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*
1   Departamento de Física e Química, Faculdade de Ciências Farmacêuticas de Ribeirão Preto, Universidade de São Paulo, Ribeirão Preto, SP, Brazil
,
Fausto Carnevale Neto*
1   Departamento de Física e Química, Faculdade de Ciências Farmacêuticas de Ribeirão Preto, Universidade de São Paulo, Ribeirão Preto, SP, Brazil
,
Daniel Pecoraro Demarque
1   Departamento 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
2   Centro de Ciências da Saúde, Faculdade Escritor Osman da Costa Lins, Vitória de Santo Antão, PE, Brazil
,
Rômulo César Sampaio Peixoto Filho
3   Departamento de Antibióticos, Universidade Federal de Pernambuco, Recife, PE, Brazil
,
Sebastião José de Melo
3   Departamento de Antibióticos, Universidade Federal de Pernambuco, Recife, PE, Brazil
,
Jackson Roberto Guedes da Silva Almeida
4   Núcleo de Estudos e Pesquisas de Plantas Medicinais, Universidade Federal do Vale do São Francisco, Petrolina, PE, Brazil
,
João Luiz Callegari Lopes
1   Departamento de Física e Química, Faculdade de Ciências Farmacêuticas de Ribeirão Preto, Universidade de São Paulo, Ribeirão Preto, SP, Brazil
,
Norberto Peporine Lopes
1   Departamento de Física e Química, Faculdade de Ciências Farmacêuticas de Ribeirão Preto, Universidade de São Paulo, Ribeirão Preto, SP, Brazil
› Institutsangaben
Weitere Informationen

Publikationsverlauf

received 03. August 2016
revised 21. September 2016

accepted 01. Oktober 2016

Publikationsdatum:
02. November 2016 (online)

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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.

* Co-first authors.


Supporting Information

The MS and MS/MS data of compounds 163 and the HRMS and NMR spectra of compound 46 are available as Supporting Information.