Proportional coexistence of okanin chalcone glycoside and okanin flavanone glycoside in Bidens pilosa leaves and theoretical investigation on the antioxidant properties of their aglycones

Abstract

Bidens pilosa plant has been shown to produce okanin flavanone glycoside and its chalcone derivative. In most other plants, due to chalcone isomerase enzyme, the flavanone tends to exist in higher proportions than their chalcone precursors. Herein we have utilized liquid chromatography–mass spectrometry approach and shown that within the leaves of Bidens pilosa plant the two okanin glycosides exist in unusual equal proportional distribution, which indicates that Bidens pilosa plant is an alternative rich source of these highly sought-after antioxidant molecules. The aglycone okanin chalcone (ONC) and okanin flavanone (ONF) have experimentally been shown to exhibit antioxidant activity. However, experimental findings have not conclusively determined which of the two compounds is a more potent antiradical than the other. Herein, the density functional theory (DFT) method is utilized to establish, from structural and thermodynamic energetic considerations, the preferred antioxidant molecule between the two aglycone okanins. A theoretical study on the antioxidant properties of ONC and ONF has been performed by considering their radical scavenging and metal cation (Mⁿ⁺, where M = Cu(II) or Fe (III)) chelation ability. The study has been performed using B3LYP/6-31 + G(d,p) method. In the case of the metal chelation mechanism, the LANL2DZ pseudo-potential was selected to describe the selected Mⁿ⁺ cations. The results of the study suggest that ONC is a better radical scavenger than ONF because of the extended electron delocalization on its neutral radical, which is due to the presence of conjugation within the ONC neutral radical after hydrogen atom abstraction. In the metal chelation mechanism, it is noted that the binding energies depend on the media, the nature of the ligand and the cation and the cation coordination site on the ligand. The charge and the spin density on Mⁿ⁺ decrease on coordination to the ligand. The ability of the ligands to reduce Mⁿ⁺ cations, coupled with the strong Mⁿ⁺ binding properties, has significant implication on the antioxidant ability of both okanins. However, since ONC⋅⋅⋅M⁺ⁿ interaction results in higher binding energy than ONF⋅⋅⋅M⁺ⁿ interaction, the implication is that ONC is a preferred free metal ion chelator than ONF.

Keywords:

• Okanin
• flavanokanin
• chemo-diversification
• atomic spin density
• chelate ring
• metal chelation

Acknowledgments

The authors also thank the CSIR Centre for High Performance Computing (CHPC) in South Africa for providing computational resources.

Disclosure statement

No potential conflict of interest was reported by the author(s). The founding sponsors had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, and in the decision to publish the results.

Additional information

Funding

The authors would like to thank the University of Johannesburg and National research foundation (NRF) for their financial support.