Synthesis and evaluation of fluorimetric and colorimetric chemosensors for anions based on (oligo)thienyl-thiosemicarbazones
Autor(a) principal: | |
---|---|
Data de Publicação: | 2012 |
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/1822/21928 |
Resumo: | A family of heterocyclic thiosemicarbazone dyes (3a-d) containing thienyl groups has been synthesized, characterized and their chromo-fluorogenic response in acetonitrile in the presence of selected anions studied. Acetonitrile solutions of 3a-d show absorption bands in the 338-425 nm range which are modulated by the groups attached to the thiosemicarbazone moiety. The fluoride, chloride, bromide, iodide, dihydrogen phosphate, hydrogen sulfate, nitrate, acetate and anions were used in the recognition studies. Only sensing features were observed for fluoride, cyanide, acetate and dihydrogen phosphate anions. Two different chromogenic responses were found, (i) a small shift of the absorption band due to coordination of the anions with the thiourea protons and (ii) the appearance of a new red shifted band due to deprotonation of the receptor. For the latter process changes in the color solutions from pale-yellow to orange-red were observed. Fluorescence studies showed a different emission behavior according to the number of thienyl rings in the π-conjugated bridges. Stability constants for the two processes (complex formation + deprotonation) for receptors 3a-d in the presence of fluoride and acetate anions were determined from spectrophotometric titrations using the HypSpec program. The interaction of 3d with fluoride was also studied through 1H NMR titrations. Semiempirical calculations to evaluate the hydrogen-donating ability of the receptors were also performed. |
id |
RCAP_150250d02cd8f5c03df87ab13f0e5b51 |
---|---|
oai_identifier_str |
oai:repositorium.sdum.uminho.pt:1822/21928 |
network_acronym_str |
RCAP |
network_name_str |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
repository_id_str |
7160 |
spelling |
Synthesis and evaluation of fluorimetric and colorimetric chemosensors for anions based on (oligo)thienyl-thiosemicarbazonesChromophoric and Fluorogenic sensorThienyl thiosemicarbazone receptorsAnion recognitionHydrogen bond complexationDeprotonationThiopheneSynthesisHeterocyclesScience & TechnologyA family of heterocyclic thiosemicarbazone dyes (3a-d) containing thienyl groups has been synthesized, characterized and their chromo-fluorogenic response in acetonitrile in the presence of selected anions studied. Acetonitrile solutions of 3a-d show absorption bands in the 338-425 nm range which are modulated by the groups attached to the thiosemicarbazone moiety. The fluoride, chloride, bromide, iodide, dihydrogen phosphate, hydrogen sulfate, nitrate, acetate and anions were used in the recognition studies. Only sensing features were observed for fluoride, cyanide, acetate and dihydrogen phosphate anions. Two different chromogenic responses were found, (i) a small shift of the absorption band due to coordination of the anions with the thiourea protons and (ii) the appearance of a new red shifted band due to deprotonation of the receptor. For the latter process changes in the color solutions from pale-yellow to orange-red were observed. Fluorescence studies showed a different emission behavior according to the number of thienyl rings in the π-conjugated bridges. Stability constants for the two processes (complex formation + deprotonation) for receptors 3a-d in the presence of fluoride and acetate anions were determined from spectrophotometric titrations using the HypSpec program. The interaction of 3d with fluoride was also studied through 1H NMR titrations. Semiempirical calculations to evaluate the hydrogen-donating ability of the receptors were also performed.Fundação para a Ciência e a Tecnologia (FCT) , Acções Integradas Luso-Espanholas/CRUP, Generalitat ValenciaElsevierUniversidade do MinhoSantos-Figueroa, Luis E.Moragues, María E.Raposo, M. Manuela M.Batista, Rosa Maria FerreiraFerreira, R. Cristina M.Costa, Susana P. G.Sancenón, FélixMartínez-Máñez, RamónSoto, JuanRos-Lis, José Vicente20122012-01-01T00:00:00Zinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/1822/21928eng0040-402010.1016/j.tet.2012.06.021info: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:RCAAP2023-07-21T12:45:16Zoai:repositorium.sdum.uminho.pt:1822/21928Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T19:43:06.548491Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãofalse |
dc.title.none.fl_str_mv |
Synthesis and evaluation of fluorimetric and colorimetric chemosensors for anions based on (oligo)thienyl-thiosemicarbazones |
title |
Synthesis and evaluation of fluorimetric and colorimetric chemosensors for anions based on (oligo)thienyl-thiosemicarbazones |
spellingShingle |
Synthesis and evaluation of fluorimetric and colorimetric chemosensors for anions based on (oligo)thienyl-thiosemicarbazones Santos-Figueroa, Luis E. Chromophoric and Fluorogenic sensor Thienyl thiosemicarbazone receptors Anion recognition Hydrogen bond complexation Deprotonation Thiophene Synthesis Heterocycles Science & Technology |
title_short |
Synthesis and evaluation of fluorimetric and colorimetric chemosensors for anions based on (oligo)thienyl-thiosemicarbazones |
title_full |
Synthesis and evaluation of fluorimetric and colorimetric chemosensors for anions based on (oligo)thienyl-thiosemicarbazones |
title_fullStr |
Synthesis and evaluation of fluorimetric and colorimetric chemosensors for anions based on (oligo)thienyl-thiosemicarbazones |
title_full_unstemmed |
Synthesis and evaluation of fluorimetric and colorimetric chemosensors for anions based on (oligo)thienyl-thiosemicarbazones |
title_sort |
Synthesis and evaluation of fluorimetric and colorimetric chemosensors for anions based on (oligo)thienyl-thiosemicarbazones |
author |
Santos-Figueroa, Luis E. |
author_facet |
Santos-Figueroa, Luis E. Moragues, María E. Raposo, M. Manuela M. Batista, Rosa Maria Ferreira Ferreira, R. Cristina M. Costa, Susana P. G. Sancenón, Félix Martínez-Máñez, Ramón Soto, Juan Ros-Lis, José Vicente |
author_role |
author |
author2 |
Moragues, María E. Raposo, M. Manuela M. Batista, Rosa Maria Ferreira Ferreira, R. Cristina M. Costa, Susana P. G. Sancenón, Félix Martínez-Máñez, Ramón Soto, Juan Ros-Lis, José Vicente |
author2_role |
author author author author author author author author author |
dc.contributor.none.fl_str_mv |
Universidade do Minho |
dc.contributor.author.fl_str_mv |
Santos-Figueroa, Luis E. Moragues, María E. Raposo, M. Manuela M. Batista, Rosa Maria Ferreira Ferreira, R. Cristina M. Costa, Susana P. G. Sancenón, Félix Martínez-Máñez, Ramón Soto, Juan Ros-Lis, José Vicente |
dc.subject.por.fl_str_mv |
Chromophoric and Fluorogenic sensor Thienyl thiosemicarbazone receptors Anion recognition Hydrogen bond complexation Deprotonation Thiophene Synthesis Heterocycles Science & Technology |
topic |
Chromophoric and Fluorogenic sensor Thienyl thiosemicarbazone receptors Anion recognition Hydrogen bond complexation Deprotonation Thiophene Synthesis Heterocycles Science & Technology |
description |
A family of heterocyclic thiosemicarbazone dyes (3a-d) containing thienyl groups has been synthesized, characterized and their chromo-fluorogenic response in acetonitrile in the presence of selected anions studied. Acetonitrile solutions of 3a-d show absorption bands in the 338-425 nm range which are modulated by the groups attached to the thiosemicarbazone moiety. The fluoride, chloride, bromide, iodide, dihydrogen phosphate, hydrogen sulfate, nitrate, acetate and anions were used in the recognition studies. Only sensing features were observed for fluoride, cyanide, acetate and dihydrogen phosphate anions. Two different chromogenic responses were found, (i) a small shift of the absorption band due to coordination of the anions with the thiourea protons and (ii) the appearance of a new red shifted band due to deprotonation of the receptor. For the latter process changes in the color solutions from pale-yellow to orange-red were observed. Fluorescence studies showed a different emission behavior according to the number of thienyl rings in the π-conjugated bridges. Stability constants for the two processes (complex formation + deprotonation) for receptors 3a-d in the presence of fluoride and acetate anions were determined from spectrophotometric titrations using the HypSpec program. The interaction of 3d with fluoride was also studied through 1H NMR titrations. Semiempirical calculations to evaluate the hydrogen-donating ability of the receptors were also performed. |
publishDate |
2012 |
dc.date.none.fl_str_mv |
2012 2012-01-01T00:00:00Z |
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/1822/21928 |
url |
http://hdl.handle.net/1822/21928 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
0040-4020 10.1016/j.tet.2012.06.021 |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
application/pdf |
dc.publisher.none.fl_str_mv |
Elsevier |
publisher.none.fl_str_mv |
Elsevier |
dc.source.none.fl_str_mv |
reponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação instacron:RCAAP |
instname_str |
Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
instacron_str |
RCAAP |
institution |
RCAAP |
reponame_str |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
collection |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
repository.name.fl_str_mv |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
repository.mail.fl_str_mv |
|
_version_ |
1799132986541604864 |