Chemometric analysis of ESIMS and NMR data from Piper species

Abstract

O perfil metabólito baseado na aplicação de análises multivariadas (análise de componentes principais, PCA) dos dados de espectrometria de massas com ionização electrospray (ESIMS) no modo positivo e de ressonância magnética nuclear (RMN) do 1 H de extratos brutos de espécies de Piper destacou algumas espécies caracterizadas pela produção de lignanas (P. solmsianum, P. truncatum e P. cernuum), neolignanas (P. regnellii) e cromenos (P. gaudichaudianum). Análises específicas em conjunto de espécies caracterizadas morfologicamente por apresentarem inflorescências pêndulas e globosas (P. caldense, P. carniconnectivum, P. bowiei e P. permucronatum) ou em espécies que produzem amidas indicaram o potencial mais significativo para tais análises como critério para estudos fitoquímicos posteriores. Análises intraespecíficas de plântulas das espécies P. solmsianum, P. regnellii e P. gaudichaudianum indicaram uma composição química nas folhas baseada na presença dos fenilpropanóides dilapiol e apiol, diferentemente do que produzem as plantas adultas. No caso das espécies que produzem amidas, a composição apresentou-se relativamente constante independentemente do estágio de desenvolvimento.The metabolomic profiling based on the application of multivariate analysis (principal component analysis, PCA) of positive mode electrospray ionization mass spectrometric (ESIMS) and 1 H nuclear magnetic resonance (NMR) data of crude extracts highlighted some species characterized by lignans (P. solmsianum, P. truncatum and P. cernuum), neolignans (P. regnellii) and chromenes (P. gaudichaudianum). A specific analysis focusing on species having pendant and globular inflorescences (P. caldense, P. carniconnectivum, P. bowiei and P. permucronatum) or amides-producing species indicated higher potential of the methodology in determining similarities and establishing priorities for further phytochemical investigation. Such intraspecific analysis applied to analyzed seedling leaves of the P. solmsianum, P. regnellii and P. gaudichaudianum species revealed the production of dillapiole and apiole instead of lignans, neolignans or prenylated benzoic acid, produced by the adult leaves, respectively. In case of amides-producing species, a similar profile was observed regardless the developmental stage.Keywords: Piperaceae, principal component analysis, secondary metabolites, fingerprinting Chemometric Analysis of ESIMS and NMR Data from Piper Species J. Braz. Chem. Soc. 2372 IntroductionThe knowledge on secondary chemistry of tropical plant species is limited to approximately 5-10% of the total species described so far. In fact, this limited study indicates the potential for finding novel lead compounds from tropical biodiversity. Despite the availability of high throughput technology platforms to detect bioactive compounds, the process of cataloguing their composition possesses a significant challenge since it still involves largely the isolation and spectroscopic characterization of individual components. Additionally, the determination of a m...

Ontogenetic Changes in the Chemical Profiles of Piper Species

“…The analysis of the crude extracts from adult leaves of P. richardiaefolium by HPLC-UV, GCMS and 1 H NMR indicated the presence of two dibenzylbutyrolactone and two dibenzylbutyrolactol lignans. The lignans were identified as hinokinin (13a), kusunokinin (13b), cubebin (13c), and 13d [44] as previously reported for P. richardiaefolium [44,49,50]. Nevertheless, its seedling leaves (Figure S14) contained piperine (19) [51], piplartine (17) and pellitorine (18) [52], with these identities supported by 1 H NMR (Figure S14), HRESIMS data and the use of standard compounds.…”

“…Piplartine (17) is the dominant compound in adult and seedling leaves of P. tuberculatum (Figure S9), as evidenced in the loading plot by signals assigned to methoxy groups (δ 3.86 and 3.88) of piplartine [8]. Piper amalago (Figure S10) had signals assigned to nigrinodine (21) for both adult and seedling leaves (δ 5.90 and 5.92 of methylenedioxy groups) (Figure S11) [44].…”

“…The group of species consisting of P. tuberculatum Jacq., P. amalago L. and P. reticulatum L., is characterized by the production of amides in their adult leaves [8,[43][44][45]. The PCA of 1 H NMR data of crude extracts from seedlings and adult leaves shows P. amalago and P. tuberculatum are chemically distinct, but their chemistry does not change across ontogeny (Figure 10).…”

Biossíntese da pellucidina A em <i>Peperomia pellucida</i> (L.) HBK

“…Entre as análises mais usadas estão a ressonância magnética nuclear (RMN), cromatografia à gás acoplada à espectrometria de massas (CG-EM), cromatografia líquida acoplada à espectrometria de massas (CL-EM), cromatografia líquida de alta eficiência (CLAE), eletroforese capilar acoplada à espectrometria de massas (EC-EM) e, em alguns casos, uma combinação dessas técnicas. As aplicações dessas técnicas são importantes, pois permitem a detecção e identificação de dezenas de compostos em uma única análise (Dunn et al, 2011;Kim et al, 2010;Obata and Fernie, 2012;Schripsema, 2009;Yamaguchi et al, 2011).…”

“…As análises multivariadas são capazes de extrair importantes informações das amostras, permitindo assim uma interpretação das possíveis variações metabólicas ocorridas no organismo (Kim et al, 2010;Schripsema, 2009;Yamaguchi et al, 2011).…”