Fragmentation studies on labdane-type diterpenes isolated from Copaifera langsdorffii oleoresin using tandem mass spectrometry

• Grant number: 12/22832-5
• Support type: Scholarships in Brazil - Master
• Effective date (Start): March 01, 2013
• Effective date (End): February 28, 2015
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Organic Chemistry
• Principal researcher: Vladimir Constantino Gomes Heleno
• Grantee: Gabriela de Paula Aguiar
• Home Institution: Pró-Reitoria Adjunta de Pesquisa e Pós-Graduação. Universidade de Franca (UNIFRAN). Franca , SP, Brazil
• Associated research grant: 11/13630-7 - Chemical and pharmacological validation of extracts and active compounds of Copaifera species, AP.TEM

Abstract

Copaifera (Leguminoseae) species produce oleoresins of high commercial importance, which are sold from the Amazon region to other Brazilian regions or exported to Europe and North America countries. These oils are very used in cosmetics industries due to their emollient, antibacterial and anti-inflammatory properties, being also used for medicinal purposes, such as anti-inflammatory, antiseptic, antiasthmatic, analgesic, antidiarrheal, healing, aphrodisiac, antioxidant, antitetanic, antiherpes, antimicrobial, anticancer and antitumor, among others. However, in despite of their pharmacological importance, most of the Copaifera oleoresins are generically commercialized as "copaiba oils", without the correct identification of the species the oleoresin was extracted from. In this context, aiming to assure the efficacy, safety and quality of these phytotherapeutics, it was recently approved by FAPESP a thematic project to validate the chemistry and the pharmacology of extracts and active principles of Copaifera species (proc. FAPESP 2011/13630-7). Thus, as part of the dereplication studies of Copaifera oleoresins proposed in that Project, the goals of this proposal are the isolatation and structural elucidation of labdane-type diterpenes from the Copaifera langsdorffii oleoresin, and the investigation of the fragmentation pathways of their protonated and/or deprotonated molecules using tandem mass spectrometry (MS/MS). These diterpenes are amongst the major chemical constituents of the oleoresin of Copaifera. Firstly, they will be analyzed using atmospheric pressure chemical ionization (APCI) and electrospray (ESI) sources in the positive and negative ion modes in order to identify the most adequate ionization source and analysis mode for further dereplication studies proposed in the thematic project. After, the main diagnostic fragment ions will be identified and their formation will be rationalized from structure-fragmentation correlations. Finally, the mechanistic pathways will be elucidated on the basis of thermochemical data obtained by Computational Quantic Chemistry.

Scientific publications

(References retrieved automatically from Web of Science and SciELO through information on FAPESP grants and their corresponding numbers as mentioned in the publications by the authors)

AGUIAR, GABRIELA P.; CREVELIN, EDUARDO J.; DIAS, HERBERT J.; AMBROSIO, SERGIO R.; BASTOS, JAIRO K.; HELENO, VLADIMIR C. G.; VESSECCHI, RICARDO; CROTTI, ANTONIO E. M. Electrospray ionization tandem mass spectrometry of labdane-type acid diterpenes. Journal of Mass Spectrometry, v. 53, n. 11, p. 1086-1096, NOV 2018. Web of Science Citations: 1.