Characterization of aporphine alkaloids by electrospray ionization tandem mass spectrometry and density functional theory calculations.

RATIONALE: Aporphine alkaloids represent a large group of isoquinoline natural products with important roles in biological and biomedical areas. Their characterization by electrospray ionization tandem mass spectrometry (ESI-MS/MS) can contribute to their rapid identification in complex biological matrices. METHODS: We report the fragmentation of protonated 7,7-dimethylaporphine alkaloids by ESI-MS/MS, and the putative annotation of aporphine alkaloids in plant extracts. We used low- and high-resolution MS/MS analyses to rationalize the fragmentation pathways, and employed the B3LYP/6-31 + G(d,p) density functional theory (DFT) model to provide thermochemical parameters and to obtain the reactive sites. RESULTS: DFT calculations of a set of 7,7-dimethylaporphine alkaloids suggested the heterocyclic amino group as the most basic site due to the proton affinity of the nitrogen atom. Collision-induced dissociation experiments promoted • OCH3 elimination instead of the expected neutral loss of the heterocyclic amino group, pointing to the [M - 15 + H]•+ ion as the diagnostic fragment for 7,7-dimethylaporphine alkaloids. The analysis of plant extracts led to the annotation of 25 aporphine alkaloids. Their fragmentation initiated with the loss of the amino group followed by formation of a cyclic carbocation. Further reactions derived from consecutive charge-remote and/or charge-induced fragmentations of the substituents attached to the aromatic system. The mechanisms were re-examined based on plausible gas-phase ion chemistry reactions. CONCLUSIONS: Taken together, the diagnostic product ions and the series of radical and neutral eliminations provided information about the location of methylenedioxy, aromatic methoxy, and vicinal methoxy and hydroxy groups in aporphine alkaloids, assisting their characterization via MS/MS.

Chemical Characterization, Antioxidant Capacity and Antimicrobial Potential of Essential Oil from the Leaves of Baccharis oreophila Malme.

This is the first time that composition, antimicrobial potential and antioxidant ability of essential oil from the leaves of Baccharis oreophila are reported. Essential oil was obtained by hydrodistillation and analyzed by GC/MS. Antimicrobial potential was evaluated by diffusion disk and broth microdilution methods. ABTS.+ , DPPH. and FRAP methods were employed for antioxidant activity evaluation. Essential oil yield was 0.47 %. Sixty-five compounds were identified, representing 88.53 % of the total essential oil, which showed to be rich in oxygenated (37.88 %) and hydrocarbons sesquiterpenes (34.84 %). The main constituents were khusimone (16.37 %) and spathulenol (16.12 %). Antimicrobial activity was verified against S. aureus (10.33±0.5 mm, MIC: 1250 µg mL-1 ) and C. albicans (8.66±0.5 mm, MIC: >2500 µg mL.1 ). Antioxidant ability was evidenced by FRAP (4.09 µmol FeSO4 E mL-1 ), ABTS.+ (1.45 µmol TE mL-1 ) and DPPH. (1.04 µmol TE mL-1 ) scavenging capacity. Results showed that this essential oil has interesting biological potential, encouraging further investigations especially in relation to action mechanisms of antimicrobial and antioxidant activity.