5,10,15,20-meso-tetrapiridilporphyrin europium: synthesis, characterization ans spectroscopic investigations
Autor(a) principal: | |
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Data de Publicação: | 2015 |
Tipo de documento: | Dissertação |
Idioma: | por |
Título da fonte: | Biblioteca Digital de Teses e Dissertações da UFC |
Texto Completo: | http://www.teses.ufc.br/tde_busca/arquivo.php?codArquivo=14722 |
Resumo: | Increasingly, porphyrins have gained a position of detached interest in scientific circles. Its high biological compatibility, being a molecule found naturally in plants and many red blood animals, coupled with the possibility of forming complexes with lanthanide atoms, makes these compounds are particularly attractive in a branch of medicine quite promising in terms respect to combat cancer, called photodynamic therapy. The lanthanide-porphyrin complex act as photosensitizers in the production of singlet oxygen, a cytotoxic species, may be soaked in organic tissue of interest, promoting the cancer cell death. The synthesis of some Ln-porphyrin complexes [Ln (Ln = Gd, Er, Yb)] are already reported in the literature. However, with increasing ionic radius of metal that is intended to complex in the porphyrin, the energy barrier which prevails opposite the occurrence of this synthesis also increases, hindering the occurrence of the metalation process. Thus, this study seeks to promote metalation with europium, in 5,10,15,20 - meso - tetrapyridilporphyrin (H2TPyP). Was used the europium acetylacetonate salt [Eu(acac)3] in the synthesis as a source of Eu3+ ion. The obtained compound was purified by column chromatography on elution of alumina (Al2O3) and further characterized by absorption spectroscopy in the ultraviolet-visible region (UV-VIS) and infrared region (IR), luminescence and termogravimetric analysis (TG). The results obtained for the UV-vis spectra show for complex synthesized 3 Q bands, a lower number compared to the spectrum of the free base porphyrin, which has 4 Q bands, which discloses the formation of a compound with higher symmetry, which rose from D2h to D4h due to insertion of the metal ion in the porphyrin ring. It was observed also a bathochromic shift of the Soret band in the complex shifted from 417 to 429nm, consistent with the fact that the metallation occurred. The IR results and suggest the occurrence of metalation of the suppression band 3304cm-1, indicating deprotonation of the central atoms of Nytrogen, also suggested maintaining the acetylacetonate ion in stabilizing the structure of the complex. The luminescence showed that there was enhancement of emission bands, which is consistent with the formation of a metal complex. In the TG results, it was found that the compound formed to the amount of residue obtained was much higher than that for H2TPyP, suggesting the formation of metal oxide in the first case, consistent with the fact that formation of europium metalloporphyrin. |
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info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesis5,10,15,20-meso-tetrapiridilporphyrin europium: synthesis, characterization ans spectroscopic investigations5,10,15,20-meso-tetrapiridilporfirina de eurÃpio: sÃntese, caracterizaÃÃo e investigaÃÃes espectroscÃpicas2015-05-21Francisco AudÃsio Dias Filho47790385372http://lattes.cnpq.br/2090415373875792Jackson Rodrigues de Sousa41560922320http://lattes.cnpq.br/0168499006683936TÃrcio de Freitas Paulo93709579368http://lattes.cnpq.br/831044960962683702083265378http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4947350A6Alexandre Carreira da Cruz SousaUniversidade Federal do CearÃPrograma de PÃs-GraduaÃÃo em QuÃmica UFCBRMetalaÃÃo EurÃpio MetaloporfirinaPorfirinas Metalation EuropiumetalloporphyrinQUIMICA INORGANICAIncreasingly, porphyrins have gained a position of detached interest in scientific circles. Its high biological compatibility, being a molecule found naturally in plants and many red blood animals, coupled with the possibility of forming complexes with lanthanide atoms, makes these compounds are particularly attractive in a branch of medicine quite promising in terms respect to combat cancer, called photodynamic therapy. The lanthanide-porphyrin complex act as photosensitizers in the production of singlet oxygen, a cytotoxic species, may be soaked in organic tissue of interest, promoting the cancer cell death. The synthesis of some Ln-porphyrin complexes [Ln (Ln = Gd, Er, Yb)] are already reported in the literature. However, with increasing ionic radius of metal that is intended to complex in the porphyrin, the energy barrier which prevails opposite the occurrence of this synthesis also increases, hindering the occurrence of the metalation process. Thus, this study seeks to promote metalation with europium, in 5,10,15,20 - meso - tetrapyridilporphyrin (H2TPyP). Was used the europium acetylacetonate salt [Eu(acac)3] in the synthesis as a source of Eu3+ ion. The obtained compound was purified by column chromatography on elution of alumina (Al2O3) and further characterized by absorption spectroscopy in the ultraviolet-visible region (UV-VIS) and infrared region (IR), luminescence and termogravimetric analysis (TG). The results obtained for the UV-vis spectra show for complex synthesized 3 Q bands, a lower number compared to the spectrum of the free base porphyrin, which has 4 Q bands, which discloses the formation of a compound with higher symmetry, which rose from D2h to D4h due to insertion of the metal ion in the porphyrin ring. It was observed also a bathochromic shift of the Soret band in the complex shifted from 417 to 429nm, consistent with the fact that the metallation occurred. The IR results and suggest the occurrence of metalation of the suppression band 3304cm-1, indicating deprotonation of the central atoms of Nytrogen, also suggested maintaining the acetylacetonate ion in stabilizing the structure of the complex. The luminescence showed that there was enhancement of emission bands, which is consistent with the formation of a metal complex. In the TG results, it was found that the compound formed to the amount of residue obtained was much higher than that for H2TPyP, suggesting the formation of metal oxide in the first case, consistent with the fact that formation of europium metalloporphyrin.Cada vez mais, as porfirinas vÃm conquistando uma posiÃÃo de destacado interesse no meio cientÃfico. Sua elevada compatibilidade biolÃgica, sendo uma molÃcula encontrada naturalmente em plantas e em diversos animais de sangue vermelho, aliada a possibilidade da formaÃÃo de complexos com Ãtomos de lantanÃdeos, faz com que esses compostos sejam particularmente atrativos em um ramo bastante promissor da medicina no que diz respeito ao combate ao cÃncer, denominado de terapia fotodinÃmica. Isso porque os complexos lantanÃdeos-porfirina atuam como fotossensibilizadores na produÃÃo de oxigÃnio singlete, uma espÃcie citotÃxica, podendo esses complexos serem saturados em tecidos orgÃnicos de interesse, promovendo a morte de cÃlulas cancerÃgenas. A sÃntese de alguns complexos Ln-porfirina (Ln= Gd, Er, Yb) jà sÃo reportadas na literatura. Entretanto, com o aumento do raio iÃnico do metal que se pretende complexar a porfirina, a barreira energÃtica que se impera frente a ocorrÃncia desta sÃntese tambÃm aumenta, dificultando a ocorrÃncia do processo de metalaÃÃo. Dessa forma, o presente estudo busca promover a metalaÃÃo de eurÃpio na 5,10,15,20 â meso â tetrapiridilporfirina (H2TPyP). Utilizou-se o sal acetilacetonato de eurÃpio [Eu(acac)3] na sÃntese como fonte do Ãon Eu3+. O composto obtido foi purificado por eluiÃÃo em coluna cromatogrÃfica de alumina (Al2O3) e posteriormente caracterizado por espectroscopia de absorÃÃo na regiÃo do ultravioleta-visÃvel (UV-Vis) e infravermelho (IR), luminescÃncia e anÃlise termogravimÃtica (TG). Os resultados obtidos por UV-Vis para o complexo sintetizado mostraram espectros com 3 bandas Q, um menor nÃmero comparado ao espectro da porfirina base livre que apresenta 4 bandas Q, o que sugere a formaÃÃo de um composto com maior simetria, que passou de D2h para D4h, devido a inserÃÃo do Ãon metÃlico no anel porfirÃnico. Observou-se tambÃm um deslocamento batocrÃmico da banda Soret no complexo que deslocou de 417 para 429nm, fato condizente com a ocorrÃncia da metalaÃÃo. Os resultados de IR, alÃm de sugerirem a ocorrÃncia da metalaÃÃo pela supressÃo da banda em 3304cm-1, indicando a desprotonaÃÃo dos nitrogÃnios centrais, tambÃm sugeriram a manutenÃÃo do Ãon acetilacetonato na estabilizaÃÃo da estrutura do complexo. A luminescÃncia mostrou que houve intensificaÃÃo das bandas de emissÃo, o que condiz com a formaÃÃo de um complexo metÃlico. Nos resultados de TG constatou-se que para o composto formado a quantidade de resÃduo obtido foi bastante superior de que para a H2TPyP, sugerindo a formaÃÃo de Ãxido metÃlico no primeiro caso, fato condizente com a formaÃÃo da metaloporfirina de eurÃpio.Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgicohttp://www.teses.ufc.br/tde_busca/arquivo.php?codArquivo=14722application/pdfinfo:eu-repo/semantics/openAccessporreponame:Biblioteca Digital de Teses e Dissertações da UFCinstname:Universidade Federal do Cearáinstacron:UFC2019-01-21T11:28:46Zmail@mail.com - |
dc.title.en.fl_str_mv |
5,10,15,20-meso-tetrapiridilporphyrin europium: synthesis, characterization ans spectroscopic investigations |
dc.title.alternative.pt.fl_str_mv |
5,10,15,20-meso-tetrapiridilporfirina de eurÃpio: sÃntese, caracterizaÃÃo e investigaÃÃes espectroscÃpicas |
title |
5,10,15,20-meso-tetrapiridilporphyrin europium: synthesis, characterization ans spectroscopic investigations |
spellingShingle |
5,10,15,20-meso-tetrapiridilporphyrin europium: synthesis, characterization ans spectroscopic investigations Alexandre Carreira da Cruz Sousa MetalaÃÃo EurÃpio Metaloporfirina Porfirinas Metalation Europium etalloporphyrin QUIMICA INORGANICA |
title_short |
5,10,15,20-meso-tetrapiridilporphyrin europium: synthesis, characterization ans spectroscopic investigations |
title_full |
5,10,15,20-meso-tetrapiridilporphyrin europium: synthesis, characterization ans spectroscopic investigations |
title_fullStr |
5,10,15,20-meso-tetrapiridilporphyrin europium: synthesis, characterization ans spectroscopic investigations |
title_full_unstemmed |
5,10,15,20-meso-tetrapiridilporphyrin europium: synthesis, characterization ans spectroscopic investigations |
title_sort |
5,10,15,20-meso-tetrapiridilporphyrin europium: synthesis, characterization ans spectroscopic investigations |
author |
Alexandre Carreira da Cruz Sousa |
author_facet |
Alexandre Carreira da Cruz Sousa |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Francisco AudÃsio Dias Filho |
dc.contributor.advisor1ID.fl_str_mv |
47790385372 |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/2090415373875792 |
dc.contributor.referee1.fl_str_mv |
Jackson Rodrigues de Sousa |
dc.contributor.referee1ID.fl_str_mv |
41560922320 |
dc.contributor.referee1Lattes.fl_str_mv |
http://lattes.cnpq.br/0168499006683936 |
dc.contributor.referee2.fl_str_mv |
TÃrcio de Freitas Paulo |
dc.contributor.referee2ID.fl_str_mv |
93709579368 |
dc.contributor.referee2Lattes.fl_str_mv |
http://lattes.cnpq.br/8310449609626837 |
dc.contributor.authorID.fl_str_mv |
02083265378 |
dc.contributor.authorLattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4947350A6 |
dc.contributor.author.fl_str_mv |
Alexandre Carreira da Cruz Sousa |
contributor_str_mv |
Francisco AudÃsio Dias Filho Jackson Rodrigues de Sousa TÃrcio de Freitas Paulo |
dc.subject.por.fl_str_mv |
MetalaÃÃo EurÃpio Metaloporfirina Porfirinas |
topic |
MetalaÃÃo EurÃpio Metaloporfirina Porfirinas Metalation Europium etalloporphyrin QUIMICA INORGANICA |
dc.subject.eng.fl_str_mv |
Metalation Europium etalloporphyrin |
dc.subject.cnpq.fl_str_mv |
QUIMICA INORGANICA |
dc.description.sponsorship.fl_txt_mv |
Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico |
dc.description.abstract.por.fl_txt_mv |
Increasingly, porphyrins have gained a position of detached interest in scientific circles. Its high biological compatibility, being a molecule found naturally in plants and many red blood animals, coupled with the possibility of forming complexes with lanthanide atoms, makes these compounds are particularly attractive in a branch of medicine quite promising in terms respect to combat cancer, called photodynamic therapy. The lanthanide-porphyrin complex act as photosensitizers in the production of singlet oxygen, a cytotoxic species, may be soaked in organic tissue of interest, promoting the cancer cell death. The synthesis of some Ln-porphyrin complexes [Ln (Ln = Gd, Er, Yb)] are already reported in the literature. However, with increasing ionic radius of metal that is intended to complex in the porphyrin, the energy barrier which prevails opposite the occurrence of this synthesis also increases, hindering the occurrence of the metalation process. Thus, this study seeks to promote metalation with europium, in 5,10,15,20 - meso - tetrapyridilporphyrin (H2TPyP). Was used the europium acetylacetonate salt [Eu(acac)3] in the synthesis as a source of Eu3+ ion. The obtained compound was purified by column chromatography on elution of alumina (Al2O3) and further characterized by absorption spectroscopy in the ultraviolet-visible region (UV-VIS) and infrared region (IR), luminescence and termogravimetric analysis (TG). The results obtained for the UV-vis spectra show for complex synthesized 3 Q bands, a lower number compared to the spectrum of the free base porphyrin, which has 4 Q bands, which discloses the formation of a compound with higher symmetry, which rose from D2h to D4h due to insertion of the metal ion in the porphyrin ring. It was observed also a bathochromic shift of the Soret band in the complex shifted from 417 to 429nm, consistent with the fact that the metallation occurred. The IR results and suggest the occurrence of metalation of the suppression band 3304cm-1, indicating deprotonation of the central atoms of Nytrogen, also suggested maintaining the acetylacetonate ion in stabilizing the structure of the complex. The luminescence showed that there was enhancement of emission bands, which is consistent with the formation of a metal complex. In the TG results, it was found that the compound formed to the amount of residue obtained was much higher than that for H2TPyP, suggesting the formation of metal oxide in the first case, consistent with the fact that formation of europium metalloporphyrin. Cada vez mais, as porfirinas vÃm conquistando uma posiÃÃo de destacado interesse no meio cientÃfico. Sua elevada compatibilidade biolÃgica, sendo uma molÃcula encontrada naturalmente em plantas e em diversos animais de sangue vermelho, aliada a possibilidade da formaÃÃo de complexos com Ãtomos de lantanÃdeos, faz com que esses compostos sejam particularmente atrativos em um ramo bastante promissor da medicina no que diz respeito ao combate ao cÃncer, denominado de terapia fotodinÃmica. Isso porque os complexos lantanÃdeos-porfirina atuam como fotossensibilizadores na produÃÃo de oxigÃnio singlete, uma espÃcie citotÃxica, podendo esses complexos serem saturados em tecidos orgÃnicos de interesse, promovendo a morte de cÃlulas cancerÃgenas. A sÃntese de alguns complexos Ln-porfirina (Ln= Gd, Er, Yb) jà sÃo reportadas na literatura. Entretanto, com o aumento do raio iÃnico do metal que se pretende complexar a porfirina, a barreira energÃtica que se impera frente a ocorrÃncia desta sÃntese tambÃm aumenta, dificultando a ocorrÃncia do processo de metalaÃÃo. Dessa forma, o presente estudo busca promover a metalaÃÃo de eurÃpio na 5,10,15,20 â meso â tetrapiridilporfirina (H2TPyP). Utilizou-se o sal acetilacetonato de eurÃpio [Eu(acac)3] na sÃntese como fonte do Ãon Eu3+. O composto obtido foi purificado por eluiÃÃo em coluna cromatogrÃfica de alumina (Al2O3) e posteriormente caracterizado por espectroscopia de absorÃÃo na regiÃo do ultravioleta-visÃvel (UV-Vis) e infravermelho (IR), luminescÃncia e anÃlise termogravimÃtica (TG). Os resultados obtidos por UV-Vis para o complexo sintetizado mostraram espectros com 3 bandas Q, um menor nÃmero comparado ao espectro da porfirina base livre que apresenta 4 bandas Q, o que sugere a formaÃÃo de um composto com maior simetria, que passou de D2h para D4h, devido a inserÃÃo do Ãon metÃlico no anel porfirÃnico. Observou-se tambÃm um deslocamento batocrÃmico da banda Soret no complexo que deslocou de 417 para 429nm, fato condizente com a ocorrÃncia da metalaÃÃo. Os resultados de IR, alÃm de sugerirem a ocorrÃncia da metalaÃÃo pela supressÃo da banda em 3304cm-1, indicando a desprotonaÃÃo dos nitrogÃnios centrais, tambÃm sugeriram a manutenÃÃo do Ãon acetilacetonato na estabilizaÃÃo da estrutura do complexo. A luminescÃncia mostrou que houve intensificaÃÃo das bandas de emissÃo, o que condiz com a formaÃÃo de um complexo metÃlico. Nos resultados de TG constatou-se que para o composto formado a quantidade de resÃduo obtido foi bastante superior de que para a H2TPyP, sugerindo a formaÃÃo de Ãxido metÃlico no primeiro caso, fato condizente com a formaÃÃo da metaloporfirina de eurÃpio. |
description |
Increasingly, porphyrins have gained a position of detached interest in scientific circles. Its high biological compatibility, being a molecule found naturally in plants and many red blood animals, coupled with the possibility of forming complexes with lanthanide atoms, makes these compounds are particularly attractive in a branch of medicine quite promising in terms respect to combat cancer, called photodynamic therapy. The lanthanide-porphyrin complex act as photosensitizers in the production of singlet oxygen, a cytotoxic species, may be soaked in organic tissue of interest, promoting the cancer cell death. The synthesis of some Ln-porphyrin complexes [Ln (Ln = Gd, Er, Yb)] are already reported in the literature. However, with increasing ionic radius of metal that is intended to complex in the porphyrin, the energy barrier which prevails opposite the occurrence of this synthesis also increases, hindering the occurrence of the metalation process. Thus, this study seeks to promote metalation with europium, in 5,10,15,20 - meso - tetrapyridilporphyrin (H2TPyP). Was used the europium acetylacetonate salt [Eu(acac)3] in the synthesis as a source of Eu3+ ion. The obtained compound was purified by column chromatography on elution of alumina (Al2O3) and further characterized by absorption spectroscopy in the ultraviolet-visible region (UV-VIS) and infrared region (IR), luminescence and termogravimetric analysis (TG). The results obtained for the UV-vis spectra show for complex synthesized 3 Q bands, a lower number compared to the spectrum of the free base porphyrin, which has 4 Q bands, which discloses the formation of a compound with higher symmetry, which rose from D2h to D4h due to insertion of the metal ion in the porphyrin ring. It was observed also a bathochromic shift of the Soret band in the complex shifted from 417 to 429nm, consistent with the fact that the metallation occurred. The IR results and suggest the occurrence of metalation of the suppression band 3304cm-1, indicating deprotonation of the central atoms of Nytrogen, also suggested maintaining the acetylacetonate ion in stabilizing the structure of the complex. The luminescence showed that there was enhancement of emission bands, which is consistent with the formation of a metal complex. In the TG results, it was found that the compound formed to the amount of residue obtained was much higher than that for H2TPyP, suggesting the formation of metal oxide in the first case, consistent with the fact that formation of europium metalloporphyrin. |
publishDate |
2015 |
dc.date.issued.fl_str_mv |
2015-05-21 |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/masterThesis |
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publishedVersion |
format |
masterThesis |
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http://www.teses.ufc.br/tde_busca/arquivo.php?codArquivo=14722 |
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http://www.teses.ufc.br/tde_busca/arquivo.php?codArquivo=14722 |
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por |
language |
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Universidade Federal do Cearà |
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Programa de PÃs-GraduaÃÃo em QuÃmica |
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UFC |
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BR |
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Universidade Federal do Cearà |
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