Amplified singlet oxygen generation in metallated-porphyrin doped conjugated polymer nanoparticles
Abstract We report on the mechanism and efficiencies of singlet oxygen O<sub>2</sub>(<sup>1</sup>Δ<sub>g</sub>) generation of nanoparticles (NP) of the conjugated polymer (CP) poly(9,9-dioctylfluorene- alt -benzothiadiazole) (F8BT) doped with platinum octaethylpor...
| Autores principales: | , , , , , , , |
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| Formato: | Articulo |
| Lenguaje: | Inglés |
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2018
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| Acceso en línea: | http://sedici.unlp.edu.ar/handle/10915/124432 |
| Aporte de: |
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I19-R120-10915-124432 |
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| record_format |
dspace |
| institution |
Universidad Nacional de La Plata |
| institution_str |
I-19 |
| repository_str |
R-120 |
| collection |
SEDICI (UNLP) |
| language |
Inglés |
| topic |
Ciencias Exactas Química Conjugated polymer nanoparticles Metallated porphyrin Photosensitization Singlet oxygen quantum yield Dye adsorption |
| spellingShingle |
Ciencias Exactas Química Conjugated polymer nanoparticles Metallated porphyrin Photosensitization Singlet oxygen quantum yield Dye adsorption Spada, Ramiro Martín Macor, Lorena Paola Hernández, Laura Ponzio, Rodrigo Andrés Ibarra, Luis Lorente, Carolina Chesta, Carlos A. Palacios, Rodrigo Emiliano Amplified singlet oxygen generation in metallated-porphyrin doped conjugated polymer nanoparticles |
| topic_facet |
Ciencias Exactas Química Conjugated polymer nanoparticles Metallated porphyrin Photosensitization Singlet oxygen quantum yield Dye adsorption |
| description |
Abstract We report on the mechanism and efficiencies of singlet oxygen O<sub>2</sub>(<sup>1</sup>Δ<sub>g</sub>) 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 O<sub>2</sub>(<sup>1</sup>Δ<sub>g</sub>) is generated by the triplet excited state of F8BT and not by that of PtOEP, as previously observed for other porphyrin doped CP NP. O<sub>2</sub> (<sup>1</sup>Δ<sub>g</sub>) quantum yields (Φ<sub>Δ</sub>) were measured by quantifying the characteristic phosphorescence of O<sub>2</sub>(<sup>1</sup>Δ<sub>g</sub>) 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 Φ<sub>Δ</sub>. NP containing 10% PtOEP (w/w) show a Φ<sub>Δ</sub> ∼ 0.24, which is 3 times larger than that observed for undoped F8BT NP, and larger than the reported for most water-soluble porphyrins. Φ<sub>Δ</sub> were also calculated from the oxidation rates ( v 0 ) of 3-[10-(2-carboxyethyl)anthracen-9-yl]propanoic acid (ADPA), a well-known chemical O<sub>2</sub>(<sup>1</sup>Δ<sub>g</sub>) trap. Unexpectedly, this method was found to significantly overestimate the Φ<sub>Δ</sub> 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 × 10<sup>3</sup> M<sup>−1</sup> and an (average) number of NP-binding sites of ∼14000. These results necessarily caution about the use of ADPA as a probe to evaluate Φ<sub>Δ</sub> 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. |
| format |
Articulo Articulo |
| author |
Spada, Ramiro Martín Macor, Lorena Paola Hernández, Laura Ponzio, Rodrigo Andrés Ibarra, Luis Lorente, Carolina Chesta, Carlos A. Palacios, Rodrigo Emiliano |
| author_facet |
Spada, Ramiro Martín Macor, Lorena Paola Hernández, Laura Ponzio, Rodrigo Andrés Ibarra, Luis Lorente, Carolina Chesta, Carlos A. Palacios, Rodrigo Emiliano |
| author_sort |
Spada, Ramiro Martín |
| title |
Amplified singlet oxygen generation in metallated-porphyrin doped conjugated polymer nanoparticles |
| 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 |
| publishDate |
2018 |
| url |
http://sedici.unlp.edu.ar/handle/10915/124432 |
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Repositorios |
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