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Highly photostable luminescent poly(caprolactone)siloxane biohybrids doped with europium complexes

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Resumo:In this paper, we propose for the first time that the combination of a sol-gel derived diurethane cross-linked siloxane-based biohybrid host including short poly(ε-caprolactone) segments (PCL(530)) and lanthanide aquocomplexes incorporating β-diketonate ligands yields an effective protecting cage that efficiently encapsulates the emitting centers and reduces luminescence quenching. The results obtained using the Eu(tta) 3 (H 2 O) 2 (where tta - is 2-thenoyltrifluoracetonate) complex demonstrate that 1 (2) carbonyl oxygen atoms of the host matrix enter the Eu 3+ coordination shell, thus replacing the labile water molecule-(s). The significant increase in the quantum efficiency q of the doped hybrid with respect to that of Eu(tta) 3 (H 2 O) 2 (44.2 versus 29.0%, respectively) reveals that complex anchoring to the PCL(530)-based host structure contributes to enhancement of the 5 D 0 quantum efficiency. However, when a complex that contains only strong chelating ligands, such as Eu(tta) 3 phen (where phen is 1,10-phenantroline), is incorporated into the same host medium, the effect is lost and the 5 D 0 nonradiative paths in the doped hybrid are higher than those existing in the complex itself. Under UVA exposure, the emission intensity of PCL(530)/siloxane/Eu(tta) 3 (H 2 O) 2 decreased 10% in 11 h, whereas that of PCL(530)/siloxane/Eu-(tta) 3 phen decreased 25% in the same period of time.
Autores principais:Fernandes, M.
Outros Autores:Zea Bermudez, V. de; Ferreira, R. A. Sá; Carlos, Luís; Charas, A.; Morgado, J.; Silva, Maria Manuela; Smith, Michael John
Assunto:Biohybrid Luminescent polymer Eu3+ doped network
Ano:2007
País:Portugal
Tipo de documento:artigo
Tipo de acesso:acesso restrito
Instituição associada:Universidade do Minho
Idioma:inglês
Origem:RepositóriUM - Universidade do Minho
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author Fernandes, M.
author2 Zea Bermudez, V. de
Ferreira, R. A. Sá
Carlos, Luís
Charas, A.
Morgado, J.
Silva, Maria Manuela
Smith, Michael John
author2_role author
author
author
author
author
author
author
author_facet Fernandes, M.
Zea Bermudez, V. de
Ferreira, R. A. Sá
Carlos, Luís
Charas, A.
Morgado, J.
Silva, Maria Manuela
Smith, Michael John
author_role author
contributor_name_str_mv Universidade do Minho
country_str PT
creators_json_txt [{\"Person.name\":\"Fernandes, M.\"},{\"Person.name\":\"Zea Bermudez, V. de\"},{\"Person.name\":\"Ferreira, R. A. Sá\"},{\"Person.name\":\"Carlos, Luís\"},{\"Person.name\":\"Charas, A.\"},{\"Person.name\":\"Morgado, J.\"},{\"Person.name\":\"Silva, Maria Manuela\"},{\"Person.name\":\"Smith, Michael John\"}]
datacite.contributors.contributor.contributorName.fl_str_mv Universidade do Minho
datacite.creators.creator.creatorName.fl_str_mv Fernandes, M.
Zea Bermudez, V. de
Ferreira, R. A. Sá
Carlos, Luís
Charas, A.
Morgado, J.
Silva, Maria Manuela
Smith, Michael John
datacite.date.Accepted.fl_str_mv 2007-01-01T00:00:00Z
datacite.date.available.fl_str_mv 2008-01-08T19:51:08Z
datacite.date.embargoed.fl_str_mv 2008-01-08T19:51:08Z
datacite.rights.fl_str_mv http://purl.org/coar/access_right/c_16ec
datacite.subjects.subject.fl_str_mv Biohybrid
Luminescent polymer
Eu3+ doped network
datacite.titles.title.fl_str_mv Highly photostable luminescent poly(caprolactone)siloxane biohybrids doped with europium complexes
dc.contributor.none.fl_str_mv Universidade do Minho
dc.creator.none.fl_str_mv Fernandes, M.
Zea Bermudez, V. de
Ferreira, R. A. Sá
Carlos, Luís
Charas, A.
Morgado, J.
Silva, Maria Manuela
Smith, Michael John
dc.date.Accepted.fl_str_mv 2007-01-01T00:00:00Z
dc.date.available.fl_str_mv 2008-01-08T19:51:08Z
dc.date.embargoed.fl_str_mv 2008-01-08T19:51:08Z
dc.format.none.fl_str_mv application/pdf
dc.identifier.none.fl_str_mv https://hdl.handle.net/1822/7416
dc.language.none.fl_str_mv eng
dc.publisher.none.fl_str_mv ACS Publications
dc.rights.none.fl_str_mv http://purl.org/coar/access_right/c_16ec
dc.subject.none.fl_str_mv Biohybrid
Luminescent polymer
Eu3+ doped network
dc.title.fl_str_mv Highly photostable luminescent poly(caprolactone)siloxane biohybrids doped with europium complexes
dc.type.none.fl_str_mv http://purl.org/coar/resource_type/c_6501
description In this paper, we propose for the first time that the combination of a sol-gel derived diurethane cross-linked siloxane-based biohybrid host including short poly(ε-caprolactone) segments (PCL(530)) and lanthanide aquocomplexes incorporating β-diketonate ligands yields an effective protecting cage that efficiently encapsulates the emitting centers and reduces luminescence quenching. The results obtained using the Eu(tta) 3 (H 2 O) 2 (where tta - is 2-thenoyltrifluoracetonate) complex demonstrate that 1 (2) carbonyl oxygen atoms of the host matrix enter the Eu 3+ coordination shell, thus replacing the labile water molecule-(s). The significant increase in the quantum efficiency q of the doped hybrid with respect to that of Eu(tta) 3 (H 2 O) 2 (44.2 versus 29.0%, respectively) reveals that complex anchoring to the PCL(530)-based host structure contributes to enhancement of the 5 D 0 quantum efficiency. However, when a complex that contains only strong chelating ligands, such as Eu(tta) 3 phen (where phen is 1,10-phenantroline), is incorporated into the same host medium, the effect is lost and the 5 D 0 nonradiative paths in the doped hybrid are higher than those existing in the complex itself. Under UVA exposure, the emission intensity of PCL(530)/siloxane/Eu(tta) 3 (H 2 O) 2 decreased 10% in 11 h, whereas that of PCL(530)/siloxane/Eu-(tta) 3 phen decreased 25% in the same period of time.
dirty 0
eu_rights_str_mv restrictedAccess
format article
fulltext.url.fl_str_mv https://prod-dspace.uminho.pt/bitstreams/0ec9b38c-5aaa-49e6-bdd0-8a22f058b560/download
id rum_f01a080790c8f34713ccfb03531d6fec
identifier.url.fl_str_mv https://hdl.handle.net/1822/7416
instacron_str repositorium
institution Universidade do Minho
instname_str Universidade do Minho
language eng
network_acronym_str rum
network_name_str RepositóriUM - Universidade do Minho
oai_identifier_str oai:repositorium.uminho.pt:1822/7416
organization_str_mv urn:organizationAcronym:repositorium
person_str_mv Fernandes, M.
Zea Bermudez, V. de
Ferreira, R. A. Sá
Carlos, Luís
Charas, A.
Morgado, J.
Silva, Maria Manuela
Smith, Michael John
publishDate 2007
publisher.none.fl_str_mv ACS Publications
reponame_str RepositóriUM - Universidade do Minho
repository_id_str urn:repositoryAcronym:rum
service_str_mv urn:repositoryAcronym:rum
spelling engACS PublicationsengIn this paper, we propose for the first time that the combination of a sol-gel derived diurethane cross-linked siloxane-based biohybrid host including short poly(ε-caprolactone) segments (PCL(530)) and lanthanide aquocomplexes incorporating β-diketonate ligands yields an effective protecting cage that efficiently encapsulates the emitting centers and reduces luminescence quenching. The results obtained using the Eu(tta) 3 (H 2 O) 2 (where tta - is 2-thenoyltrifluoracetonate) complex demonstrate that 1 (2) carbonyl oxygen atoms of the host matrix enter the Eu 3+ coordination shell, thus replacing the labile water molecule-(s). The significant increase in the quantum efficiency q of the doped hybrid with respect to that of Eu(tta) 3 (H 2 O) 2 (44.2 versus 29.0%, respectively) reveals that complex anchoring to the PCL(530)-based host structure contributes to enhancement of the 5 D 0 quantum efficiency. However, when a complex that contains only strong chelating ligands, such as Eu(tta) 3 phen (where phen is 1,10-phenantroline), is incorporated into the same host medium, the effect is lost and the 5 D 0 nonradiative paths in the doped hybrid are higher than those existing in the complex itself. Under UVA exposure, the emission intensity of PCL(530)/siloxane/Eu(tta) 3 (H 2 O) 2 decreased 10% in 11 h, whereas that of PCL(530)/siloxane/Eu-(tta) 3 phen decreased 25% in the same period of time.application/pdfengHighly photostable luminescent poly(caprolactone)siloxane biohybrids doped with europium complexesFernandes, M.Zea Bermudez, V. deFerreira, R. A. SáCarlos, LuísCharas, A.Morgado, J.Silva, Maria ManuelaSmith, Michael JohnHostingInstitutionOrganizationalUniversidade do Minhoe-mailmailto:repositorium@usdb.uminho.ptrepositorium@usdb.uminho.ptISSNIsPartOf0897-4756ISSNIsPartOf1520-5002DOIIsPartOf10.1021/cm062832n2008-01-08T19:51:08Z200720062007-01-01T00:00:00ZHandlehttps://hdl.handle.net/1822/7416http://purl.org/coar/access_right/c_16ecrestricted accessBiohybridLuminescent polymerEu3+ doped network445351 bytesliteraturehttp://purl.org/coar/resource_type/c_6501journal articlehttp://purl.org/coar/access_right/c_16ecapplication/pdffulltexthttps://prod-dspace.uminho.pt/bitstreams/0ec9b38c-5aaa-49e6-bdd0-8a22f058b560/download
spellingShingle Highly photostable luminescent poly(caprolactone)siloxane biohybrids doped with europium complexes
Fernandes, M.
Biohybrid
Luminescent polymer
Eu3+ doped network
status SINGLETON
subject.fl_str_mv Biohybrid
Luminescent polymer
Eu3+ doped network
title Highly photostable luminescent poly(caprolactone)siloxane biohybrids doped with europium complexes
title_full Highly photostable luminescent poly(caprolactone)siloxane biohybrids doped with europium complexes
title_fullStr Highly photostable luminescent poly(caprolactone)siloxane biohybrids doped with europium complexes
title_full_unstemmed Highly photostable luminescent poly(caprolactone)siloxane biohybrids doped with europium complexes
title_short Highly photostable luminescent poly(caprolactone)siloxane biohybrids doped with europium complexes
title_sort Highly photostable luminescent poly(caprolactone)siloxane biohybrids doped with europium complexes
topic Biohybrid
Luminescent polymer
Eu3+ doped network
topic_facet Biohybrid
Luminescent polymer
Eu3+ doped network
url https://hdl.handle.net/1822/7416
visible 1