ESTUDOS ESPECTROSCÓPICOS DE PORFIRINAS COMPLEXADAS COM Cu²+

Detalhes bibliográficos
Ano de defesa: 2011
Autor(a) principal: Gonçalves, Joyce Laura da Silva lattes
Orientador(a): Tominaga, Tania Toyomi lattes
Banca de defesa: Não Informado pela instituição
Tipo de documento: Dissertação
Tipo de acesso: Acesso aberto
Idioma: por
Instituição de defesa: UNICENTRO - Universidade Estadual do Centro Oeste
Programa de Pós-Graduação: Programa de Pós-Graduação em Química (Mestrado)
Departamento: Unicentro::Departamento de Química
País: BR
Palavras-chave em Português:
Palavras-chave em Inglês:
Área do conhecimento CNPq:
Link de acesso: http://localhost:8080/tede/handle/tede/320
Resumo: Porphyrins are very interesting because their favorables characteristics on biomedical applications. Paramagnetic metalloporphyrins have been studied and were exhibited promising results as contrast agents in nuclear magnetic resonance imaging. In aqueous medium, these compounds have the ability to form aggregates that minimize their effectiveness for therapeutic purposes. Therefore, the investigation of properties of porphyrin in the presence of biological systems model can support a better understanding of the interaction of porphyrins with tissues in the blood. In the present study we used spectroscopic techniques, to investigated the influence of pH, ionic strength in the two porphyrins complexed with Cu²+: meso-tetrakis (N-methyl-4-pyridyl),CuTMPyP and meso-tetrakis(2-bipyridinil-2-chlorine--ruthenium)CuTPyP{Ru(bipy)2Cl}4, and their interaction with biological model systems. As model systems we used the cationic surfactant cetyltrimethylammonium bromide (CTAB), the nonionic polyoxyethylene stearyl ether (20) (Brij 78) and anionic sodium dodecyl sulfate (SDS) in micellar form. The optical absorption showed that the CuTMPyP was insensitive in the pH range of 0,5 to 13,0 and only one specie was observed. This porphyrin were not influenced by ionic strength. No significant interaction of porphyrin with micelles of CTAB and Brij 78 were occurred. However, in the presence of SDS an effective interaction of porphyrin and SDS was observed. Optical spectra reveal a decrease of de Soret band at 425 nm with increasing SDS concentration until 3,12 x10 -4 mol L?¹. Over this range there is a small red shift in the Soret band and its absorbance increasing with SDS concentration. In conclusion, due to preferential interaction with anionic micelles, the electrostatic factor seems to be more relevant. This result was confirmed by EPR and MCD results. A superhyperfine structure corresponds to four equally coupled nitrogens, i.e., nine lines pattern was observed. Then in the used pH range there is neither change in the binding of Cu in the porphyrin ring nor axial ligands exchanges. The value of g0?2,075 was calculated. Three distinct species in solution equilibrium to the optical absorption spectrum for CuTPyP{Ru(bipy)2Cl}4 were showed. The pK1=3,5± 0,5 and pK2=10,6± 0,6, whose forms are diprotonated, monoprotonated and no protonated were reported. In this case, the ionic strength above 5,9x10-1 mol.L?¹ were denoted. No significant interaction of porphyrin with micelles of CTAB and Brij 78 were occurred again. However, there was a high interaction with anionic surfactant. A decrease of de Soret band at 417 nm with increasing SDS concentration until 5,1x10-4 mol.L?¹ were observed. Thereafter, a small red shift in the Soret band and its absorbance increasing with SDS concentration were observed. One more time, the electrostatic factor was very relevant. The MCD and EPR were in agreement with this results. The hyperfine structure resulted from the interaction between delocalized ? electron and N magnetic nuclei was just observed in presence of SDS micelles. EPR data at 77 K presented a typical axial spectrum with g//?2.345 and g??2.026 for all situations. Due to high concentration of both porphyrins used, only free form of porphyrin and theirself interaction of SDS micelles were observed in MCD and EPR spectra. M oreover, the electrostatic factor proved to be the most important factor in interactions of porphyrins.
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spelling Tominaga, Tania ToyomiCPF:78657845746http://lattes.cnpq.br/6909363427100376CPF:05798154980http://lattes.cnpq.br/6163800361294977Gonçalves, Joyce Laura da Silva2016-09-20T12:27:16Z2011-05-252011-02-28GONÇALVES, Joyce Laura da Silva. Spectroscopies studies of porphyrins complexed with Cu²+. 2011. 104 f. Dissertação (Mestrado em Metodologias Analíticas e Aplicações) - UNICENTRO - Universidade Estadual do Centro Oeste, Guarapuava, 2011.http://localhost:8080/tede/handle/tede/320Porphyrins are very interesting because their favorables characteristics on biomedical applications. Paramagnetic metalloporphyrins have been studied and were exhibited promising results as contrast agents in nuclear magnetic resonance imaging. In aqueous medium, these compounds have the ability to form aggregates that minimize their effectiveness for therapeutic purposes. Therefore, the investigation of properties of porphyrin in the presence of biological systems model can support a better understanding of the interaction of porphyrins with tissues in the blood. In the present study we used spectroscopic techniques, to investigated the influence of pH, ionic strength in the two porphyrins complexed with Cu²+: meso-tetrakis (N-methyl-4-pyridyl),CuTMPyP and meso-tetrakis(2-bipyridinil-2-chlorine--ruthenium)CuTPyP{Ru(bipy)2Cl}4, and their interaction with biological model systems. As model systems we used the cationic surfactant cetyltrimethylammonium bromide (CTAB), the nonionic polyoxyethylene stearyl ether (20) (Brij 78) and anionic sodium dodecyl sulfate (SDS) in micellar form. The optical absorption showed that the CuTMPyP was insensitive in the pH range of 0,5 to 13,0 and only one specie was observed. This porphyrin were not influenced by ionic strength. No significant interaction of porphyrin with micelles of CTAB and Brij 78 were occurred. However, in the presence of SDS an effective interaction of porphyrin and SDS was observed. Optical spectra reveal a decrease of de Soret band at 425 nm with increasing SDS concentration until 3,12 x10 -4 mol L?¹. Over this range there is a small red shift in the Soret band and its absorbance increasing with SDS concentration. In conclusion, due to preferential interaction with anionic micelles, the electrostatic factor seems to be more relevant. This result was confirmed by EPR and MCD results. A superhyperfine structure corresponds to four equally coupled nitrogens, i.e., nine lines pattern was observed. Then in the used pH range there is neither change in the binding of Cu in the porphyrin ring nor axial ligands exchanges. The value of g0?2,075 was calculated. Three distinct species in solution equilibrium to the optical absorption spectrum for CuTPyP{Ru(bipy)2Cl}4 were showed. The pK1=3,5± 0,5 and pK2=10,6± 0,6, whose forms are diprotonated, monoprotonated and no protonated were reported. In this case, the ionic strength above 5,9x10-1 mol.L?¹ were denoted. No significant interaction of porphyrin with micelles of CTAB and Brij 78 were occurred again. However, there was a high interaction with anionic surfactant. A decrease of de Soret band at 417 nm with increasing SDS concentration until 5,1x10-4 mol.L?¹ were observed. Thereafter, a small red shift in the Soret band and its absorbance increasing with SDS concentration were observed. One more time, the electrostatic factor was very relevant. The MCD and EPR were in agreement with this results. The hyperfine structure resulted from the interaction between delocalized ? electron and N magnetic nuclei was just observed in presence of SDS micelles. EPR data at 77 K presented a typical axial spectrum with g//?2.345 and g??2.026 for all situations. Due to high concentration of both porphyrins used, only free form of porphyrin and theirself interaction of SDS micelles were observed in MCD and EPR spectra. M oreover, the electrostatic factor proved to be the most important factor in interactions of porphyrins.As porfirinas são interessantes devido as suas favoráveis características de aplicação biomédicas. Estudos mostram que as metaloporfirinas paramagnéticas têm apresentado resultados promissores como agentes de contraste em imagens por ressonância magnética nuclear. Em meio aquoso, estes compostos têm a capacidade de formar agregados moleculares que minimizam sua eficiência para fins terapêuticos. Portanto, o estudo das propriedades espectroscópicas de porfirina na presença de sistemas biofísicos modelo pode subsidiar uma maior compreensão da interação das porfirinas com tecidos existentes em meio fisiológico.No presente trabalho, foram utilizadas técnicas espectroscópicas para investigar a influência do pH, força iônica em duas porfirinas complexas com Cu²+: meso-tetrakis (N-metil-4-piridil),CuTMPyP e meso-tetrakis(2-bipiridinil-2-cloro-1-rutênio) CuTPyP{Ru(bipy)2Cl}4 e interação destas com sistemas biofísicos modelo. Como modelo simplificado de membranas utilizou-se os surfactantes iônicos brometo de cetiltrimetilamônio (CTAB), dodecil sulfato de sódio (SDS) e o surfactante não iônico éter estearílico de polioxietileno 20 (Brij 78) na forma micelar. Os espectros eletrônicos mostraram que o comportamento espectroscópico da CuTMPyP foi independente do pH e da força iônica, pois variando-se o pH de 0,5 a 13,0 apenas uma espécie é observada em solução. Na presença de surfactantes foi observado que devido a fatores eletrostáticos não há uma interação efetiva dessa porfirina com as micelas de CTAB e BRIJ 78. Entretanto, na presença de SDS foi observada uma interação efetiva entre a porfirina e as micelas de SDS. Com o aumento da concentração de SDS em solução observou-se um decréscimo gradual na intensidade da banda de Soret inicialmente centrada em 425 nm até que a concentração de SDS atinja 3,12x10-4 mol.L?¹. Posteriormente a essa concentração inicia-se um deslocamento espectral para comprimento de ondas maiores e a intensidade de absorção da banda de Soret passa a aumentar com o aumento da concentração de SDS. Portanto, devido à interação preferencial com micelas aniônicas, ressalta-se a importância do fator eletrostático. Esses resultados foram confirmados por RPE e DCM. A estrutura hiperfina correspondente ao acoplamento com os quatros nitrogênios do anel macrocíclico. Não foram identificadas mudanças em função do pH nos ligantes axiais ao Cu. O valor calculado foi g0?2,075. Para a porfirina CuTPyP{Ru(bipy)2Cl}4 foram observadas três espécies distintas em solução, cujos valores de pH de transição foram pK1=3,5± 0,5 e pK2= 10,6± 0,6, para as formas diprotonada, monoprotonada e desprotonada. Neste caso, o comportamento espectral da porfirina sofre influência da força iônica, quando da presença de NaCl com concentração superior a 5,9x10 -1mol.L?¹. Não há interações efetivas entre a porfirina e os surfactantes CTAB e Brij 78. Todavia, a uma intensa interação com o surfactante aniônico. Um decréscimo da banda de Soret centrada em 417 nm foi observado com o aumento da concentração de SDS em solução até uma concentração igual a 5,1x10-4 mol.L?¹. Posteriormente, um discreto efeito batocrômico foi observado. Cita-se novamente, a influência dos fatores eletrostáticos. Os resultados de DCM e RPE corroboram com os obtidos por UV-Vis. A estrutura hiperfina resultante da interação do dos elétrons ? delocalizados sobre os núcleos de nitrogênios foram observado apenas na presença de micelas de SDS. Os espectros de RPE a 77K apresentam simetria axial com g//?2.345 e g??2.026 na presença e ausência de micelas. Devido à alta concentração de ambas as porfirinas empregadas, apenas a forma livre da porfirina e sua interação com micelas de SDS foram observadas através de DCM e RPE. Em suma, os fatores eletrostáticos se apresentaram como o fator mais importante no processo de interação das porfirinas.Made available in DSpace on 2016-09-20T12:27:16Z (GMT). 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dc.title.por.fl_str_mv ESTUDOS ESPECTROSCÓPICOS DE PORFIRINAS COMPLEXADAS COM Cu²+
dc.title.alternative.eng.fl_str_mv Spectroscopies studies of porphyrins complexed with Cu²+
title ESTUDOS ESPECTROSCÓPICOS DE PORFIRINAS COMPLEXADAS COM Cu²+
spellingShingle ESTUDOS ESPECTROSCÓPICOS DE PORFIRINAS COMPLEXADAS COM Cu²+
Gonçalves, Joyce Laura da Silva
porfirina
espectroscopia
micelas
porphyrins
spectroscopy
micelles
CIENCIAS EXATAS E DA TERRA::QUIMICA
title_short ESTUDOS ESPECTROSCÓPICOS DE PORFIRINAS COMPLEXADAS COM Cu²+
title_full ESTUDOS ESPECTROSCÓPICOS DE PORFIRINAS COMPLEXADAS COM Cu²+
title_fullStr ESTUDOS ESPECTROSCÓPICOS DE PORFIRINAS COMPLEXADAS COM Cu²+
title_full_unstemmed ESTUDOS ESPECTROSCÓPICOS DE PORFIRINAS COMPLEXADAS COM Cu²+
title_sort ESTUDOS ESPECTROSCÓPICOS DE PORFIRINAS COMPLEXADAS COM Cu²+
author Gonçalves, Joyce Laura da Silva
author_facet Gonçalves, Joyce Laura da Silva
author_role author
dc.contributor.advisor1.fl_str_mv Tominaga, Tania Toyomi
dc.contributor.advisor1ID.fl_str_mv CPF:78657845746
dc.contributor.advisor1Lattes.fl_str_mv http://lattes.cnpq.br/6909363427100376
dc.contributor.authorID.fl_str_mv CPF:05798154980
dc.contributor.authorLattes.fl_str_mv http://lattes.cnpq.br/6163800361294977
dc.contributor.author.fl_str_mv Gonçalves, Joyce Laura da Silva
contributor_str_mv Tominaga, Tania Toyomi
dc.subject.por.fl_str_mv porfirina
espectroscopia
micelas
topic porfirina
espectroscopia
micelas
porphyrins
spectroscopy
micelles
CIENCIAS EXATAS E DA TERRA::QUIMICA
dc.subject.eng.fl_str_mv porphyrins
spectroscopy
micelles
dc.subject.cnpq.fl_str_mv CIENCIAS EXATAS E DA TERRA::QUIMICA
description Porphyrins are very interesting because their favorables characteristics on biomedical applications. Paramagnetic metalloporphyrins have been studied and were exhibited promising results as contrast agents in nuclear magnetic resonance imaging. In aqueous medium, these compounds have the ability to form aggregates that minimize their effectiveness for therapeutic purposes. Therefore, the investigation of properties of porphyrin in the presence of biological systems model can support a better understanding of the interaction of porphyrins with tissues in the blood. In the present study we used spectroscopic techniques, to investigated the influence of pH, ionic strength in the two porphyrins complexed with Cu²+: meso-tetrakis (N-methyl-4-pyridyl),CuTMPyP and meso-tetrakis(2-bipyridinil-2-chlorine--ruthenium)CuTPyP{Ru(bipy)2Cl}4, and their interaction with biological model systems. As model systems we used the cationic surfactant cetyltrimethylammonium bromide (CTAB), the nonionic polyoxyethylene stearyl ether (20) (Brij 78) and anionic sodium dodecyl sulfate (SDS) in micellar form. The optical absorption showed that the CuTMPyP was insensitive in the pH range of 0,5 to 13,0 and only one specie was observed. This porphyrin were not influenced by ionic strength. No significant interaction of porphyrin with micelles of CTAB and Brij 78 were occurred. However, in the presence of SDS an effective interaction of porphyrin and SDS was observed. Optical spectra reveal a decrease of de Soret band at 425 nm with increasing SDS concentration until 3,12 x10 -4 mol L?¹. Over this range there is a small red shift in the Soret band and its absorbance increasing with SDS concentration. In conclusion, due to preferential interaction with anionic micelles, the electrostatic factor seems to be more relevant. This result was confirmed by EPR and MCD results. A superhyperfine structure corresponds to four equally coupled nitrogens, i.e., nine lines pattern was observed. Then in the used pH range there is neither change in the binding of Cu in the porphyrin ring nor axial ligands exchanges. The value of g0?2,075 was calculated. Three distinct species in solution equilibrium to the optical absorption spectrum for CuTPyP{Ru(bipy)2Cl}4 were showed. The pK1=3,5± 0,5 and pK2=10,6± 0,6, whose forms are diprotonated, monoprotonated and no protonated were reported. In this case, the ionic strength above 5,9x10-1 mol.L?¹ were denoted. No significant interaction of porphyrin with micelles of CTAB and Brij 78 were occurred again. However, there was a high interaction with anionic surfactant. A decrease of de Soret band at 417 nm with increasing SDS concentration until 5,1x10-4 mol.L?¹ were observed. Thereafter, a small red shift in the Soret band and its absorbance increasing with SDS concentration were observed. One more time, the electrostatic factor was very relevant. The MCD and EPR were in agreement with this results. The hyperfine structure resulted from the interaction between delocalized ? electron and N magnetic nuclei was just observed in presence of SDS micelles. EPR data at 77 K presented a typical axial spectrum with g//?2.345 and g??2.026 for all situations. Due to high concentration of both porphyrins used, only free form of porphyrin and theirself interaction of SDS micelles were observed in MCD and EPR spectra. M oreover, the electrostatic factor proved to be the most important factor in interactions of porphyrins.
publishDate 2011
dc.date.available.fl_str_mv 2011-05-25
dc.date.issued.fl_str_mv 2011-02-28
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dc.identifier.citation.fl_str_mv GONÇALVES, Joyce Laura da Silva. Spectroscopies studies of porphyrins complexed with Cu²+. 2011. 104 f. Dissertação (Mestrado em Metodologias Analíticas e Aplicações) - UNICENTRO - Universidade Estadual do Centro Oeste, Guarapuava, 2011.
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identifier_str_mv GONÇALVES, Joyce Laura da Silva. Spectroscopies studies of porphyrins complexed with Cu²+. 2011. 104 f. Dissertação (Mestrado em Metodologias Analíticas e Aplicações) - UNICENTRO - Universidade Estadual do Centro Oeste, Guarapuava, 2011.
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