Chemical diversity and ontogeny of Piper species
Autor(a) principal: | |
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Data de Publicação: | 2021 |
Tipo de documento: | Tese |
Idioma: | eng |
Título da fonte: | Biblioteca Digital de Teses e Dissertações da USP |
Texto Completo: | https://www.teses.usp.br/teses/disponiveis/46/46136/tde-02122022-120839/ |
Resumo: | Piper (Piperaceae) is a genus of economic and medicinal importance, with over 1000 species, having the highest species diversity among the basal angiosperms. However, a considerable number of species have not been studied despite their widespread and traditional uses. In the case of P. auritum, a comprehensive phytochemical analysis was conducted for adults and plants at early stages. Leaves, fruits and roots were extracted, and the major metabolites were identified by spectrometric and spectroscopic methods. C-glycosylflavonoids, phenylbutenolides, amides and phenylpropanoids were the main sets of compounds in the species. After chromatographic profiling using HPLC-UV-HRESI, a comparison between adults (leaves, root and fruit) and seedlings (leaves) showed the rise of Cglycosylflavonoids and amide pellitorine during the early stage of ontogeny as well as the lack of phenylbutenolides and other amides, suggesting that the chemistry of the early stages corresponds to a hybrid between young leaves and roots. The species P. lindbergii and P. chimonantifolium were also studied; several metabolites like dihydrochalcones myrigalone H, dihydroflavokawain C and asebogenin, as well as chalcone stercurensin, were identified by HPLC-ESI-HRMS and NMR (1D and 2D). Several other chalcone-type metabolites were annotated for both species, suggesting them as promising sources of chalcone-type metabolites. Additionally, seven species of Piper (P. umbellatum, P. glabratum, P. diospyrifolium, P. caldense, P. regnellii, P. crassinervium (IQ and Colombia) and P. chimonantifolium were planted. Six-month-old seedlings were collected, extracted, and their HPLC and 1H NMR profiles were compared with the adults by multivariate analysis and through the differences in their composition. Two methodologies were used: individuals of P. umbellatum, P. glabratum and P. diospyrifolium; and pooled P. caldense, P. regnellii, P. crassinervium (IQ and Colombia) and P. chimonantifolium. Multivariate analysis displayed visible differences between species and phenological stage, especially for the pooled species with better clustering while individuals showed a high dispersion. HPLC results were also superior to NMR, showing the strong effect of interferents and extraction procedure in the latter. P. glabratum was compared using both methodologies, with the PCA discriminating the individual, pooled and adult samples in a better way for HPLC data. HPLC-ESIHRMS annotations showed that C-glycosylflavonoids are conspicuous in all species, adult and seedlings, while the adults become more variated, producing lignoids, chalcones, dihydrochalcones, prenylated benzoic acids and quinones. Finally, due to the ubiquitous occurrence of aristolactams in the studied species, an HPLC-FLD methodology was developed and validated to quantify the total amount of these compounds in EtOAc extracts from roots of eighteen species of Piper. During the standard cepharanone B isolation, piperolactams A-C and aristolactam DIII were identified. P. aduncum, P. aleyreanum, P. hispidum, P. cubataonum and P. krukoffi displayed the highest content of these compounds. The method was highly selective and sensitive for this study and also demonstrated high ruggedness. In general, the data obtained demonstrated the presence of compounds such as glycosylated flavonoids and aristolactams as ubiquitous in Piper species and that plant studies along ontogeny could contribute to the discovery of new secondary metabolites. |
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Chemical diversity and ontogeny of Piper speciesDiversidade química e ontogenia de espécies de PiperAristolactamasAristolactamsFitoquímicaMetabólitos secundáriosOntogeníaOntogenyPhytochemistryPiperPiperSecondary metabolitesPiper (Piperaceae) is a genus of economic and medicinal importance, with over 1000 species, having the highest species diversity among the basal angiosperms. However, a considerable number of species have not been studied despite their widespread and traditional uses. In the case of P. auritum, a comprehensive phytochemical analysis was conducted for adults and plants at early stages. Leaves, fruits and roots were extracted, and the major metabolites were identified by spectrometric and spectroscopic methods. C-glycosylflavonoids, phenylbutenolides, amides and phenylpropanoids were the main sets of compounds in the species. After chromatographic profiling using HPLC-UV-HRESI, a comparison between adults (leaves, root and fruit) and seedlings (leaves) showed the rise of Cglycosylflavonoids and amide pellitorine during the early stage of ontogeny as well as the lack of phenylbutenolides and other amides, suggesting that the chemistry of the early stages corresponds to a hybrid between young leaves and roots. The species P. lindbergii and P. chimonantifolium were also studied; several metabolites like dihydrochalcones myrigalone H, dihydroflavokawain C and asebogenin, as well as chalcone stercurensin, were identified by HPLC-ESI-HRMS and NMR (1D and 2D). Several other chalcone-type metabolites were annotated for both species, suggesting them as promising sources of chalcone-type metabolites. Additionally, seven species of Piper (P. umbellatum, P. glabratum, P. diospyrifolium, P. caldense, P. regnellii, P. crassinervium (IQ and Colombia) and P. chimonantifolium were planted. Six-month-old seedlings were collected, extracted, and their HPLC and 1H NMR profiles were compared with the adults by multivariate analysis and through the differences in their composition. Two methodologies were used: individuals of P. umbellatum, P. glabratum and P. diospyrifolium; and pooled P. caldense, P. regnellii, P. crassinervium (IQ and Colombia) and P. chimonantifolium. Multivariate analysis displayed visible differences between species and phenological stage, especially for the pooled species with better clustering while individuals showed a high dispersion. HPLC results were also superior to NMR, showing the strong effect of interferents and extraction procedure in the latter. P. glabratum was compared using both methodologies, with the PCA discriminating the individual, pooled and adult samples in a better way for HPLC data. HPLC-ESIHRMS annotations showed that C-glycosylflavonoids are conspicuous in all species, adult and seedlings, while the adults become more variated, producing lignoids, chalcones, dihydrochalcones, prenylated benzoic acids and quinones. Finally, due to the ubiquitous occurrence of aristolactams in the studied species, an HPLC-FLD methodology was developed and validated to quantify the total amount of these compounds in EtOAc extracts from roots of eighteen species of Piper. During the standard cepharanone B isolation, piperolactams A-C and aristolactam DIII were identified. P. aduncum, P. aleyreanum, P. hispidum, P. cubataonum and P. krukoffi displayed the highest content of these compounds. The method was highly selective and sensitive for this study and also demonstrated high ruggedness. In general, the data obtained demonstrated the presence of compounds such as glycosylated flavonoids and aristolactams as ubiquitous in Piper species and that plant studies along ontogeny could contribute to the discovery of new secondary metabolites.Piper (Piperaceae) é um gênero de grande importância econômica e medicinal, com mais de 1000 espécies, tendo a maior diversidade entre as angiospermas basais. No entanto, apesar dos inúmeros usos tradicionais, um número considerável de espécies não foi ainda estudado sob o ponto de vista químico. No caso de P. auritum, uma análise fitoquímica completa foi conduzida para adultos e plântulas. Folhas, frutos e raízes foram extraídos e os principais metabólitos identificados por métodos espectrométricos e espectroscópicos. Flavonoides C-glicosilados, fenilbutenolidos, amidas e fenilpropanoides foram as principais famílias de compostos caracterizados. Análises de HPLC possibilitaram uma comparação entre adultos (folhas, raiz e frutos) e plântulas (folhas) onde evidenciou-se o aumento dos flavonoides C-glicosilados ao longo da ontogenia, além da presença da amida pelitorina durante o estágio inicial, bem como a ausência de fenilbutenolidos e de outras amidas, sugerindo que a química dos estágios iniciais corresponde a uma composição híbrida entre folhas jovens e raízes. As espécies P. lindbergii e P. chimonantifolium também foram estudadas; vários metabólitos como as dihidrochalconas mirigalona H, dihidroflavokawaina C e asebogenina, assim como a chalcona stercurensina, foram identificadas por HPLC-ESI-HRMS e NMR (1D e 2D). Vários outros metabólitos análogos foram anotados para ambas as espécies, projetando-os como fontes promissoras de metabólitos do tipo chalcona. Além disso, sete espécies de Piper foram cultivadas. Mudas de seis meses foram extraídas e seus perfis de HPLC e RMN de 1H foram comparados com os adultos por análise multivariada objetivando caracterizar diferenças em suas composições. Duas metodologias foram utilizadas: uma para indivíduos de P. umbellatum, P. glabratum e P. diospyrifolium; e outra para indivíduos de P. caldense, P. regnellii, P. crassinervium (IQ e Colômbia) e P. chimonantifolium. O PCA mostrou diferenças entre as espécies e o estágio fenológico. As análises por HPLC também foram mais informativas do que por NMR, mostrando o forte efeito dos interferentes e do procedimento de extração. P. glabratum foi comparada usando ambas as metodologias, com o PCA discriminando o indivíduo, os agrupados e os adultos de uma maneira melhor através dos dados de HPLC. As anotações feitas por HPLC-ESI-HRMS mostraram que flavonoides C-glicosilados são recorrentes em todas as espécies, adultas e plântulas, enquanto os adultos tornam-se mais variados, produzindo lignoides, chalconas, dihidrocalconas, ácidos benzoicos prenilados e quinonas. Finalmente, devido à ocorrência persistente de aristolactamas nas espécies estudadas, uma metodologia de HPLC-FLD foi desenvolvida e validada para se quantificar a esses compostos em extratos de EtOAc de raízes de dezessete espécies de Piper. Durante o isolamento do padrão de cefaranona B, foram identificados os compostos piperolactamas A-C e aristolactama DIII. P. aduncum, P. aleyreanum, P. hispidum, P. cubataonum e P. krukoffi exibiram o maior conteúdo desses compostos. O método foi altamente seletivo e sensível para este estudo e demonstrou alta robustez. De uma forma geral, os dados obtidos demonstraram a presença de compostos como flavonoides glicosilados e de aristolactamas como onipresentes em espécies de Piper e que estudos das plantas ao longo da ontogenia podem contribuir para a descoberta de novos metabólitos secundários.Biblioteca Digitais de Teses e Dissertações da USPKato, Massuo JorgeGuerrero-Perilla, Andres Camilo 2021-12-10info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisapplication/pdfhttps://www.teses.usp.br/teses/disponiveis/46/46136/tde-02122022-120839/reponame:Biblioteca Digital de Teses e Dissertações da USPinstname:Universidade de São Paulo (USP)instacron:USPLiberar o conteúdo para acesso público.info:eu-repo/semantics/openAccesseng2022-12-19T20:18:46Zoai:teses.usp.br:tde-02122022-120839Biblioteca Digital de Teses e Dissertaçõeshttp://www.teses.usp.br/PUBhttp://www.teses.usp.br/cgi-bin/mtd2br.plvirginia@if.usp.br|| atendimento@aguia.usp.br||virginia@if.usp.bropendoar:27212022-12-19T20:18:46Biblioteca Digital de Teses e Dissertações da USP - Universidade de São Paulo (USP)false |
dc.title.none.fl_str_mv |
Chemical diversity and ontogeny of Piper species Diversidade química e ontogenia de espécies de Piper |
title |
Chemical diversity and ontogeny of Piper species |
spellingShingle |
Chemical diversity and ontogeny of Piper species Guerrero-Perilla, Andres Camilo Aristolactamas Aristolactams Fitoquímica Metabólitos secundários Ontogenía Ontogeny Phytochemistry Piper Piper Secondary metabolites |
title_short |
Chemical diversity and ontogeny of Piper species |
title_full |
Chemical diversity and ontogeny of Piper species |
title_fullStr |
Chemical diversity and ontogeny of Piper species |
title_full_unstemmed |
Chemical diversity and ontogeny of Piper species |
title_sort |
Chemical diversity and ontogeny of Piper species |
author |
Guerrero-Perilla, Andres Camilo |
author_facet |
Guerrero-Perilla, Andres Camilo |
author_role |
author |
dc.contributor.none.fl_str_mv |
Kato, Massuo Jorge |
dc.contributor.author.fl_str_mv |
Guerrero-Perilla, Andres Camilo |
dc.subject.por.fl_str_mv |
Aristolactamas Aristolactams Fitoquímica Metabólitos secundários Ontogenía Ontogeny Phytochemistry Piper Piper Secondary metabolites |
topic |
Aristolactamas Aristolactams Fitoquímica Metabólitos secundários Ontogenía Ontogeny Phytochemistry Piper Piper Secondary metabolites |
description |
Piper (Piperaceae) is a genus of economic and medicinal importance, with over 1000 species, having the highest species diversity among the basal angiosperms. However, a considerable number of species have not been studied despite their widespread and traditional uses. In the case of P. auritum, a comprehensive phytochemical analysis was conducted for adults and plants at early stages. Leaves, fruits and roots were extracted, and the major metabolites were identified by spectrometric and spectroscopic methods. C-glycosylflavonoids, phenylbutenolides, amides and phenylpropanoids were the main sets of compounds in the species. After chromatographic profiling using HPLC-UV-HRESI, a comparison between adults (leaves, root and fruit) and seedlings (leaves) showed the rise of Cglycosylflavonoids and amide pellitorine during the early stage of ontogeny as well as the lack of phenylbutenolides and other amides, suggesting that the chemistry of the early stages corresponds to a hybrid between young leaves and roots. The species P. lindbergii and P. chimonantifolium were also studied; several metabolites like dihydrochalcones myrigalone H, dihydroflavokawain C and asebogenin, as well as chalcone stercurensin, were identified by HPLC-ESI-HRMS and NMR (1D and 2D). Several other chalcone-type metabolites were annotated for both species, suggesting them as promising sources of chalcone-type metabolites. Additionally, seven species of Piper (P. umbellatum, P. glabratum, P. diospyrifolium, P. caldense, P. regnellii, P. crassinervium (IQ and Colombia) and P. chimonantifolium were planted. Six-month-old seedlings were collected, extracted, and their HPLC and 1H NMR profiles were compared with the adults by multivariate analysis and through the differences in their composition. Two methodologies were used: individuals of P. umbellatum, P. glabratum and P. diospyrifolium; and pooled P. caldense, P. regnellii, P. crassinervium (IQ and Colombia) and P. chimonantifolium. Multivariate analysis displayed visible differences between species and phenological stage, especially for the pooled species with better clustering while individuals showed a high dispersion. HPLC results were also superior to NMR, showing the strong effect of interferents and extraction procedure in the latter. P. glabratum was compared using both methodologies, with the PCA discriminating the individual, pooled and adult samples in a better way for HPLC data. HPLC-ESIHRMS annotations showed that C-glycosylflavonoids are conspicuous in all species, adult and seedlings, while the adults become more variated, producing lignoids, chalcones, dihydrochalcones, prenylated benzoic acids and quinones. Finally, due to the ubiquitous occurrence of aristolactams in the studied species, an HPLC-FLD methodology was developed and validated to quantify the total amount of these compounds in EtOAc extracts from roots of eighteen species of Piper. During the standard cepharanone B isolation, piperolactams A-C and aristolactam DIII were identified. P. aduncum, P. aleyreanum, P. hispidum, P. cubataonum and P. krukoffi displayed the highest content of these compounds. The method was highly selective and sensitive for this study and also demonstrated high ruggedness. In general, the data obtained demonstrated the presence of compounds such as glycosylated flavonoids and aristolactams as ubiquitous in Piper species and that plant studies along ontogeny could contribute to the discovery of new secondary metabolites. |
publishDate |
2021 |
dc.date.none.fl_str_mv |
2021-12-10 |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/doctoralThesis |
format |
doctoralThesis |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
https://www.teses.usp.br/teses/disponiveis/46/46136/tde-02122022-120839/ |
url |
https://www.teses.usp.br/teses/disponiveis/46/46136/tde-02122022-120839/ |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
|
dc.rights.driver.fl_str_mv |
Liberar o conteúdo para acesso público. info:eu-repo/semantics/openAccess |
rights_invalid_str_mv |
Liberar o conteúdo para acesso público. |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
application/pdf |
dc.coverage.none.fl_str_mv |
|
dc.publisher.none.fl_str_mv |
Biblioteca Digitais de Teses e Dissertações da USP |
publisher.none.fl_str_mv |
Biblioteca Digitais de Teses e Dissertações da USP |
dc.source.none.fl_str_mv |
reponame:Biblioteca Digital de Teses e Dissertações da USP instname:Universidade de São Paulo (USP) instacron:USP |
instname_str |
Universidade de São Paulo (USP) |
instacron_str |
USP |
institution |
USP |
reponame_str |
Biblioteca Digital de Teses e Dissertações da USP |
collection |
Biblioteca Digital de Teses e Dissertações da USP |
repository.name.fl_str_mv |
Biblioteca Digital de Teses e Dissertações da USP - Universidade de São Paulo (USP) |
repository.mail.fl_str_mv |
virginia@if.usp.br|| atendimento@aguia.usp.br||virginia@if.usp.br |
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1809090323124584448 |