Dereplication of Flavonoid Glycoconjugates from Adenocalymma imperatoris-maximilianii by Untargeted Tandem Mass Spectrometry-Based Molecular Networking

Gibson Gomes de Oliveira; Fausto Carnevale Neto; Daniel Pecoraro Demarque; José Antônio de Sousa Pereira-Junior; Rômulo César Sampaio Peixoto Filho; Sebastião José de Melo; Jackson Roberto Guedes da Silva Almeida; João Luiz Callegari Lopes; Norberto Peporine Lopes

doi:10.1055/s-0042-118712

Planta Medica, Table of Contents

Planta Med 2017; 83(07): 636-646
DOI: 10.1055/s-0042-118712

Natural Product Chemistry and Analytical Studies

Original Papers

Georg Thieme Verlag KG Stuttgart · New York

Dereplication of Flavonoid Glycoconjugates from Adenocalymma imperatoris-maximilianii by Untargeted Tandem Mass Spectrometry-Based Molecular Networking

Gibson Gomes de Oliveira^*

¹Departamento de Física e Química, Faculdade de Ciências Farmacêuticas de Ribeirão Preto, Universidade de São Paulo, Ribeirão Preto, SP, Brazil

,

Fausto Carnevale Neto^*

¹Departamento de Física e Química, Faculdade de Ciências Farmacêuticas de Ribeirão Preto, Universidade de São Paulo, Ribeirão Preto, SP, Brazil

,

Daniel Pecoraro Demarque

¹Departamento de Física e Química, Faculdade de Ciências Farmacêuticas de Ribeirão Preto, Universidade de São Paulo, Ribeirão Preto, SP, Brazil

,

José Antônio de Sousa Pereira-Junior

²Centro de Ciências da Saúde, Faculdade Escritor Osman da Costa Lins, Vitória de Santo Antão, PE, Brazil

,

Rômulo César Sampaio Peixoto Filho

³Departamento de Antibióticos, Universidade Federal de Pernambuco, Recife, PE, Brazil

,

Sebastião José de Melo

³Departamento de Antibióticos, Universidade Federal de Pernambuco, Recife, PE, Brazil

,

Jackson Roberto Guedes da Silva Almeida

⁴Núcleo de Estudos e Pesquisas de Plantas Medicinais, Universidade Federal do Vale do São Francisco, Petrolina, PE, Brazil

,

João Luiz Callegari Lopes

¹Departamento de Física e Química, Faculdade de Ciências Farmacêuticas de Ribeirão Preto, Universidade de São Paulo, Ribeirão Preto, SP, Brazil

,

Norberto Peporine Lopes

¹Departamento de Física e Química, Faculdade de Ciências Farmacêuticas de Ribeirão Preto, Universidade de São Paulo, Ribeirão Preto, SP, Brazil

› Author Affiliations

Abstract

The interpretation of large datasets acquired using high performance liquid chromatography coupled with tandem mass spectrometry represents one of the major challenges in natural products research. Here we propose the use of molecular networking to rapid identify the known secondary metabolites from untargeted MS/MS analysis of Adenocalymma imperatoris-maximilianii plant extracts. The leaves, stems and roots of A. imperatoris-maximilianii were extracted using different solvents according to Snyder selectivity triangle. The samples were analyzed by HPLC coupled with ion trap mass spectrometer in a collision-induced dissociation MS/MS configuration in both positive and negative electrospray ionization modes. Molecular networking simultaneously organized the spectra by cosine similarity. The chemical identification was performed based on the systematic study of the main fragmentation pathways observed for the resulting network. The untargeted tandem mass spectrometry-based molecular networking allowed for the identification of 63 metabolites, mainly mono-, di- and tri-, C- and/or O-glycosyl flavones. Molecular networking was capable not only to dereplicate known flavonoids, but also to point out related prenyl derivatives, described for the first time in Adenocalymma species. The gas-phase reaction route to form the characteristic [M-H₂O-(30/60/90)]⁺ fragments in C-glycosyl flavones was suggested as sequential sugar ring opening followed by retro-aldol elimination involving aldose-ketose isomerization. The use of molecular networking with LC–CID-MS/MS assisted the identification of various isomeric and isobaric flavonoid glycoconjugates by establishing clusters according to the fragmentation similarities. Additionally, the proposed cross-ring sugar cleavages can contribute to the identification of C-glycosides by MS/MS analysis.

Key words

Adenocalymma imperatoris-maximilianii - Bignoniaceae - molecular networking - flavonoid glycosides - aldose-ketose isomerization - retro-aldol

Full Text

References

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