Síntese, caracterização e aplicação fotobiológica de 10-{[(piridin-4-il)vinil]fenil}corrol e seus complexos de Pt(II) e Pd(II)
Autor(a) principal: | |
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Data de Publicação: | 2022 |
Tipo de documento: | Dissertação |
Idioma: | por |
Título da fonte: | Manancial - Repositório Digital da UFSM |
Texto Completo: | http://repositorio.ufsm.br/handle/1/26755 |
Resumo: | The purpose of this work was the synthesis of the free-base corrole 5,15- bis(pentafluorophenyl)-10-{[(pyridin-4-yl)vinyl]phenyl}corrole and its metallic derivatives containing bipyridine complexes of platinum(II) and palladium(II), having as starting materials 5-(pentafluorophenyl)dipyrromethane, 4-[(pyridin-4-yl)vinyl]benzaldehyde, cisdichloro(2,2'-bipyridine)platinum(II) and cis-dichloro (2,2'-bipyridine)palladium(II). The compounds were characterized by elemental analysis (CHN%) and High-Resolution Mass Spectrometry, as well as by electron spectroscopy in the ultraviolet and visible regions, fluorescence emission spectroscopy (steady state and time-resolved) and electrochemistry (cyclic voltammetry). In order to evaluate the photobiological properties of the compounds, aggregation studies in different solvents, photostability measurements, partition coefficient calculations, as well as assays for the generation of reactive oxygen species, such as singlet oxygen and superoxide radical, were also developed. Furthermore, the interaction of the compounds with DNA was investigated experimentally via spectroscopy in the UV-Vis regions and fluorescence emission, and also by viscosimetry, using competing dyes for interaction sites in the biomolecule, such as: acridine orange, ethidium bromide, methyl green and 4',6-diamidino-2-phenylindole. All compounds studied showed good photostability. The free-base corrole H3VpyCor showed a reasonable quantum yield of fluorescence and displays hydrophobic behavior. Possibly, it interacts more effectively in the minor groove of DNA, according to high values of suppression constants (Ksv and kq), and also by theoretical molecular docking calculations. The PtVpyCor derivative showed relevant results in the generation of superoxide radicals, as well as the possibility of interacting with DNA in an intercalative form and through the minor groove. Finally, the PdVpyCor derivative presented the best result in the generation of singlet oxygen, according to values of quantum yield (ΦΔ) and photo-oxidation constant (kfo), and also exhibited the possibility of intercalation with DNA, besides to interaction with the minor groove. |
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Síntese, caracterização e aplicação fotobiológica de 10-{[(piridin-4-il)vinil]fenil}corrol e seus complexos de Pt(II) e Pd(II)Synthesis, characterization and photobiological application of 10-{[(pyridin-4-yl)vinyl]phenyl}corrole and its Pt(II) and Pd(II) complexesCorróisFotofísicaInteração com DNACorrolesPhotophysicsDNA interactionsCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAThe purpose of this work was the synthesis of the free-base corrole 5,15- bis(pentafluorophenyl)-10-{[(pyridin-4-yl)vinyl]phenyl}corrole and its metallic derivatives containing bipyridine complexes of platinum(II) and palladium(II), having as starting materials 5-(pentafluorophenyl)dipyrromethane, 4-[(pyridin-4-yl)vinyl]benzaldehyde, cisdichloro(2,2'-bipyridine)platinum(II) and cis-dichloro (2,2'-bipyridine)palladium(II). The compounds were characterized by elemental analysis (CHN%) and High-Resolution Mass Spectrometry, as well as by electron spectroscopy in the ultraviolet and visible regions, fluorescence emission spectroscopy (steady state and time-resolved) and electrochemistry (cyclic voltammetry). In order to evaluate the photobiological properties of the compounds, aggregation studies in different solvents, photostability measurements, partition coefficient calculations, as well as assays for the generation of reactive oxygen species, such as singlet oxygen and superoxide radical, were also developed. Furthermore, the interaction of the compounds with DNA was investigated experimentally via spectroscopy in the UV-Vis regions and fluorescence emission, and also by viscosimetry, using competing dyes for interaction sites in the biomolecule, such as: acridine orange, ethidium bromide, methyl green and 4',6-diamidino-2-phenylindole. All compounds studied showed good photostability. The free-base corrole H3VpyCor showed a reasonable quantum yield of fluorescence and displays hydrophobic behavior. Possibly, it interacts more effectively in the minor groove of DNA, according to high values of suppression constants (Ksv and kq), and also by theoretical molecular docking calculations. The PtVpyCor derivative showed relevant results in the generation of superoxide radicals, as well as the possibility of interacting with DNA in an intercalative form and through the minor groove. Finally, the PdVpyCor derivative presented the best result in the generation of singlet oxygen, according to values of quantum yield (ΦΔ) and photo-oxidation constant (kfo), and also exhibited the possibility of intercalation with DNA, besides to interaction with the minor groove.Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPqEste trabalho teve como propósito a síntese do corrol base-livre 5,15-bis(pentafluorofenil)-10- {[(piridin-4-il)vinil]fenil}corrol e seus derivados metalados contendo complexos bipiridínicos de platina(II) e paládio(II), tendo como materiais de partida 5- (pentafluorofenil)dipirrometano, 4-[(piridin-4-il)vinil]benzaldeído, cis-dicloro(2,2'- bipiridina)platina(II) e cis-dicloro(2,2'-bipiridina)paládio(II). Os compostos foram caracterizados por análise elementar (CHN%) e espectrometria de massas de alta resolução, bem como por espectroscopia eletrônica nas regiões do ultravioleta e do visível, espectroscopia de emissão de fluorescência (estado estacionário e resolvida no tempo) e eletroquímica (voltametria cíclica). Para avaliar as propriedades fotobiológicas dos compostos, também foram desenvolvidos estudos de agregação em diferentes solventes, medidas de fotoestabilidade, cálculos dos coeficientes de partição, bem como ensaios de geração de espécies reativas de oxigênio, tais como oxigênio singleto e radical superóxido. Além disso, a interação dos compostos com DNA foi investigada experimentalmente via espectroscopia de absorção eletrônica nas regiões UV-Vis e de emissão de fluorescência, e também por viscosimetria, utilizando corantes competidores por sítios de interação na biomolécula, tais como:alaranjado de acridina, brometo de etídio, verde de metila e 4',6- diamidino-2-fenilindol. Todos os compostos estudados apresentaram boa fotoestabilidade. O corrol base-livre H3VpyCor apresentou um rendimento quântico de fluorescência razoável e exibiu comportamento hidrofóbico. Possivelmente, interage de forma mais eficaz no sulco menor do DNA, conforme valores elevados das constantes de supressão (Ksv e kq), e também pelos cálculos teóricos de docking molecular. O derivado PtVpyCor mostrou resultados relevantes na geração de radicais superóxido, assim como a possibilidade de interação com o DNA de forma intercalativa e pelo sulco menor. Finalmente, o derivado PdVpyCor apresentou o melhor resultado na geração de oxigênio singleto, de acordo com valores de rendimento quântico (ΦΔ) e da constante de foto-oxidação (kfo), e ainda exibiu possibilidade de intercalação com o DNA, além de interação com o sulco menor.Universidade Federal de Santa MariaBrasilQuímicaUFSMPrograma de Pós-Graduação em QuímicaCentro de Ciências Naturais e ExatasIglesias, Bernardo Almeidahttp://lattes.cnpq.br/4402375533322977Back, Davi FernandoCosta, Luiz Antônio SodréDiógenes, Izaura Cirino NogueiraDozza, Bianca2022-11-04T16:37:39Z2022-11-04T16:37:39Z2022-09-27info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisapplication/pdfhttp://repositorio.ufsm.br/handle/1/26755porAttribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessreponame:Manancial - Repositório Digital da UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSM2022-11-04T16:37:39Zoai:repositorio.ufsm.br:1/26755Biblioteca Digital de Teses e Dissertaçõeshttps://repositorio.ufsm.br/ONGhttps://repositorio.ufsm.br/oai/requestatendimento.sib@ufsm.br||tedebc@gmail.comopendoar:2022-11-04T16:37:39Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.none.fl_str_mv |
Síntese, caracterização e aplicação fotobiológica de 10-{[(piridin-4-il)vinil]fenil}corrol e seus complexos de Pt(II) e Pd(II) Synthesis, characterization and photobiological application of 10-{[(pyridin-4-yl)vinyl]phenyl}corrole and its Pt(II) and Pd(II) complexes |
title |
Síntese, caracterização e aplicação fotobiológica de 10-{[(piridin-4-il)vinil]fenil}corrol e seus complexos de Pt(II) e Pd(II) |
spellingShingle |
Síntese, caracterização e aplicação fotobiológica de 10-{[(piridin-4-il)vinil]fenil}corrol e seus complexos de Pt(II) e Pd(II) Dozza, Bianca Corróis Fotofísica Interação com DNA Corroles Photophysics DNA interactions CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Síntese, caracterização e aplicação fotobiológica de 10-{[(piridin-4-il)vinil]fenil}corrol e seus complexos de Pt(II) e Pd(II) |
title_full |
Síntese, caracterização e aplicação fotobiológica de 10-{[(piridin-4-il)vinil]fenil}corrol e seus complexos de Pt(II) e Pd(II) |
title_fullStr |
Síntese, caracterização e aplicação fotobiológica de 10-{[(piridin-4-il)vinil]fenil}corrol e seus complexos de Pt(II) e Pd(II) |
title_full_unstemmed |
Síntese, caracterização e aplicação fotobiológica de 10-{[(piridin-4-il)vinil]fenil}corrol e seus complexos de Pt(II) e Pd(II) |
title_sort |
Síntese, caracterização e aplicação fotobiológica de 10-{[(piridin-4-il)vinil]fenil}corrol e seus complexos de Pt(II) e Pd(II) |
author |
Dozza, Bianca |
author_facet |
Dozza, Bianca |
author_role |
author |
dc.contributor.none.fl_str_mv |
Iglesias, Bernardo Almeida http://lattes.cnpq.br/4402375533322977 Back, Davi Fernando Costa, Luiz Antônio Sodré Diógenes, Izaura Cirino Nogueira |
dc.contributor.author.fl_str_mv |
Dozza, Bianca |
dc.subject.por.fl_str_mv |
Corróis Fotofísica Interação com DNA Corroles Photophysics DNA interactions CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
topic |
Corróis Fotofísica Interação com DNA Corroles Photophysics DNA interactions CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
The purpose of this work was the synthesis of the free-base corrole 5,15- bis(pentafluorophenyl)-10-{[(pyridin-4-yl)vinyl]phenyl}corrole and its metallic derivatives containing bipyridine complexes of platinum(II) and palladium(II), having as starting materials 5-(pentafluorophenyl)dipyrromethane, 4-[(pyridin-4-yl)vinyl]benzaldehyde, cisdichloro(2,2'-bipyridine)platinum(II) and cis-dichloro (2,2'-bipyridine)palladium(II). The compounds were characterized by elemental analysis (CHN%) and High-Resolution Mass Spectrometry, as well as by electron spectroscopy in the ultraviolet and visible regions, fluorescence emission spectroscopy (steady state and time-resolved) and electrochemistry (cyclic voltammetry). In order to evaluate the photobiological properties of the compounds, aggregation studies in different solvents, photostability measurements, partition coefficient calculations, as well as assays for the generation of reactive oxygen species, such as singlet oxygen and superoxide radical, were also developed. Furthermore, the interaction of the compounds with DNA was investigated experimentally via spectroscopy in the UV-Vis regions and fluorescence emission, and also by viscosimetry, using competing dyes for interaction sites in the biomolecule, such as: acridine orange, ethidium bromide, methyl green and 4',6-diamidino-2-phenylindole. All compounds studied showed good photostability. The free-base corrole H3VpyCor showed a reasonable quantum yield of fluorescence and displays hydrophobic behavior. Possibly, it interacts more effectively in the minor groove of DNA, according to high values of suppression constants (Ksv and kq), and also by theoretical molecular docking calculations. The PtVpyCor derivative showed relevant results in the generation of superoxide radicals, as well as the possibility of interacting with DNA in an intercalative form and through the minor groove. Finally, the PdVpyCor derivative presented the best result in the generation of singlet oxygen, according to values of quantum yield (ΦΔ) and photo-oxidation constant (kfo), and also exhibited the possibility of intercalation with DNA, besides to interaction with the minor groove. |
publishDate |
2022 |
dc.date.none.fl_str_mv |
2022-11-04T16:37:39Z 2022-11-04T16:37:39Z 2022-09-27 |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/masterThesis |
format |
masterThesis |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/26755 |
url |
http://repositorio.ufsm.br/handle/1/26755 |
dc.language.iso.fl_str_mv |
por |
language |
por |
dc.rights.driver.fl_str_mv |
Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/ info:eu-repo/semantics/openAccess |
rights_invalid_str_mv |
Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/ |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
application/pdf |
dc.publisher.none.fl_str_mv |
Universidade Federal de Santa Maria Brasil Química UFSM Programa de Pós-Graduação em Química Centro de Ciências Naturais e Exatas |
publisher.none.fl_str_mv |
Universidade Federal de Santa Maria Brasil Química UFSM Programa de Pós-Graduação em Química Centro de Ciências Naturais e Exatas |
dc.source.none.fl_str_mv |
reponame:Manancial - Repositório Digital da UFSM instname:Universidade Federal de Santa Maria (UFSM) instacron:UFSM |
instname_str |
Universidade Federal de Santa Maria (UFSM) |
instacron_str |
UFSM |
institution |
UFSM |
reponame_str |
Manancial - Repositório Digital da UFSM |
collection |
Manancial - Repositório Digital da UFSM |
repository.name.fl_str_mv |
Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM) |
repository.mail.fl_str_mv |
atendimento.sib@ufsm.br||tedebc@gmail.com |
_version_ |
1805922146775465984 |