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Molecular structure of cyanidin metal complexes: Al(III) versus Mg(II)

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Abstract

Metal complexation by anthocyanins is a very efficient mechanism for protecting plants. While Mg is an essential metal for life, typically found bound to anthocyanins, Al interferes with the metabolism of the former. Density functional theory and the polarizable continuum model are used to study cyanin (the simplest anthocyanin bearing a catechol unit) complexes with Mg(II) and Al(III), considering different metal ligand stoichiometries. Results obtained for metal-binding energies indicate that Al(III) complexes are always more stable than those of Mg(II). Furthermore, reaction energies for the metal exchange process show that free Al(III) (hexaaquo complex) is always able to displace Mg(II). This displacement is more favored when the metal ligand ratio decreases. Thus, anthocyanins are implied in suppressing Al(III) toxicity by enabling its accumulation and reducing its migration to ecosystems. The characteristics of Al(III)–cyanidin and Mg(II)–cyanidin bonds are investigated using the quantum theory of atoms in molecules. We find these complexes are more stabilized by ion–dipole electrostatic interactions than by electron pair sharing, as predicted by the Hard and Soft Acids Theory. Globally, two factors increase the covalent character: replacement of Mg(II) by Al(III) and replacement of water by cyanidin ligands.

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Acknowledgments

Authors thank “Centro de Supercomputación de Galicia” (CESGA) for free access to its computational facilities and the Galician Government for funding this research through project INCITE09E1R3141091ES.

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Authors and Affiliations

  1. Departamento de Química Física, Universidade de Vigo, Lagoas-Marcosende s/n, 36310, Vigo, Spain

    Laura Estévez, Nicolás Otero & Ricardo A. Mosquera

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  1. Laura Estévez
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  2. Nicolás Otero
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  3. Ricardo A. Mosquera
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Correspondence to Ricardo A. Mosquera.

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Published as part of the special issue celebrating theoretical and computational chemistry in Spain.

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Estévez, L., Otero, N. & Mosquera, R.A. Molecular structure of cyanidin metal complexes: Al(III) versus Mg(II). Theor Chem Acc 128, 485–495 (2011). https://doi.org/10.1007/s00214-010-0829-0

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