Síntese, caracterizaҫão e reatividade de novos complexos de rutênio do tipo cis-[Ru(bpy)2L(X)](PF6)n (n= 1 e 3), bpy=2,2’-BIPIRIDINA, X=Cl− , NO2− , NO+ e L= 4-phpy e 4-pybz

Detalhes bibliográficos
Ano de defesa: 2023
Autor(a) principal: Manigat, Woodruff
Orientador(a): Lopes, Luiz Gonzaga de França
Banca de defesa: Não Informado pela instituição
Tipo de documento: Dissertação
Tipo de acesso: Acesso aberto
Idioma: por
Instituição de defesa: Não Informado pela instituição
Programa de Pós-Graduação: Não Informado pela instituição
Departamento: Não Informado pela instituição
País: Não Informado pela instituição
Palavras-chave em Português:
Link de acesso: http://www.repositorio.ufc.br/handle/riufc/72258
Resumo: Coordination compounds based on Ru(II) metal center have presented biological activities and applications for various diseases such as cancer, cardiovascular diseases (DCV), parasitosis, etc. Additionally, metallocomplex NO donors have been widely studied successfully as nitric oxide releasing agents, allowing them to act as pro-drugs stimulated by chemical or photochemical reduction to supplement nitric oxide deficiency that is associated with certain pathological states. Nitrosyl metal coordination compounds are successfully used as metallodrugs in the treatment of DCV, cancer etc. In view of the facts mentioned, this work aims to synthesize, characterize and study the reactivity of new ruthenium complexes of the type cis-[Ru(bpy)2L(X)](PF6)n (n=1 ou 3), bpy=2,2’- bipyridine, X= Cl−, NO2−, NO+ and L= 4- phenylpyridine (4-phpy) and analogue 4-pyridyl benzimidazole (4-pybz). The characterization was performed through vibrational spectroscopic techniques in the infrared region, uv-visible as well as computer simulations, 1H nuclear magnetic resonance and cyclic voltametry, supporting the proposed structures. The nitrosyl summed up complexes were then analyzed as to their ability to release nitric oxide (NO°) under different conditions. Spectroscopic follow-up during electrical potential application and under light irradiation (λirr=460nm) indicated the formation of aque-complex, suggesting the release of NOo. cPTIO was also used as a probe for detection of nitric oxide and indicated the release of NO/HNO after irradiation. Furthermore, nitrosyl complexes are likely to release NO/HNO when they react with thiol reducers (L-cysteine). Through the nitrosyl/nitro interconveration study for complexes cis-[Ru(NO)(bpy)2(4-phpy)]3+e cis-[Ru(NO)(bpy)2(4-pybz)]3+, it was found that the complexes react with the OH-ion forming the respective complex nitrite and that this reaction is reversible by pH adjustment. The first complex has an inflection point with pH and balance 2.10 and the second has two points of inflections with equilibrium pH 1,16 e 6,02. In the vascular relaxation test, the complexes cis-[Ru(NO2)(bpy)2(4-phpy)]+e cis-[Ru(NO2)(bpy)2(4-pybz)]+ are very promising, demonstrating excellent hypotensive activity.
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spelling Manigat, WoodruffSilva, Eduardo Henrique de SousaLopes, Luiz Gonzaga de França2023-05-12T18:17:14Z2023-05-12T18:17:14Z2023MANIGAT, Woodruff. Síntese, caracterizaҫão e reatividade de novos complexos de rutênio do tipo cis-[Ru(bpy)2L(X)](PF6)n (n= 1 e 3), bpy=2,2’-BIPIRIDINA, X= Cl−, NO2−, NO+ e L= 4-phpy e 4-pybz. 2023. 112 f. Dissertação (Mestrado em Química) - Universidade Federal do Ceará, Fortaleza, 2023.http://www.repositorio.ufc.br/handle/riufc/72258Coordination compounds based on Ru(II) metal center have presented biological activities and applications for various diseases such as cancer, cardiovascular diseases (DCV), parasitosis, etc. Additionally, metallocomplex NO donors have been widely studied successfully as nitric oxide releasing agents, allowing them to act as pro-drugs stimulated by chemical or photochemical reduction to supplement nitric oxide deficiency that is associated with certain pathological states. Nitrosyl metal coordination compounds are successfully used as metallodrugs in the treatment of DCV, cancer etc. In view of the facts mentioned, this work aims to synthesize, characterize and study the reactivity of new ruthenium complexes of the type cis-[Ru(bpy)2L(X)](PF6)n (n=1 ou 3), bpy=2,2’- bipyridine, X= Cl−, NO2−, NO+ and L= 4- phenylpyridine (4-phpy) and analogue 4-pyridyl benzimidazole (4-pybz). The characterization was performed through vibrational spectroscopic techniques in the infrared region, uv-visible as well as computer simulations, 1H nuclear magnetic resonance and cyclic voltametry, supporting the proposed structures. The nitrosyl summed up complexes were then analyzed as to their ability to release nitric oxide (NO°) under different conditions. Spectroscopic follow-up during electrical potential application and under light irradiation (λirr=460nm) indicated the formation of aque-complex, suggesting the release of NOo. cPTIO was also used as a probe for detection of nitric oxide and indicated the release of NO/HNO after irradiation. Furthermore, nitrosyl complexes are likely to release NO/HNO when they react with thiol reducers (L-cysteine). Through the nitrosyl/nitro interconveration study for complexes cis-[Ru(NO)(bpy)2(4-phpy)]3+e cis-[Ru(NO)(bpy)2(4-pybz)]3+, it was found that the complexes react with the OH-ion forming the respective complex nitrite and that this reaction is reversible by pH adjustment. The first complex has an inflection point with pH and balance 2.10 and the second has two points of inflections with equilibrium pH 1,16 e 6,02. In the vascular relaxation test, the complexes cis-[Ru(NO2)(bpy)2(4-phpy)]+e cis-[Ru(NO2)(bpy)2(4-pybz)]+ are very promising, demonstrating excellent hypotensive activity.CAPES. Período Abril 2020 - Agosto 2022.Compostos de coordenação tendo como centro metálico Ru(II) têm apresentado atividades biológicas e aplicações para diversas doenças como câncer, doenças cardiovasculares (DCV), parasitoses etc. Adicionalmente, metalocomplexos doadores de NO tem sido amplamente estudados com sucesso como agentes liberadores de óxido nítrico, permitindo atuarem como pro-drogas estimuladas por redução química ou fotoquímica para suplementar a deficiência de óxido nítrico que está associado a certos estados patológicos. Compostos de coordenação de metal nitrosil são usados com sucesso como metalofármacos no tratamento de DCV, câncer etc. Diante dos fatos mencionados, este trabalho tem como objetivo sintetizar, caracterizar e estudar a reatividade de novos complexos de rutênio do tipo cis-[Ru(bpy)2L(X)](PF6)n (n=1 e 3), bpy=2,2’-bipiridina, X= Cl−, NO2−, NO+ e L= 4-fenilpiridina (4-phpy) e do análogo 4-piridilbenzimidazol (4-pybz). A caracterização foi realizada através de técnicas espectroscópicas vibracional na região do infravermelho, UV-visível bem como simulações computacionais, ressonância magnética nuclear 1H e voltametria cíclica, sustentando as estruturas propostas. Os nitrosilo complexos sintetizados foram então analisados quanto a sua capacidade de liberação de óxido nítrico (NOo) sob diferentes condições. O acompanhamento espectroscópico durante aplicação de potencial elétrico e sob irradiação de luz (λirr=460nm) indicou a formação de aquo-complexo, sugerindo a liberação de NOo. cPTIO foi utilizado como sonda para deteção de óxido nítrico e indicou a liberação de NO/HNO após irradiação. Além disso, os nitrosilocomplexos mostram susceptíveis a liberar o NO/HNO quando reagem com redutores tiólicos (L-cisteína). Através do estudo de interconverção nitrosil/nitro para os complexos cis-[Ru(NO)(bpy)2(4-phpy)]3+ e cis-[Ru(NO)(bpy)2(4-pybz)]3+, verificou-se que os compostos reagem com o íon OH- formando os respectivos nitritocomplexos e que esta reação é reversível mediante ajuste do pH. O primeiro complexo apresenta um ponto de inflexão com pH e equilibro 2,10 e o segundo tem dois pontos de inflexões com pH de equilibro 1,16 e 6,02. No teste de relaxamento vascular, os complexos cis-[Ru(NO2)(bpy)2(4-phpy)]+ e cis-[Ru(NO2)(bpy)2(4-pybz)]+ se mostram bastante promissores demonstrando uma excelente atividade hipotensora.Óxido nítricoRutênioDoador de NOSíntese, caracterizaҫão e reatividade de novos complexos de rutênio do tipo cis-[Ru(bpy)2L(X)](PF6)n (n= 1 e 3), bpy=2,2’-BIPIRIDINA, X=Cl− , NO2− , NO+ e L= 4-phpy e 4-pybzSynthesis, characterization and reactivity of new ruthenium complexs of the type cis-[Ru(bpy)2L(X)](PF6)n (n= 1 and 3), bpy=2,2'-BIPYRIDINE, X= Cl−, NO2−, NO+ and L= 4-phpy and 4-pybzSynthesis, characterization and reactivity of new ruthenium complex of the type cis-[Ru(bpy)2L(X)](PF6)n (n= 1 and 3), bpy=2,2'-BIPYRIDINE, X= Cl−, NO2−, NO+ and L= 4-phpy and 4-pybzinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisporreponame:Repositório Institucional da Universidade Federal do Ceará (UFC)instname:Universidade Federal do Ceará (UFC)instacron:UFCinfo:eu-repo/semantics/openAccessLICENSElicense.txtlicense.txttext/plain; charset=utf-81748http://repositorio.ufc.br/bitstream/riufc/72258/6/license.txt8a4605be74aa9ea9d79846c1fba20a33MD56ORIGINAL2023_dis_wmanigat.pdf2023_dis_wmanigat.pdfapplication/pdf8377452http://repositorio.ufc.br/bitstream/riufc/72258/5/2023_dis_wmanigat.pdf64c56b893a6889b398b5a6ecf4b2f301MD55riufc/722582023-05-15 12:21:31.867oai:repositorio.ufc.br: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Repositório InstitucionalPUBhttp://www.repositorio.ufc.br/ri-oai/requestbu@ufc.br || repositorio@ufc.bropendoar:2023-05-15T15:21:31Repositório Institucional da Universidade Federal do Ceará (UFC) - Universidade Federal do Ceará (UFC)false
dc.title.pt_BR.fl_str_mv Síntese, caracterizaҫão e reatividade de novos complexos de rutênio do tipo cis-[Ru(bpy)2L(X)](PF6)n (n= 1 e 3), bpy=2,2’-BIPIRIDINA, X=Cl− , NO2− , NO+ e L= 4-phpy e 4-pybz
dc.title.alternative.pt_BR.fl_str_mv Synthesis, characterization and reactivity of new ruthenium complexs of the type cis-[Ru(bpy)2L(X)](PF6)n (n= 1 and 3), bpy=2,2'-BIPYRIDINE, X= Cl−, NO2−, NO+ and L= 4-phpy and 4-pybz
dc.title.en.pt_BR.fl_str_mv Synthesis, characterization and reactivity of new ruthenium complex of the type cis-[Ru(bpy)2L(X)](PF6)n (n= 1 and 3), bpy=2,2'-BIPYRIDINE, X= Cl−, NO2−, NO+ and L= 4-phpy and 4-pybz
title Síntese, caracterizaҫão e reatividade de novos complexos de rutênio do tipo cis-[Ru(bpy)2L(X)](PF6)n (n= 1 e 3), bpy=2,2’-BIPIRIDINA, X=Cl− , NO2− , NO+ e L= 4-phpy e 4-pybz
spellingShingle Síntese, caracterizaҫão e reatividade de novos complexos de rutênio do tipo cis-[Ru(bpy)2L(X)](PF6)n (n= 1 e 3), bpy=2,2’-BIPIRIDINA, X=Cl− , NO2− , NO+ e L= 4-phpy e 4-pybz
Manigat, Woodruff
Óxido nítrico
Rutênio
Doador de NO
title_short Síntese, caracterizaҫão e reatividade de novos complexos de rutênio do tipo cis-[Ru(bpy)2L(X)](PF6)n (n= 1 e 3), bpy=2,2’-BIPIRIDINA, X=Cl− , NO2− , NO+ e L= 4-phpy e 4-pybz
title_full Síntese, caracterizaҫão e reatividade de novos complexos de rutênio do tipo cis-[Ru(bpy)2L(X)](PF6)n (n= 1 e 3), bpy=2,2’-BIPIRIDINA, X=Cl− , NO2− , NO+ e L= 4-phpy e 4-pybz
title_fullStr Síntese, caracterizaҫão e reatividade de novos complexos de rutênio do tipo cis-[Ru(bpy)2L(X)](PF6)n (n= 1 e 3), bpy=2,2’-BIPIRIDINA, X=Cl− , NO2− , NO+ e L= 4-phpy e 4-pybz
title_full_unstemmed Síntese, caracterizaҫão e reatividade de novos complexos de rutênio do tipo cis-[Ru(bpy)2L(X)](PF6)n (n= 1 e 3), bpy=2,2’-BIPIRIDINA, X=Cl− , NO2− , NO+ e L= 4-phpy e 4-pybz
title_sort Síntese, caracterizaҫão e reatividade de novos complexos de rutênio do tipo cis-[Ru(bpy)2L(X)](PF6)n (n= 1 e 3), bpy=2,2’-BIPIRIDINA, X=Cl− , NO2− , NO+ e L= 4-phpy e 4-pybz
author Manigat, Woodruff
author_facet Manigat, Woodruff
author_role author
dc.contributor.co-advisor.none.fl_str_mv Silva, Eduardo Henrique de Sousa
dc.contributor.author.fl_str_mv Manigat, Woodruff
dc.contributor.advisor1.fl_str_mv Lopes, Luiz Gonzaga de França
contributor_str_mv Lopes, Luiz Gonzaga de França
dc.subject.por.fl_str_mv Óxido nítrico
Rutênio
Doador de NO
topic Óxido nítrico
Rutênio
Doador de NO
description Coordination compounds based on Ru(II) metal center have presented biological activities and applications for various diseases such as cancer, cardiovascular diseases (DCV), parasitosis, etc. Additionally, metallocomplex NO donors have been widely studied successfully as nitric oxide releasing agents, allowing them to act as pro-drugs stimulated by chemical or photochemical reduction to supplement nitric oxide deficiency that is associated with certain pathological states. Nitrosyl metal coordination compounds are successfully used as metallodrugs in the treatment of DCV, cancer etc. In view of the facts mentioned, this work aims to synthesize, characterize and study the reactivity of new ruthenium complexes of the type cis-[Ru(bpy)2L(X)](PF6)n (n=1 ou 3), bpy=2,2’- bipyridine, X= Cl−, NO2−, NO+ and L= 4- phenylpyridine (4-phpy) and analogue 4-pyridyl benzimidazole (4-pybz). The characterization was performed through vibrational spectroscopic techniques in the infrared region, uv-visible as well as computer simulations, 1H nuclear magnetic resonance and cyclic voltametry, supporting the proposed structures. The nitrosyl summed up complexes were then analyzed as to their ability to release nitric oxide (NO°) under different conditions. Spectroscopic follow-up during electrical potential application and under light irradiation (λirr=460nm) indicated the formation of aque-complex, suggesting the release of NOo. cPTIO was also used as a probe for detection of nitric oxide and indicated the release of NO/HNO after irradiation. Furthermore, nitrosyl complexes are likely to release NO/HNO when they react with thiol reducers (L-cysteine). Through the nitrosyl/nitro interconveration study for complexes cis-[Ru(NO)(bpy)2(4-phpy)]3+e cis-[Ru(NO)(bpy)2(4-pybz)]3+, it was found that the complexes react with the OH-ion forming the respective complex nitrite and that this reaction is reversible by pH adjustment. The first complex has an inflection point with pH and balance 2.10 and the second has two points of inflections with equilibrium pH 1,16 e 6,02. In the vascular relaxation test, the complexes cis-[Ru(NO2)(bpy)2(4-phpy)]+e cis-[Ru(NO2)(bpy)2(4-pybz)]+ are very promising, demonstrating excellent hypotensive activity.
publishDate 2023
dc.date.accessioned.fl_str_mv 2023-05-12T18:17:14Z
dc.date.available.fl_str_mv 2023-05-12T18:17:14Z
dc.date.issued.fl_str_mv 2023
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.citation.fl_str_mv MANIGAT, Woodruff. Síntese, caracterizaҫão e reatividade de novos complexos de rutênio do tipo cis-[Ru(bpy)2L(X)](PF6)n (n= 1 e 3), bpy=2,2’-BIPIRIDINA, X= Cl−, NO2−, NO+ e L= 4-phpy e 4-pybz. 2023. 112 f. Dissertação (Mestrado em Química) - Universidade Federal do Ceará, Fortaleza, 2023.
dc.identifier.uri.fl_str_mv http://www.repositorio.ufc.br/handle/riufc/72258
identifier_str_mv MANIGAT, Woodruff. Síntese, caracterizaҫão e reatividade de novos complexos de rutênio do tipo cis-[Ru(bpy)2L(X)](PF6)n (n= 1 e 3), bpy=2,2’-BIPIRIDINA, X= Cl−, NO2−, NO+ e L= 4-phpy e 4-pybz. 2023. 112 f. Dissertação (Mestrado em Química) - Universidade Federal do Ceará, Fortaleza, 2023.
url http://www.repositorio.ufc.br/handle/riufc/72258
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