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(Reference retrieved automatically from Web of Science through information on FAPESP grant and its corresponding number as mentioned in the publication by the authors.)

Combined use of tandem mass spectrometry and computational chemistry to study 2H-chromenes from Piper aduncum

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Souza, Amauri Alves [1] ; Vessecchi, Ricardo [2] ; Castro-Gamboa, Ian [1] ; Furlan, Maysa [1]
Total Authors: 4
[1] Univ Estadual Paulista UNESP, Inst Quim, Rua Prof Francisco Degni 55, BR-14800900 Araraquara, SP - Brazil
[2] Univ Sao Paulo, Fac Filosofia Ciencias & Letras Ribeirao Preto, Dept Quim, Ave Bandeirantes 3900, BR-14040901 Ribeirao Preto, SP - Brazil
Total Affiliations: 2
Document type: Journal article
Source: Journal of Mass Spectrometry; v. 54, n. 7, p. 634-642, JUL 2019.
Web of Science Citations: 1

Natural 2H-chromenes were isolated from the crude extract of Piper aduncum (Piperaceae) and analyzed by electrospray ionization tandem mass spectrometry (ESI-MS/MS) applying collision-induced dissociation. Density functional theory (DFT) calculations were used to explain the preferred protonation sites of the 2H-chromenes based on thermochemical parameters, including atomic charges, proton affinity, and gas-phase basicity. After identifying the nucleophilic sites, the pathways were proposed to justify the formation of the diagnostic ions under ESI-MS/MS conditions. The calculated relative energy for each pathway was in good agreement with the energy-resolved plot obtained from ESI-MS/MS data. Moreover, the 2H-chromene underwent proton attachment on the prenyl moiety via a six-membered transition state. This behavior resulted in the formation of a diagnostic ion due to 2-methylpropene loss. These studies provide novel insights into gas-phase dissociation for natural benzopyran compounds, indicating how reactivity is correlated to the intrinsic acid-base equilibrium and structural aspects, including the substitution pattern on the aromatic moiety. Therefore, these results can be applied in the identification of benzopyran derivatives in a variety of biological samples. (AU)

FAPESP's process: 13/07600-3 - CIBFar - Center for Innovation in Biodiversity and Drug Discovery
Grantee:Glaucius Oliva
Support type: Research Grants - Research, Innovation and Dissemination Centers - RIDC
FAPESP's process: 14/50265-3 - Distribution and metabolism of natural and synthetic xenobiotics: from the comprehension of reactional process to tissue imaging generation
Grantee:Norberto Peporine Lopes
Support type: BIOTA-FAPESP Program - Thematic Grants
FAPESP's process: 17/15014-8 - MS and NMR predict datasets of benzopyrans from Piperaceae species for new insights into metabolomic studies
Grantee:Amauri Alves de Souza Júnior
Support type: Scholarships abroad - Research Internship - Doctorate
FAPESP's process: 14/22239-8 - Metabolomic studies of Piperaceae species by MS and NMR: development of analytical methods and dereplication strategies for exploitation of substances of therapeutic interest
Grantee:Amauri Alves de Souza Júnior
Support type: Scholarships in Brazil - Doctorate
FAPESP's process: 14/23604-1 - Computational chemistry: a tool to studies of mass spectrometry, reactivity and fragmentation/reaction mechanisms of organic compounds
Grantee:Ricardo Vessecchi Lourenço
Support type: Regular Research Grants