A solid-state fluorescence sensor for nitroaromatics and nitroanilines based on a conjugated Calix[4]arene polymer
Autor(a) principal: | |
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Data de Publicação: | 2020 |
Outros Autores: | , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
Texto Completo: | http://hdl.handle.net/10400.21/11779 |
Resumo: | A new conjugated polymer possessing calix[4]arene-oxacyclophane units wired-in-series by phenyleneethynylene linkers was synthesized by a Sonogashira-Hagihara cross-coupling method in high yield. The polymer was structurally characterized by FTIR and 1H/13C/HSQC NMR techniques, and its average Mn (38.5 kDa) retrieved from GPC analysis. The polymer is highly emissive (ΦF =0.55) and exhibits a longer-than-usual excited-state lifetime (1.80 ns) for a phenyleneethynylene type polymer. Similar photo physical properties (absorption and fluorescence emission) were observed in solution and insolid-state. This stems from the presence of bulky calixarene moieties along the polymer chains which prevent interchain staking and the formation of ground-state aggregates and/or non-emissive exciplexes, both deleterious to solid-state materials envisioned for fluorescence sensing applications. Moreover, the intrinsic molecular recognition capabilities of its two rigid inner cavities (calixarene and cyclophane sub-units), allied with the high three-dimensionality of the macromolecule that creates additional interstitial voids around the molecular receptors, can boost its sensory responses towards specific analytes. A high sensitive response was observed in the detection of nitroaromatics and nitroanilines in neat vapour phases by casted films of the polymer. The largest sensitivitieswereobtainedfor2,4-dinitrotoluene (a taggant for the explosive TNT;>85% of fluorescence quenching upon 1 min exposure) and ortho-nitroaniline (90% of emission reduction in 30s).The sensory responses attained in solid-state are discussed on the basis of the electron affinities of the analytes and their electrostatic interactions with polymer films. |
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A solid-state fluorescence sensor for nitroaromatics and nitroanilines based on a conjugated Calix[4]arene polymerFluorescenceCalix[4]areneOxacyclophanePolymerNitroanilinesNitroaromaticsSensorExplosivesA new conjugated polymer possessing calix[4]arene-oxacyclophane units wired-in-series by phenyleneethynylene linkers was synthesized by a Sonogashira-Hagihara cross-coupling method in high yield. The polymer was structurally characterized by FTIR and 1H/13C/HSQC NMR techniques, and its average Mn (38.5 kDa) retrieved from GPC analysis. The polymer is highly emissive (ΦF =0.55) and exhibits a longer-than-usual excited-state lifetime (1.80 ns) for a phenyleneethynylene type polymer. Similar photo physical properties (absorption and fluorescence emission) were observed in solution and insolid-state. This stems from the presence of bulky calixarene moieties along the polymer chains which prevent interchain staking and the formation of ground-state aggregates and/or non-emissive exciplexes, both deleterious to solid-state materials envisioned for fluorescence sensing applications. Moreover, the intrinsic molecular recognition capabilities of its two rigid inner cavities (calixarene and cyclophane sub-units), allied with the high three-dimensionality of the macromolecule that creates additional interstitial voids around the molecular receptors, can boost its sensory responses towards specific analytes. A high sensitive response was observed in the detection of nitroaromatics and nitroanilines in neat vapour phases by casted films of the polymer. The largest sensitivitieswereobtainedfor2,4-dinitrotoluene (a taggant for the explosive TNT;>85% of fluorescence quenching upon 1 min exposure) and ortho-nitroaniline (90% of emission reduction in 30s).The sensory responses attained in solid-state are discussed on the basis of the electron affinities of the analytes and their electrostatic interactions with polymer films.SpringerRCIPLPrata, José V.Costa, Alexandra I.Teixeira, Carlos2020-06-05T12:43:01Z2020-012020-01-01T00:00:00Zinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10400.21/11779engPRATA, José V.; COSTA, Alexandra I.; TEIXEIRA, Carlos M. – A solid-state fluorescence sensor for nitroaromatics and nitroanilines based on a conjugated Calix[4]arene polymer. Journal of Fluorescence. ISSN 1053-0509. Vol. 30, N.º 1 (2020), pp. 41-501053-0509https://doi.org/10.1007/s10895-019-02466-1metadata only accessinfo:eu-repo/semantics/openAccessreponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãoinstacron:RCAAP2023-08-03T10:03:27ZPortal AgregadorONG |
dc.title.none.fl_str_mv |
A solid-state fluorescence sensor for nitroaromatics and nitroanilines based on a conjugated Calix[4]arene polymer |
title |
A solid-state fluorescence sensor for nitroaromatics and nitroanilines based on a conjugated Calix[4]arene polymer |
spellingShingle |
A solid-state fluorescence sensor for nitroaromatics and nitroanilines based on a conjugated Calix[4]arene polymer Prata, José V. Fluorescence Calix[4]arene Oxacyclophane Polymer Nitroanilines Nitroaromatics Sensor Explosives |
title_short |
A solid-state fluorescence sensor for nitroaromatics and nitroanilines based on a conjugated Calix[4]arene polymer |
title_full |
A solid-state fluorescence sensor for nitroaromatics and nitroanilines based on a conjugated Calix[4]arene polymer |
title_fullStr |
A solid-state fluorescence sensor for nitroaromatics and nitroanilines based on a conjugated Calix[4]arene polymer |
title_full_unstemmed |
A solid-state fluorescence sensor for nitroaromatics and nitroanilines based on a conjugated Calix[4]arene polymer |
title_sort |
A solid-state fluorescence sensor for nitroaromatics and nitroanilines based on a conjugated Calix[4]arene polymer |
author |
Prata, José V. |
author_facet |
Prata, José V. Costa, Alexandra I. Teixeira, Carlos |
author_role |
author |
author2 |
Costa, Alexandra I. Teixeira, Carlos |
author2_role |
author author |
dc.contributor.none.fl_str_mv |
RCIPL |
dc.contributor.author.fl_str_mv |
Prata, José V. Costa, Alexandra I. Teixeira, Carlos |
dc.subject.por.fl_str_mv |
Fluorescence Calix[4]arene Oxacyclophane Polymer Nitroanilines Nitroaromatics Sensor Explosives |
topic |
Fluorescence Calix[4]arene Oxacyclophane Polymer Nitroanilines Nitroaromatics Sensor Explosives |
description |
A new conjugated polymer possessing calix[4]arene-oxacyclophane units wired-in-series by phenyleneethynylene linkers was synthesized by a Sonogashira-Hagihara cross-coupling method in high yield. The polymer was structurally characterized by FTIR and 1H/13C/HSQC NMR techniques, and its average Mn (38.5 kDa) retrieved from GPC analysis. The polymer is highly emissive (ΦF =0.55) and exhibits a longer-than-usual excited-state lifetime (1.80 ns) for a phenyleneethynylene type polymer. Similar photo physical properties (absorption and fluorescence emission) were observed in solution and insolid-state. This stems from the presence of bulky calixarene moieties along the polymer chains which prevent interchain staking and the formation of ground-state aggregates and/or non-emissive exciplexes, both deleterious to solid-state materials envisioned for fluorescence sensing applications. Moreover, the intrinsic molecular recognition capabilities of its two rigid inner cavities (calixarene and cyclophane sub-units), allied with the high three-dimensionality of the macromolecule that creates additional interstitial voids around the molecular receptors, can boost its sensory responses towards specific analytes. A high sensitive response was observed in the detection of nitroaromatics and nitroanilines in neat vapour phases by casted films of the polymer. The largest sensitivitieswereobtainedfor2,4-dinitrotoluene (a taggant for the explosive TNT;>85% of fluorescence quenching upon 1 min exposure) and ortho-nitroaniline (90% of emission reduction in 30s).The sensory responses attained in solid-state are discussed on the basis of the electron affinities of the analytes and their electrostatic interactions with polymer films. |
publishDate |
2020 |
dc.date.none.fl_str_mv |
2020-06-05T12:43:01Z 2020-01 2020-01-01T00:00:00Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/article |
format |
article |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://hdl.handle.net/10400.21/11779 |
url |
http://hdl.handle.net/10400.21/11779 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
PRATA, José V.; COSTA, Alexandra I.; TEIXEIRA, Carlos M. – A solid-state fluorescence sensor for nitroaromatics and nitroanilines based on a conjugated Calix[4]arene polymer. Journal of Fluorescence. ISSN 1053-0509. Vol. 30, N.º 1 (2020), pp. 41-50 1053-0509 https://doi.org/10.1007/s10895-019-02466-1 |
dc.rights.driver.fl_str_mv |
metadata only access info:eu-repo/semantics/openAccess |
rights_invalid_str_mv |
metadata only access |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
application/pdf |
dc.publisher.none.fl_str_mv |
Springer |
publisher.none.fl_str_mv |
Springer |
dc.source.none.fl_str_mv |
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Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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RCAAP |
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RCAAP |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
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