Fragmentation study of clerodane diterpenes from Casearia species by tandem mass spectrometry (quadrupole time-of-flight and ion trap)

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Danuello, Amanda ; de Castro, Rogerio Cardoso ; Pilon, Alan Cesar ; Pires Bueno, Paula Carolina ; Pivatto, Marcos ; Vieira Junior, Gerardo Magela ; Carvalho, Flavio Alexandre ; Oda, Fernando Bombarda ; Perez, Consuelo Javiera ; Lopes, Norberto Peporine ; Dos Santos, Andre Gonzaga ; Ifa, Demian Rocha ; Cavalheiro, Alberto Jose

• Tipo de documento: Artigo Científico
• Fonte: RAPID COMMUNICATIONS IN MASS SPECTROMETRY; v. 34, p. 7-pg., 2020-05-20.

Resumo

Rationale Clerodane-type diterpenes from Casearia species show important pharmacological activites such as antitumor, antimicrobial and anti-inflamatory. There are several mass spectrometry (MS)-based methods for identification of diterpenes; however, there is still a lack of MS procedures capable of providing characteristic fragmentation pathways for a rapid and unambiguous elucidation of casearin-like compounds. Methods Casearin-like compounds were investigated by electrospray ionization tandem mass spectrometry (ESI-MS/MS). The fragmentation studies were carried out by tandem mass spectrometry in space (quadrupole time-of-flight (QTOF)) using different collision energies and also by tandem mass spectrometry in time (QIT) by selective isolation of product ions. Results Casearin-like compounds presented a predominance of sodium- and potassium-cationized precursor ions. Both QIT and QTOF techniques provided sequential neutral losses of esters related to the R-1 to R-5 substituents linked to the nucleus of the clerodane diterpenes. The fragmentation pathway is initiated with a cleavage of the ester moieties R-2 followed by the elimination of the ester groups R-3, both losing neutral carboxylic acids. Using QIT, it was also possible to observe the cleavage of the ester groups R-1 or R-5 by MS4 experiments. Conclusions Through a rational analysis of the fragmentation mechanisms of Casearia diterpenes it was possible to suggest an annotation strategy based on the sequential cleavages of the ester groups related to the R-2, R-3 and R-5 substituents. These results will assist studies of the dereplication and metabolomics involving casearin-like compounds present in complex extracts of Casearia species. (AU)

• Processo FAPESP: 14/50926-0 - INCT 2014: biodiversidade e produtos naturais
• Beneficiário: Vanderlan da Silva Bolzani
• Modalidade de apoio: Auxílio à Pesquisa - Programa BIOTA - Temático
• Processo FAPESP: 16/13292-8 - Análise do conteúdo nitrogenado em áreas sob ação atrófica na Floresta Amazônica e Atlântica utilizando de ferramentas metabolômicas
• Beneficiário: Alan Cesar Pilon
• Modalidade de apoio: Bolsas no Brasil - Pós-Doutorado
• Processo FAPESP: 13/07600-3 - CIBFar - Centro de Inovação em Biodiversidade e Fármacos
• Beneficiário: Glaucius Oliva
• Modalidade de apoio: Auxílio à Pesquisa - Centros de Pesquisa, Inovação e Difusão - CEPIDs
• Processo FAPESP: 11/21440-3 - Variabilidade química infra-específica e dinâmica de metabólitos secundários fenólicos e diterpênicos em Casearia sylvestris Sw. (Salicaceae) provenientes de diferentes ecossistemas brasileiros: correlação metabolômica e proteômica
• Beneficiário: Paula Carolina Pires Bueno
• Modalidade de apoio: Bolsas no Brasil - Doutorado
• Processo FAPESP: 17/19702-6 - Abordagens ômicas integradas para a avaliação da dinâmica micromolecular fenotípica de cultivares de Glycine max (soja) geneticamente modificados com vistas a tolerância à estresses hídricos
• Beneficiário: Paula Carolina Pires Bueno
• Modalidade de apoio: Bolsas no Brasil - Pós-Doutorado