Electrospray ionization mass spectrometry screening of piperidine alkaloids from Senna spectabilis (Fabaceae) extracts: fast identification of new constituents and co-metabolites

Abstract

O padrão de fragmentação de uma série homóloga de alcalóides piperidínicos isolados de Senna spectabilis foi investigado utilizando-se espectrometria de massas tandem com ionização por electrospray (ESI-EM/EM). A análise dos extratos EtOH e frações das flores e dos frutos de S. spectabilis por ESI-EM e ESI-EM/EM permitiu elucidar a estrutura de quatro componentes pertencentes a uma série homóloga destes alcalóides, bem como de quatro co-metabólitos inéditos. A elucidação estrutural dos co-metabólitos, com base no padrão de fragmentação de alcalóides piperidínicos previamente isolados, e confirmados pelos dados de EM de alta resolução, demonstra a importância desta técnica para a determinação do "perfil metabolômico" de uma espécie de importância farmacológica.The fragmentation pattern of a homologous series of piperidine alkaloids isolated from S. spectabilis was investigated using electrospray ionization tandem mass spectrometry (ESI-MS/ MS). The ESI-MS and ESI-MS/MS analyses of EtOH extracts and fractions from flowers and fruits of S. spectabilis allowed to elucidate the structures of four new compounds. The identification of these co-metabolites, based on the fragmentation patterns of previously isolated compounds, and further confirmed by accurate mass spectrometry defines this technique as a powerful tool to determine the "metabolomic profile" of species which has pharmacological importance.

Tropical biodiversity: has it been a potential source of secondary metabolites useful for medicinal chemistry?

“…88 In addition, the presence of a homologous series of novel piperidine alkaloids has been detected in the fruits of S. spectabilis by means of tandem mass spectrometry with electrospray ionization. 89 A detailed analysis of the structural features of 70 has led to identification of an acetylcholine (ACh) subunit internalized in this (Figure 17), and led to the design of several semi-synthetic derivatives, including (-)-3-O-acetyl-spectaline hydrochloride (73), prepared from 63. This derivative displays cholinergic activity both in vitro and in vivo (IC 50 = 7.32 μM).…”

Electrospray Ionization Tandem Mass Spectrometry as a Tool for the Structural Elucidation and Dereplication of Natural Products: An Overview

“…Also, the authors reported that the extracts obtained from flowers contained more oxygen atoms than those obtained from fruits. On the other hand, the formation of some ions as evidenced in the spectrum of the precursor ion could not be explained on the basis of their ESI-MS/MS data, but they can also be of great importance when this technique is used in combination with NMR (Pivatto et al, 2005). The dereplication of alkaloids has also been achieved by means of UV-Vis spectroscopy in combination with tandem mass spectrometry (MS/MS).…”

Spectaline, cassine and semi-synthetic analogues as potential candidate drugs for the treatment of Alzheimer disease

“…Foi ainda demonstrada a atividade potencialmente antitumoral dos alcaloides − -3-O-acetil-espectalina (11), − -7-hidróxi-espectalina, iso-6-espectalina (3 , − -espectalina (7), obtidos das flores e de frutos verdes de Senna spectabilis, por meio do bioensaio usando linhagens mutantes de Saccharomyces cerevisae com deficiência para atuar no reparo do DNA. 25,26 Figura 2. Estruturas de alcaloides piperidínicos isolados de S. spectabilis Senna spectabilis é a espécie nativa do Brasil que biossintetiza a maior diversidade de alcaloides piperidínicos bioativos, sendo que algumas dessas substâncias apresentaram efeitos farmacológicos de interesse.…”