Dereplication of Flavonoid Glycoconjugates from Adenocalymma imperatoris-maximilianii by Untargeted Tandem Mass Spectrometry-Based Molecular Networking.
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 ofAdenocalymma imperatoris-maximilianiiplant extracts. The leaves, stems and roots ofA. imperatoris-maximilianiiwere 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/orO-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 inAdenocalymmaspecies. The gas-phase reaction route to form the characteristic [M-H2O-(30/60/90)]+fragments inC-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 ofC-glycosides by MS/MS analysis.
Departamento de Física e Química, Faculdade de Ciências Farmacêuticas de Ribeirão Preto, Universidade de São Paulo, Ribeirão Preto, SP, Brazil.
Gibson Gomes
GG
de Oliveira
Departamento de Física e Química, Faculdade de Ciências Farmacêuticas de Ribeirão Preto, Universidade de São Paulo, Ribeirão Preto, SP, Brazil.
Fausto
F
Carnevale Neto
Departamento de Física e Química, Faculdade de Ciências Farmacêuticas de Ribeirão Preto, Universidade de São Paulo, Ribeirão Preto, SP, Brazil.
Daniel Pecoraro
DP
Demarque
Centro de Ciências da Saúde, Faculdade Escritor Osman da Costa Lins, Vitória de Santo Antão, PE, Brazil.
José Antônio
JA
de Sousa Pereira-Junior
Departamento de Antibióticos, Universidade Federal de Pernambuco, Recife, PE, Brazil.
Rômulo César
RC
Sampaio Peixoto Filho
Departamento de Antibióticos, Universidade Federal de Pernambuco, Recife, PE, Brazil.
Sebastião José
SJ
de Melo
Núcleo de Estudos e Pesquisas de Plantas Medicinais, Universidade Federal do Vale do São Francisco, Petrolina, PE, Brazil.
Jackson Roberto Guedes
JRG
da Silva Almeida
Departamento de Física e Química, Faculdade de Ciências Farmacêuticas de Ribeirão Preto, Universidade de São Paulo, Ribeirão Preto, SP, Brazil.
João Luiz Callegari
JLC
Lopes
Departamento de Física e Química, Faculdade de Ciências Farmacêuticas de Ribeirão Preto, Universidade de São Paulo, Ribeirão Preto, SP, Brazil.
Norberto Peporine
NP
Lopes
D029402:Bignoniaceae / Q000737:chemistry*; D001938:Brazil; D002851:Chromatography, High Pressure Liquid; D003205:Computing Methodologies; D005419:Flavonoids / Q000737:chemistry*; D006001:Glycoconjugates / Q000737:chemistry*; D010936:Plant Extracts / Q000737:chemistry*; D053719:Tandem Mass Spectrometry
D005419:Flavonoids; D006001:Glycoconjugates; D010936:Plant Extracts