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A density functional theory study on aurantinidin

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Abstract

A complete conformational analysis on the isolated and PCM modeled aqueous solution cationic, neutral, and anionic forms of aurantinidin, comprising the diverse tautomers of the latter forms, was carried out at the B3LYP/6–31 +  + G(d,p) level. The most stable conformers of isolated cationic and neutral forms of aurantinidin are completely planar, whereas ring B and 3OH are significantly twisted with regard to the AC system in the anion. In contrast, PCM calculations show that the plane of the B ring is slightly rotated with regard to the AC bicycle even in the most stable conformers of the cation and quinonoidal form. The most stable conformers of the cation, in both gas phase and aqueous solution, display anti and syn orientations for hydroxyls at 3 and 5 positions, whereas syn and anti orientation of hydroxyls at 7 and 4' positions are nearly isoenergetic. The most stable tautomer of neutral aurantinidin is obtained by deprotonating hydroxyl at C5 in gas phase, but at C7 in water solution, according to PCM. Also, the most stable tautomer of the anion is different in gas phase (hydrogens are abstracted from hydroxyls at C5 and C4') and PCM calculations for water solution (C3 and C5). Tautomeric equilibria affect substantially the geometries of the AC-B backbone providing bond length variations that basically agree with the predictions of the resonance model. Intramolecular hydrogen bond between O3 and H6' is not present in the most stable anions. Ionization potentials and O–H bond dissociation energies are consistent with an important antioxidant activity.

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Acknowledgements

We thank "Centro de Supercomputación de Galicia" (CESGA) for free access to its computational facilities. Xunta de Galicia is acknowledged for financial support through GRC 2019/24.

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Authors and Affiliations

  1. Departamento de Química Inorgánica, Facultade de Química, Universidade de Vigo, Lagoas-Marcosende S/N, 36310, Vigo, Galicia, Spain

    Mercedes Garcìa-Bugarín

  2. Departamento de Química Física, Facultade de Química, Universidade de Vigo, Lagoas-Marcosende S/N, 36310, Vigo, Galicia, Spain

    Ángeles Peña-Gallego & Ricardo A. Mosquera

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  1. Mercedes Garcìa-Bugarín
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Garcìa-Bugarín, M., Peña-Gallego, Á. & Mosquera, R.A. A density functional theory study on aurantinidin. Theor Chem Acc 142, 73 (2023). https://doi.org/10.1007/s00214-023-03021-9

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