were also calculated from the oxidation rates (v0) of 3-[10-(2-carboxyethyl)anthracen-9-yl]propanoic acid (ADPA), a well-known chemical O2(1Δg) trap. Unexpectedly, this method was found to significantly overestimate the ΦΔ values due to the adsorption of ADPA on the surface of NP. The ADPA/NP adsorption process was characterized using a simple adsorption model yielding an (average) equilibrium constant of ∼8 × 103 M−1 and an (average) number of NP-binding sites of ∼14000. These results necessarily caution about the use of ADPA as a probe to evaluate ΦΔ in these NP systems. In addition, the interaction of F8BT NP with other anionic, cationic and zwitterionic dyes (dissolved in water) was studied. It was found that even at nano-molar concentrations all the dyes efficiently adsorb on the NP surface. This general and simple self-assembly strategy can be used to prepare superficially-dye-doped CP NP with potentially interesting technological applications.
Fil: Spada, Ramiro Martín. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina
Fil: Macor, Lorena Paola. 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: Hernández, Laura. 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: Ponzio, Rodrigo Andrés. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina
Fil: Ibarra, Luis Exequiel. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Biología Molecular; Argentina
Fil: Lorente, Carolina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Chesta, Carlos Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina
Fil: Palacios, Rodrigo Emiliano. 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
-
CONJUGATED POLYMER NANOPARTICLES
DYE ADSORPTION
METALLATED PORPHYRIN
PHOTOSENSITIZATION
SINGLET OXYGEN QUANTUM YIELD - Nivel de accesibilidad
- acceso abierto
- Condiciones de uso
- https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
- Repositorio
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/100483
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oai:ri.conicet.gov.ar:11336/100483 |
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Amplified singlet oxygen generation in metallated-porphyrin doped conjugated polymer nanoparticlesSpada, Ramiro MartínMacor, Lorena PaolaHernández, LauraPonzio, Rodrigo AndrésIbarra, Luis ExequielLorente, CarolinaChesta, Carlos AlbertoPalacios, Rodrigo EmilianoCONJUGATED POLYMER NANOPARTICLESDYE ADSORPTIONMETALLATED PORPHYRINPHOTOSENSITIZATIONSINGLET OXYGEN QUANTUM YIELDhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1We report on the mechanism and efficiencies of singlet oxygen O2(1Δg) generation of nanoparticles (NP) of the conjugated polymer (CP) poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT) doped with platinum octaethylporphyrin (PtOEP) suspended in water. A detailed study of the photophysics of these NP, using stationary and time-resolved absorption and emission techniques, indicates that O2(1Δg) is generated by the triplet excited state of F8BT and not by that of PtOEP, as previously observed for other porphyrin doped CP NP. O2(1Δg) quantum yields (ΦΔ) were measured by quantifying the characteristic phosphorescence of O2(1Δg) in the NIR region (∼1268 nm). It was found that incorporation of relatively small amounts of PtOEP to F8BT NP results in a significant increase of ΦΔ. NP containing 10% PtOEP (w/w) show a ΦΔ ∼ 0.24, which is 3 times larger than that observed for undoped F8BT NP, and larger than the reported for most water-soluble porphyrins. ΦΔ were also calculated from the oxidation rates (v0) of 3-[10-(2-carboxyethyl)anthracen-9-yl]propanoic acid (ADPA), a well-known chemical O2(1Δg) trap. Unexpectedly, this method was found to significantly overestimate the ΦΔ values due to the adsorption of ADPA on the surface of NP. The ADPA/NP adsorption process was characterized using a simple adsorption model yielding an (average) equilibrium constant of ∼8 × 103 M−1 and an (average) number of NP-binding sites of ∼14000. These results necessarily caution about the use of ADPA as a probe to evaluate ΦΔ in these NP systems. In addition, the interaction of F8BT NP with other anionic, cationic and zwitterionic dyes (dissolved in water) was studied. It was found that even at nano-molar concentrations all the dyes efficiently adsorb on the NP surface. This general and simple self-assembly strategy can be used to prepare superficially-dye-doped CP NP with potentially interesting technological applications.Fil: Spada, Ramiro Martín. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; ArgentinaFil: Macor, Lorena Paola. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Hernández, Laura. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Ponzio, Rodrigo Andrés. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; ArgentinaFil: Ibarra, Luis Exequiel. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Biología Molecular; ArgentinaFil: Lorente, Carolina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Chesta, Carlos Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; ArgentinaFil: Palacios, Rodrigo Emiliano. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaElsevier2018-02info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/100483Spada, Ramiro Martín; Macor, Lorena Paola; Hernández, Laura; Ponzio, Rodrigo Andrés; Ibarra, Luis Exequiel; et al.; Amplified singlet oxygen generation in metallated-porphyrin doped conjugated polymer nanoparticles; Elsevier; Dyes and Pigments; 149; 2-2018; 212-2230143-7208CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://linkinghub.elsevier.com/retrieve/pii/S0143720817316686info:eu-repo/semantics/altIdentifier/doi/10.1016/j.dyepig.2017.09.044info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-nd/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:34:45Zoai:ri.conicet.gov.ar:11336/100483instacron: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 09:34:46.063CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse |
dc.title.none.fl_str_mv |
Amplified singlet oxygen generation in metallated-porphyrin doped conjugated polymer nanoparticles |
title |
Amplified singlet oxygen generation in metallated-porphyrin doped conjugated polymer nanoparticles |
spellingShingle |
Amplified singlet oxygen generation in metallated-porphyrin doped conjugated polymer nanoparticles Spada, Ramiro Martín CONJUGATED POLYMER NANOPARTICLES DYE ADSORPTION METALLATED PORPHYRIN PHOTOSENSITIZATION SINGLET OXYGEN QUANTUM YIELD |
title_short |
Amplified singlet oxygen generation in metallated-porphyrin doped conjugated polymer nanoparticles |
title_full |
Amplified singlet oxygen generation in metallated-porphyrin doped conjugated polymer nanoparticles |
title_fullStr |
Amplified singlet oxygen generation in metallated-porphyrin doped conjugated polymer nanoparticles |
title_full_unstemmed |
Amplified singlet oxygen generation in metallated-porphyrin doped conjugated polymer nanoparticles |
title_sort |
Amplified singlet oxygen generation in metallated-porphyrin doped conjugated polymer nanoparticles |
dc.creator.none.fl_str_mv |
Spada, Ramiro Martín Macor, Lorena Paola Hernández, Laura Ponzio, Rodrigo Andrés Ibarra, Luis Exequiel Lorente, Carolina Chesta, Carlos Alberto Palacios, Rodrigo Emiliano |
author |
Spada, Ramiro Martín |
author_facet |
Spada, Ramiro Martín Macor, Lorena Paola Hernández, Laura Ponzio, Rodrigo Andrés Ibarra, Luis Exequiel Lorente, Carolina Chesta, Carlos Alberto Palacios, Rodrigo Emiliano |
author_role |
author |
author2 |
Macor, Lorena Paola Hernández, Laura Ponzio, Rodrigo Andrés Ibarra, Luis Exequiel Lorente, Carolina Chesta, Carlos Alberto Palacios, Rodrigo Emiliano |
author2_role |
author author author author author author author |
dc.subject.none.fl_str_mv |
CONJUGATED POLYMER NANOPARTICLES DYE ADSORPTION METALLATED PORPHYRIN PHOTOSENSITIZATION SINGLET OXYGEN QUANTUM YIELD |
topic |
CONJUGATED POLYMER NANOPARTICLES DYE ADSORPTION METALLATED PORPHYRIN PHOTOSENSITIZATION SINGLET OXYGEN QUANTUM YIELD |
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 on the mechanism and efficiencies of singlet oxygen O2(1Δg) generation of nanoparticles (NP) of the conjugated polymer (CP) poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT) doped with platinum octaethylporphyrin (PtOEP) suspended in water. A detailed study of the photophysics of these NP, using stationary and time-resolved absorption and emission techniques, indicates that O2(1Δg) is generated by the triplet excited state of F8BT and not by that of PtOEP, as previously observed for other porphyrin doped CP NP. O2(1Δg) quantum yields (ΦΔ) were measured by quantifying the characteristic phosphorescence of O2(1Δg) in the NIR region (∼1268 nm). It was found that incorporation of relatively small amounts of PtOEP to F8BT NP results in a significant increase of ΦΔ. NP containing 10% PtOEP (w/w) show a ΦΔ ∼ 0.24, which is 3 times larger than that observed for undoped F8BT NP, and larger than the reported for most water-soluble porphyrins. ΦΔ were also calculated from the oxidation rates (v0) of 3-[10-(2-carboxyethyl)anthracen-9-yl]propanoic acid (ADPA), a well-known chemical O2(1Δg) trap. Unexpectedly, this method was found to significantly overestimate the ΦΔ values due to the adsorption of ADPA on the surface of NP. The ADPA/NP adsorption process was characterized using a simple adsorption model yielding an (average) equilibrium constant of ∼8 × 103 M−1 and an (average) number of NP-binding sites of ∼14000. These results necessarily caution about the use of ADPA as a probe to evaluate ΦΔ in these NP systems. In addition, the interaction of F8BT NP with other anionic, cationic and zwitterionic dyes (dissolved in water) was studied. It was found that even at nano-molar concentrations all the dyes efficiently adsorb on the NP surface. This general and simple self-assembly strategy can be used to prepare superficially-dye-doped CP NP with potentially interesting technological applications. Fil: Spada, Ramiro Martín. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina Fil: Macor, Lorena Paola. 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: Hernández, Laura. 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: Ponzio, Rodrigo Andrés. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina Fil: Ibarra, Luis Exequiel. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Biología Molecular; Argentina Fil: Lorente, Carolina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina Fil: Chesta, Carlos Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina Fil: Palacios, Rodrigo Emiliano. 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 |
We report on the mechanism and efficiencies of singlet oxygen O2(1Δg) generation of nanoparticles (NP) of the conjugated polymer (CP) poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT) doped with platinum octaethylporphyrin (PtOEP) suspended in water. A detailed study of the photophysics of these NP, using stationary and time-resolved absorption and emission techniques, indicates that O2(1Δg) is generated by the triplet excited state of F8BT and not by that of PtOEP, as previously observed for other porphyrin doped CP NP. O2(1Δg) quantum yields (ΦΔ) were measured by quantifying the characteristic phosphorescence of O2(1Δg) in the NIR region (∼1268 nm). It was found that incorporation of relatively small amounts of PtOEP to F8BT NP results in a significant increase of ΦΔ. NP containing 10% PtOEP (w/w) show a ΦΔ ∼ 0.24, which is 3 times larger than that observed for undoped F8BT NP, and larger than the reported for most water-soluble porphyrins. ΦΔ were also calculated from the oxidation rates (v0) of 3-[10-(2-carboxyethyl)anthracen-9-yl]propanoic acid (ADPA), a well-known chemical O2(1Δg) trap. Unexpectedly, this method was found to significantly overestimate the ΦΔ values due to the adsorption of ADPA on the surface of NP. The ADPA/NP adsorption process was characterized using a simple adsorption model yielding an (average) equilibrium constant of ∼8 × 103 M−1 and an (average) number of NP-binding sites of ∼14000. These results necessarily caution about the use of ADPA as a probe to evaluate ΦΔ in these NP systems. In addition, the interaction of F8BT NP with other anionic, cationic and zwitterionic dyes (dissolved in water) was studied. It was found that even at nano-molar concentrations all the dyes efficiently adsorb on the NP surface. This general and simple self-assembly strategy can be used to prepare superficially-dye-doped CP NP with potentially interesting technological applications. |
publishDate |
2018 |
dc.date.none.fl_str_mv |
2018-02 |
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/11336/100483 Spada, Ramiro Martín; Macor, Lorena Paola; Hernández, Laura; Ponzio, Rodrigo Andrés; Ibarra, Luis Exequiel; et al.; Amplified singlet oxygen generation in metallated-porphyrin doped conjugated polymer nanoparticles; Elsevier; Dyes and Pigments; 149; 2-2018; 212-223 0143-7208 CONICET Digital CONICET |
url |
http://hdl.handle.net/11336/100483 |
identifier_str_mv |
Spada, Ramiro Martín; Macor, Lorena Paola; Hernández, Laura; Ponzio, Rodrigo Andrés; Ibarra, Luis Exequiel; et al.; Amplified singlet oxygen generation in metallated-porphyrin doped conjugated polymer nanoparticles; Elsevier; Dyes and Pigments; 149; 2-2018; 212-223 0143-7208 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://linkinghub.elsevier.com/retrieve/pii/S0143720817316686 info:eu-repo/semantics/altIdentifier/doi/10.1016/j.dyepig.2017.09.044 |
dc.rights.none.fl_str_mv |
info:eu-repo/semantics/openAccess https://creativecommons.org/licenses/by-nc-nd/2.5/ar/ |
eu_rights_str_mv |
openAccess |
rights_invalid_str_mv |
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/ |
dc.format.none.fl_str_mv |
application/pdf application/pdf application/pdf application/pdf application/pdf application/pdf application/pdf |
dc.publisher.none.fl_str_mv |
Elsevier |
publisher.none.fl_str_mv |
Elsevier |
dc.source.none.fl_str_mv |
reponame:CONICET Digital (CONICET) instname:Consejo Nacional de Investigaciones Científicas y Técnicas |
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CONICET Digital (CONICET) |
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CONICET Digital (CONICET) |
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Consejo Nacional de Investigaciones Científicas y Técnicas |
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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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13.070432 |