Hidroxilação biomimética de hidrocarbonetos catalisada por Mn(III) N-alquilpiridilporfirinas suportadas em sílica-gel ou sílica-gel funcionalizada com grupo cloropropila
Autor(a) principal: | |
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Data de Publicação: | 2021 |
Tipo de documento: | Dissertação |
Idioma: | por |
Título da fonte: | Biblioteca Digital de Teses e Dissertações da UFPB |
Texto Completo: | https://repositorio.ufpb.br/jspui/handle/123456789/21289 |
Resumo: | Mn(III) porphyrins have been extensively investigated as biomimetic oxidoreductase catalysts for hydrocarbon oxidation. In this work, two classes of catalysts heterogenized in silicas were used as models of cytochrome P450. One class corresponded to the materials containing the three isomers of Mn(III) N- pyridylporphyrins covalently immobilized via quaternization on chromatographic silica gel 60 modified with chloropropyl groups (Sil-Cl) to result in the materials Sil-Cl/MnPY (Y = 1, 2, 3 , corresponding to the ortho, meta and para isomers, in that order). The other class of catalysts corresponded to the materials containing the three isomers of the N-methylpyridinioporphyrins of Mn(III) electrostatically heterogenized in unmodified chromatographic silica gel 60 (SiO2) generating the solids SiO2/MnY (Y = 4, 5, 6, corresponding to the ortho, meta and para isomers, in that order). The catalytic efficiency and selectivity of these six materials were evaluated with respect to the nature of the isomer and the support using the hydroxylation of cyclic or acyclic alkanes (cyclohexane, adamantane and n-heptane) by iodosylbenzene (PhIO) as model reactions. In addition, the oxidation of cyclohexanol to cyclohexanone was also evaluated. Control reactions with the Mn porphyrin precursors under homogeneous conditions were also carried out. The reuse studies showed that the supported catalysts were resistant to oxidative destruction and/or leaching, with little effect on efficiency and selectivity throughout the reuse. In general, Sil-Cl/MnPY materials proved to be more efficient and selective than SiO2/MnPY. This can be associated with the modification of the Sil-Cl silica surface, which renders the material more lipophilic, resembling some the biological features of the cytochromes P450. The results with both Sil-Cl/MnPY (Y = 1, 2, 3) and SiO2/MnY (Y = 4, 5, 6) materials were compared with our previous studies with mesoporous Santa Barbara Amorphous No 15 (SBA-15) silica-based materials, whose reaction conditions are the most closely related to the ones in the current study. The results showed that Sil-Cl/MnPY (Y = 1, 2, 3) and SiO2/MnPY (Y = 4, 5, 6) catalysts were more efficient hydroxylation catalysts than the corresponding materials with SBA-15 and more practical, given the widespread availability and affordability of ordinary chromatographic silica gel 60. All catalysts were evaluated in three consecutive reaction cycles with at least three replicates, showing reproducible catalytic efficiency and robustness. Sil-Cl/MnPY (Y = 1, 2, 3) materials were the most selective toward n-heptane hydroxylation. Among the catalysts, Mn(III) 2-N-pyridylporphyrin immobilized covalently via quaternization to Sil-Cl, Sil-Cl/MnP1, was considered the best catalyst in terms of stability against oxidative destruction, yields, selectivity, and recyclability. |
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Hidroxilação biomimética de hidrocarbonetos catalisada por Mn(III) N-alquilpiridilporfirinas suportadas em sílica-gel ou sílica-gel funcionalizada com grupo cloropropilaCatálise heterogêneaMn-porfirinas catiônicasOxifuncionalizaçãoAlcanosCitocromos P450Sílica-gelHeterogeneous catalysisCationic Mn-porphyrinsOxyfunctionalizationAlkanesCytochrome P450CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAMn(III) porphyrins have been extensively investigated as biomimetic oxidoreductase catalysts for hydrocarbon oxidation. In this work, two classes of catalysts heterogenized in silicas were used as models of cytochrome P450. One class corresponded to the materials containing the three isomers of Mn(III) N- pyridylporphyrins covalently immobilized via quaternization on chromatographic silica gel 60 modified with chloropropyl groups (Sil-Cl) to result in the materials Sil-Cl/MnPY (Y = 1, 2, 3 , corresponding to the ortho, meta and para isomers, in that order). The other class of catalysts corresponded to the materials containing the three isomers of the N-methylpyridinioporphyrins of Mn(III) electrostatically heterogenized in unmodified chromatographic silica gel 60 (SiO2) generating the solids SiO2/MnY (Y = 4, 5, 6, corresponding to the ortho, meta and para isomers, in that order). The catalytic efficiency and selectivity of these six materials were evaluated with respect to the nature of the isomer and the support using the hydroxylation of cyclic or acyclic alkanes (cyclohexane, adamantane and n-heptane) by iodosylbenzene (PhIO) as model reactions. In addition, the oxidation of cyclohexanol to cyclohexanone was also evaluated. Control reactions with the Mn porphyrin precursors under homogeneous conditions were also carried out. The reuse studies showed that the supported catalysts were resistant to oxidative destruction and/or leaching, with little effect on efficiency and selectivity throughout the reuse. In general, Sil-Cl/MnPY materials proved to be more efficient and selective than SiO2/MnPY. This can be associated with the modification of the Sil-Cl silica surface, which renders the material more lipophilic, resembling some the biological features of the cytochromes P450. The results with both Sil-Cl/MnPY (Y = 1, 2, 3) and SiO2/MnY (Y = 4, 5, 6) materials were compared with our previous studies with mesoporous Santa Barbara Amorphous No 15 (SBA-15) silica-based materials, whose reaction conditions are the most closely related to the ones in the current study. The results showed that Sil-Cl/MnPY (Y = 1, 2, 3) and SiO2/MnPY (Y = 4, 5, 6) catalysts were more efficient hydroxylation catalysts than the corresponding materials with SBA-15 and more practical, given the widespread availability and affordability of ordinary chromatographic silica gel 60. All catalysts were evaluated in three consecutive reaction cycles with at least three replicates, showing reproducible catalytic efficiency and robustness. Sil-Cl/MnPY (Y = 1, 2, 3) materials were the most selective toward n-heptane hydroxylation. Among the catalysts, Mn(III) 2-N-pyridylporphyrin immobilized covalently via quaternization to Sil-Cl, Sil-Cl/MnP1, was considered the best catalyst in terms of stability against oxidative destruction, yields, selectivity, and recyclability.Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPESMn(III)-porfirinas têm sido amplamente investigadas como catalisadores biomiméticos de oxidorredutases para oxidação de hidrocarbonetos. Neste trabalho, foram utilizadas duas classes de catalisadores heterogeneizados em sílica cromatográfica 60 como modelos dos citocromos P450. Uma classe corresponde aos materiais contendo os três isômeros das N-piridilporfirinas de Mn(III) covalentemente imobilizados via quaternização em sílica-gel modificada com grupos cloropropila (Sil-Cl) para resultar nos materiais Sil-Cl/MnPY (Y = 1, 2, 3, respectivos aos isômeros orto, meta e para, nesta ordem). A outra classe de catalisadores corresponde aos materiais contendo os três isômeros das N-metilpiridinioporfirinas de Mn(III) heterogeneizados eletrostaticamente em sílica-gel cromatográfica 60 não modificada (SiO2) gerando os sólidos SiO2/MnPY (Y= 4, 5, 6, respectivos aos isômeros orto, meta e para, nesta ordem). A eficiência e a seletividade catalíticas destes seis materiais foram avaliadas quanto à natureza do isômero e do suporte na hidroxilação de alcanos cíclicos e acíclico modelos (ciclohexano, adamantano e n-heptano) tendo iodosilbenzeno (PhIO) como agente oxidante. Além disto, foi avaliada a oxidação do ciclohexanol a ciclohexanona. As reações controles com os complexos porfirínicos precursores em meio homogêneo também foram realizadas. Os estudos de reúso apontaram que os catalisadores suportados foram resistentes à destruição oxidativa e/ou lixiviação, com efeito pequeno na eficiência e seletividade ao longo dos reúsos. De um modo geral, a classe Sil-Cl/MnPY se mostrou mais eficiente e seletiva do que a SiO2/MnPY. Isto pode ser associado à modificação da superfície da sílica Sil-Cl que atribui características mais lipofílicas ao material, tornando-o mais similar ao modelo biológico dos citocromos P450. Ambos os materiais Sil-Cl/MnPY (Y= 1, 2, 3) e SiO2/MnY (Y= 4, 5, 6) foram comparados com os materiais à base de sílica mesoporosa Santa Barbara Amorphous No 15 (SBA-15) de estudos anteriores do grupo de pesquisa por serem os únicos da literatura a utilizarem condições reacionais semelhantes às deste trabalho. Os resultados apontaram que os catalisadores Sil-Cl/MnPY (Y= 1, 2, 3) e SiO2/MnY (Y= 4, 5, 6) foram mais eficientes na hidroxilação do ciclohexano que os materiais respectivos com SBA-15 e mais viáveis ao uso devido à ampla disponibilidade e ao baixo custo da sílica-gel cromatográfica frente à SBA-15. Todos os catalisadores foram avaliados em três ciclos reacionais consecutivos com, no mínimo, três replicatas, mostrando a reprodutibilidade da eficiência catalítica. Os materiais da classe Sil-Cl/MnPY (Y= 1, 2, 3) foram os que conseguiram ser mais seletivos para a formação de produtos hidroxilados na reação com o substrato n-heptano. Dentre os catalisadores, a 2-N-piridilporfirina de Mn(III) imobilizada covalentemente via quaternização com na Sil-Cl, Sil-Cl/MnP1, foi considerado o melhor catalisador em termos de estabilidade à destruição oxidativa, rendimentos, seletividade e reciclabilidade.Universidade Federal da ParaíbaBrasilQuímicaPrograma de Pós-Graduação em QuímicaUFPBRebouças, Julio Santoshttp://lattes.cnpq.br/0305007181787906Pinto, Victor Hugo e Araújohttp://lattes.cnpq.br/6530603318552728Silva, Barbara de Mariz2021-10-28T16:41:44Z2021-03-102021-10-28T16:41:44Z2021-01-27info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesishttps://repositorio.ufpb.br/jspui/handle/123456789/21289porAttribution-NoDerivs 3.0 Brazilhttp://creativecommons.org/licenses/by-nd/3.0/br/info:eu-repo/semantics/openAccessreponame:Biblioteca Digital de Teses e Dissertações da UFPBinstname:Universidade Federal da Paraíba (UFPB)instacron:UFPB2022-08-09T17:22:27Zoai:repositorio.ufpb.br:123456789/21289Biblioteca Digital de Teses e Dissertaçõeshttps://repositorio.ufpb.br/PUBhttp://tede.biblioteca.ufpb.br:8080/oai/requestdiretoria@ufpb.br|| diretoria@ufpb.bropendoar:2022-08-09T17:22:27Biblioteca Digital de Teses e Dissertações da UFPB - Universidade Federal da Paraíba (UFPB)false |
dc.title.none.fl_str_mv |
Hidroxilação biomimética de hidrocarbonetos catalisada por Mn(III) N-alquilpiridilporfirinas suportadas em sílica-gel ou sílica-gel funcionalizada com grupo cloropropila |
title |
Hidroxilação biomimética de hidrocarbonetos catalisada por Mn(III) N-alquilpiridilporfirinas suportadas em sílica-gel ou sílica-gel funcionalizada com grupo cloropropila |
spellingShingle |
Hidroxilação biomimética de hidrocarbonetos catalisada por Mn(III) N-alquilpiridilporfirinas suportadas em sílica-gel ou sílica-gel funcionalizada com grupo cloropropila Silva, Barbara de Mariz Catálise heterogênea Mn-porfirinas catiônicas Oxifuncionalização Alcanos Citocromos P450 Sílica-gel Heterogeneous catalysis Cationic Mn-porphyrins Oxyfunctionalization Alkanes Cytochrome P450 CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Hidroxilação biomimética de hidrocarbonetos catalisada por Mn(III) N-alquilpiridilporfirinas suportadas em sílica-gel ou sílica-gel funcionalizada com grupo cloropropila |
title_full |
Hidroxilação biomimética de hidrocarbonetos catalisada por Mn(III) N-alquilpiridilporfirinas suportadas em sílica-gel ou sílica-gel funcionalizada com grupo cloropropila |
title_fullStr |
Hidroxilação biomimética de hidrocarbonetos catalisada por Mn(III) N-alquilpiridilporfirinas suportadas em sílica-gel ou sílica-gel funcionalizada com grupo cloropropila |
title_full_unstemmed |
Hidroxilação biomimética de hidrocarbonetos catalisada por Mn(III) N-alquilpiridilporfirinas suportadas em sílica-gel ou sílica-gel funcionalizada com grupo cloropropila |
title_sort |
Hidroxilação biomimética de hidrocarbonetos catalisada por Mn(III) N-alquilpiridilporfirinas suportadas em sílica-gel ou sílica-gel funcionalizada com grupo cloropropila |
author |
Silva, Barbara de Mariz |
author_facet |
Silva, Barbara de Mariz |
author_role |
author |
dc.contributor.none.fl_str_mv |
Rebouças, Julio Santos http://lattes.cnpq.br/0305007181787906 Pinto, Victor Hugo e Araújo http://lattes.cnpq.br/6530603318552728 |
dc.contributor.author.fl_str_mv |
Silva, Barbara de Mariz |
dc.subject.por.fl_str_mv |
Catálise heterogênea Mn-porfirinas catiônicas Oxifuncionalização Alcanos Citocromos P450 Sílica-gel Heterogeneous catalysis Cationic Mn-porphyrins Oxyfunctionalization Alkanes Cytochrome P450 CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
topic |
Catálise heterogênea Mn-porfirinas catiônicas Oxifuncionalização Alcanos Citocromos P450 Sílica-gel Heterogeneous catalysis Cationic Mn-porphyrins Oxyfunctionalization Alkanes Cytochrome P450 CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
Mn(III) porphyrins have been extensively investigated as biomimetic oxidoreductase catalysts for hydrocarbon oxidation. In this work, two classes of catalysts heterogenized in silicas were used as models of cytochrome P450. One class corresponded to the materials containing the three isomers of Mn(III) N- pyridylporphyrins covalently immobilized via quaternization on chromatographic silica gel 60 modified with chloropropyl groups (Sil-Cl) to result in the materials Sil-Cl/MnPY (Y = 1, 2, 3 , corresponding to the ortho, meta and para isomers, in that order). The other class of catalysts corresponded to the materials containing the three isomers of the N-methylpyridinioporphyrins of Mn(III) electrostatically heterogenized in unmodified chromatographic silica gel 60 (SiO2) generating the solids SiO2/MnY (Y = 4, 5, 6, corresponding to the ortho, meta and para isomers, in that order). The catalytic efficiency and selectivity of these six materials were evaluated with respect to the nature of the isomer and the support using the hydroxylation of cyclic or acyclic alkanes (cyclohexane, adamantane and n-heptane) by iodosylbenzene (PhIO) as model reactions. In addition, the oxidation of cyclohexanol to cyclohexanone was also evaluated. Control reactions with the Mn porphyrin precursors under homogeneous conditions were also carried out. The reuse studies showed that the supported catalysts were resistant to oxidative destruction and/or leaching, with little effect on efficiency and selectivity throughout the reuse. In general, Sil-Cl/MnPY materials proved to be more efficient and selective than SiO2/MnPY. This can be associated with the modification of the Sil-Cl silica surface, which renders the material more lipophilic, resembling some the biological features of the cytochromes P450. The results with both Sil-Cl/MnPY (Y = 1, 2, 3) and SiO2/MnY (Y = 4, 5, 6) materials were compared with our previous studies with mesoporous Santa Barbara Amorphous No 15 (SBA-15) silica-based materials, whose reaction conditions are the most closely related to the ones in the current study. The results showed that Sil-Cl/MnPY (Y = 1, 2, 3) and SiO2/MnPY (Y = 4, 5, 6) catalysts were more efficient hydroxylation catalysts than the corresponding materials with SBA-15 and more practical, given the widespread availability and affordability of ordinary chromatographic silica gel 60. All catalysts were evaluated in three consecutive reaction cycles with at least three replicates, showing reproducible catalytic efficiency and robustness. Sil-Cl/MnPY (Y = 1, 2, 3) materials were the most selective toward n-heptane hydroxylation. Among the catalysts, Mn(III) 2-N-pyridylporphyrin immobilized covalently via quaternization to Sil-Cl, Sil-Cl/MnP1, was considered the best catalyst in terms of stability against oxidative destruction, yields, selectivity, and recyclability. |
publishDate |
2021 |
dc.date.none.fl_str_mv |
2021-10-28T16:41:44Z 2021-03-10 2021-10-28T16:41:44Z 2021-01-27 |
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 |
https://repositorio.ufpb.br/jspui/handle/123456789/21289 |
url |
https://repositorio.ufpb.br/jspui/handle/123456789/21289 |
dc.language.iso.fl_str_mv |
por |
language |
por |
dc.rights.driver.fl_str_mv |
Attribution-NoDerivs 3.0 Brazil http://creativecommons.org/licenses/by-nd/3.0/br/ info:eu-repo/semantics/openAccess |
rights_invalid_str_mv |
Attribution-NoDerivs 3.0 Brazil http://creativecommons.org/licenses/by-nd/3.0/br/ |
eu_rights_str_mv |
openAccess |
dc.publisher.none.fl_str_mv |
Universidade Federal da Paraíba Brasil Química Programa de Pós-Graduação em Química UFPB |
publisher.none.fl_str_mv |
Universidade Federal da Paraíba Brasil Química Programa de Pós-Graduação em Química UFPB |
dc.source.none.fl_str_mv |
reponame:Biblioteca Digital de Teses e Dissertações da UFPB instname:Universidade Federal da Paraíba (UFPB) instacron:UFPB |
instname_str |
Universidade Federal da Paraíba (UFPB) |
instacron_str |
UFPB |
institution |
UFPB |
reponame_str |
Biblioteca Digital de Teses e Dissertações da UFPB |
collection |
Biblioteca Digital de Teses e Dissertações da UFPB |
repository.name.fl_str_mv |
Biblioteca Digital de Teses e Dissertações da UFPB - Universidade Federal da Paraíba (UFPB) |
repository.mail.fl_str_mv |
diretoria@ufpb.br|| diretoria@ufpb.br |
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1801842983414267904 |