Dinâmica metabólica em Piper gaudichaudianum: estudo das etapas de ciclização estereosseletiva do ácido gaudichaudianico
Autor(a) principal: | |
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Data de Publicação: | 2014 |
Tipo de documento: | Dissertação |
Idioma: | por |
Título da fonte: | Repositório Institucional da UNESP |
Texto Completo: | http://hdl.handle.net/11449/110848 |
Resumo: | The Piperaceae family comprises about 4000 species, and the genus Piper is the most abundant. Many species of this genus are used in folk medicine to treat various diseases. The wide biological potential of this family is due to the accumulation of different classes of secondary metabolites, among which stand out the prenylated derivatives of p-hydroxybenzoic acid and its cyclized products, known as chromenes and/or chromanes, which are characterized by the presence of a pyran ring fused with a benzene moieity. Piper gaudichaudianum, in particular, presents in its constitution the 2-methyl -2-(4'-methyl-3'-pentenyl)-8-(3''-methyl-2-butenyl)-2H-1-chromene-6-carboxylic acid, known as gaudichaudianic acid, a prenylated chromene that is the major metabolite in leaves and roots of this species. This compound has shown trypanocidal and antifungal activities. Chemical studies demonstrated the presence of two naturally occurring rare isomeric forms, (+)-S and (-)-R, gaudichaudianic acid, arousing the interest in further evaluations of their biosynthetic steps. Therefore, the present work aimed to study the biosynthetic pathway related to the cyclization step leading to the enantiomers of gaudichaudianic acid using prenylated benzoic acid derivatives as intermediates. The proposed chemical and enzymatic cyclizations were evaluated using as the precursor the 3-geranyl-4-hydroxy-5-(3'-methyl-2'-butenyl )benzoic acid, known as myrsinoic acid identified and isolated from P. gaudichaudianum. To evaluate the possibility of cyclization occur by chemical methods acidic media and heating conditions were used. Under these conditions the formation of gaudichaudianic acid was not observed, which shows that the cyclization may occur enzymatically, catalyzed by a cyclase-type enzyme. Enzyme assays were performed using soluble and microsomal fractions obtained from the leaves P. gaudichaudianum and using the 3-geranyl-4-hydroxy-5-(3'-methyl-2'-butenyl) benzoic... |
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Dinâmica metabólica em Piper gaudichaudianum: estudo das etapas de ciclização estereosseletiva do ácido gaudichaudianicoQuimica organicaBiossinteseAtividade antifúngicaBiosynthesisThe Piperaceae family comprises about 4000 species, and the genus Piper is the most abundant. Many species of this genus are used in folk medicine to treat various diseases. The wide biological potential of this family is due to the accumulation of different classes of secondary metabolites, among which stand out the prenylated derivatives of p-hydroxybenzoic acid and its cyclized products, known as chromenes and/or chromanes, which are characterized by the presence of a pyran ring fused with a benzene moieity. Piper gaudichaudianum, in particular, presents in its constitution the 2-methyl -2-(4'-methyl-3'-pentenyl)-8-(3''-methyl-2-butenyl)-2H-1-chromene-6-carboxylic acid, known as gaudichaudianic acid, a prenylated chromene that is the major metabolite in leaves and roots of this species. This compound has shown trypanocidal and antifungal activities. Chemical studies demonstrated the presence of two naturally occurring rare isomeric forms, (+)-S and (-)-R, gaudichaudianic acid, arousing the interest in further evaluations of their biosynthetic steps. Therefore, the present work aimed to study the biosynthetic pathway related to the cyclization step leading to the enantiomers of gaudichaudianic acid using prenylated benzoic acid derivatives as intermediates. The proposed chemical and enzymatic cyclizations were evaluated using as the precursor the 3-geranyl-4-hydroxy-5-(3'-methyl-2'-butenyl )benzoic acid, known as myrsinoic acid identified and isolated from P. gaudichaudianum. To evaluate the possibility of cyclization occur by chemical methods acidic media and heating conditions were used. Under these conditions the formation of gaudichaudianic acid was not observed, which shows that the cyclization may occur enzymatically, catalyzed by a cyclase-type enzyme. Enzyme assays were performed using soluble and microsomal fractions obtained from the leaves P. gaudichaudianum and using the 3-geranyl-4-hydroxy-5-(3'-methyl-2'-butenyl) benzoic...A família Piperaceae compreende aproximadamente 4000 espécies, sendo que o gênero Piper é o mais abundante. Muitas espécies desse gênero são utilizadas na medicina tradicional para o tratamento de diversas enfermidades. A ampla potencialidade biológica dessa família deve-se ao acúmulo de diferentes classes de metabólitos secundários, dentre os quais, destacam-se os derivados prenilados do ácido p-hidroxibenzoico e seus produtos ciclizados, denominados cromenos e/ou cromanos, que apresentam como característica química fundamental a presença de um anel pirano fundido a um anel benzeno. A espécie Piper gaudichaudianum em particular, apresenta em sua constituição o ácido 2-metil-2-(4’-metil-3’-pentenil)-8-(3’’-metil-2’’-butenil)-2H-1-cromeno-6-carboxílico, conhecido como ácido gaudichaudiânico, um cromeno prenilado que além de ser o metabólito majoritário em folhas e raízes dessa espécie, possui conhecida atividade tripanocida e antifúngica frente a fitopatógenos. Estudos químicos mostraram a rara presença das duas formas isoméricas naturais, ()-S e ()-R, do ácido gaudichaudiânico, durante o isolamento desse composto, despertando ainda mais o interesse na avaliação de suas etapas biossintéticas. Logo, o presente trabalho teve como principal objetivo estudar a etapa de formação dos enantiomeros, que devem ser formados durante o processo de ciclização de um intermediário geranilado derivado do ácido benzoico para a formação do anel benzopirânico. As propostas de ciclização química e enzimática foram avaliadas utilizando como precursor o ácido 3-geranil-4-hidroxi-5-(3’-metil-2’-butenil)benzoico conhecido como ácido myrsinoico A, identificado e isolado da espécie P. gaudichaudianum. Alguns testes para a avaliação da possibilidade da ciclização se dar por métodos químicos mostrou que em meio ácido e sob aquecimento não foi observada a formação do ácido gaudichaudiânico...Universidade Estadual Paulista (Unesp)Furlan, Maysa [UNESP]Batista Júnior, João Marcos [UNESP]Universidade Estadual Paulista (Unesp)Carvalho, Amanda Uliana de [UNESP]2014-12-02T11:16:39Z2014-12-02T11:16:39Z2014-01-24info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesis107 f. : il.application/pdfCARVALHO, Amanda Uliana de. Dinâmica metabólica em Piper gaudichaudianum: estudo das etapas de ciclização estereosseletiva do ácido gaudichaudianico. 2014. 107 f. Dissertação (mestrado) - Universidade Estadual Paulista Júlio de Mesquita Filho, Instituto de Química de Araraquara, 2014.http://hdl.handle.net/11449/110848000773472000773472.pdf33004030072P81308042794786872Alephreponame:Repositório Institucional da UNESPinstname:Universidade Estadual Paulista (UNESP)instacron:UNESPporinfo:eu-repo/semantics/openAccess2023-10-02T06:04:48Zoai:repositorio.unesp.br:11449/110848Repositório InstitucionalPUBhttp://repositorio.unesp.br/oai/requestopendoar:29462024-08-05T13:45:52.761538Repositório Institucional da UNESP - Universidade Estadual Paulista (UNESP)false |
dc.title.none.fl_str_mv |
Dinâmica metabólica em Piper gaudichaudianum: estudo das etapas de ciclização estereosseletiva do ácido gaudichaudianico |
title |
Dinâmica metabólica em Piper gaudichaudianum: estudo das etapas de ciclização estereosseletiva do ácido gaudichaudianico |
spellingShingle |
Dinâmica metabólica em Piper gaudichaudianum: estudo das etapas de ciclização estereosseletiva do ácido gaudichaudianico Carvalho, Amanda Uliana de [UNESP] Quimica organica Biossintese Atividade antifúngica Biosynthesis |
title_short |
Dinâmica metabólica em Piper gaudichaudianum: estudo das etapas de ciclização estereosseletiva do ácido gaudichaudianico |
title_full |
Dinâmica metabólica em Piper gaudichaudianum: estudo das etapas de ciclização estereosseletiva do ácido gaudichaudianico |
title_fullStr |
Dinâmica metabólica em Piper gaudichaudianum: estudo das etapas de ciclização estereosseletiva do ácido gaudichaudianico |
title_full_unstemmed |
Dinâmica metabólica em Piper gaudichaudianum: estudo das etapas de ciclização estereosseletiva do ácido gaudichaudianico |
title_sort |
Dinâmica metabólica em Piper gaudichaudianum: estudo das etapas de ciclização estereosseletiva do ácido gaudichaudianico |
author |
Carvalho, Amanda Uliana de [UNESP] |
author_facet |
Carvalho, Amanda Uliana de [UNESP] |
author_role |
author |
dc.contributor.none.fl_str_mv |
Furlan, Maysa [UNESP] Batista Júnior, João Marcos [UNESP] Universidade Estadual Paulista (Unesp) |
dc.contributor.author.fl_str_mv |
Carvalho, Amanda Uliana de [UNESP] |
dc.subject.por.fl_str_mv |
Quimica organica Biossintese Atividade antifúngica Biosynthesis |
topic |
Quimica organica Biossintese Atividade antifúngica Biosynthesis |
description |
The Piperaceae family comprises about 4000 species, and the genus Piper is the most abundant. Many species of this genus are used in folk medicine to treat various diseases. The wide biological potential of this family is due to the accumulation of different classes of secondary metabolites, among which stand out the prenylated derivatives of p-hydroxybenzoic acid and its cyclized products, known as chromenes and/or chromanes, which are characterized by the presence of a pyran ring fused with a benzene moieity. Piper gaudichaudianum, in particular, presents in its constitution the 2-methyl -2-(4'-methyl-3'-pentenyl)-8-(3''-methyl-2-butenyl)-2H-1-chromene-6-carboxylic acid, known as gaudichaudianic acid, a prenylated chromene that is the major metabolite in leaves and roots of this species. This compound has shown trypanocidal and antifungal activities. Chemical studies demonstrated the presence of two naturally occurring rare isomeric forms, (+)-S and (-)-R, gaudichaudianic acid, arousing the interest in further evaluations of their biosynthetic steps. Therefore, the present work aimed to study the biosynthetic pathway related to the cyclization step leading to the enantiomers of gaudichaudianic acid using prenylated benzoic acid derivatives as intermediates. The proposed chemical and enzymatic cyclizations were evaluated using as the precursor the 3-geranyl-4-hydroxy-5-(3'-methyl-2'-butenyl )benzoic acid, known as myrsinoic acid identified and isolated from P. gaudichaudianum. To evaluate the possibility of cyclization occur by chemical methods acidic media and heating conditions were used. Under these conditions the formation of gaudichaudianic acid was not observed, which shows that the cyclization may occur enzymatically, catalyzed by a cyclase-type enzyme. Enzyme assays were performed using soluble and microsomal fractions obtained from the leaves P. gaudichaudianum and using the 3-geranyl-4-hydroxy-5-(3'-methyl-2'-butenyl) benzoic... |
publishDate |
2014 |
dc.date.none.fl_str_mv |
2014-12-02T11:16:39Z 2014-12-02T11:16:39Z 2014-01-24 |
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 |
CARVALHO, Amanda Uliana de. Dinâmica metabólica em Piper gaudichaudianum: estudo das etapas de ciclização estereosseletiva do ácido gaudichaudianico. 2014. 107 f. Dissertação (mestrado) - Universidade Estadual Paulista Júlio de Mesquita Filho, Instituto de Química de Araraquara, 2014. http://hdl.handle.net/11449/110848 000773472 000773472.pdf 33004030072P8 1308042794786872 |
identifier_str_mv |
CARVALHO, Amanda Uliana de. Dinâmica metabólica em Piper gaudichaudianum: estudo das etapas de ciclização estereosseletiva do ácido gaudichaudianico. 2014. 107 f. Dissertação (mestrado) - Universidade Estadual Paulista Júlio de Mesquita Filho, Instituto de Química de Araraquara, 2014. 000773472 000773472.pdf 33004030072P8 1308042794786872 |
url |
http://hdl.handle.net/11449/110848 |
dc.language.iso.fl_str_mv |
por |
language |
por |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
107 f. : il. application/pdf |
dc.publisher.none.fl_str_mv |
Universidade Estadual Paulista (Unesp) |
publisher.none.fl_str_mv |
Universidade Estadual Paulista (Unesp) |
dc.source.none.fl_str_mv |
Aleph reponame:Repositório Institucional da UNESP instname:Universidade Estadual Paulista (UNESP) instacron:UNESP |
instname_str |
Universidade Estadual Paulista (UNESP) |
instacron_str |
UNESP |
institution |
UNESP |
reponame_str |
Repositório Institucional da UNESP |
collection |
Repositório Institucional da UNESP |
repository.name.fl_str_mv |
Repositório Institucional da UNESP - Universidade Estadual Paulista (UNESP) |
repository.mail.fl_str_mv |
|
_version_ |
1808128274191089664 |