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Computational Studies on Conformation, Electron Density Distributions, and Antioxidant Properties of Anthocyanidins

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Advanced Protocols in Oxidative Stress III

Part of the book series: Methods in Molecular Biology ((MIMB,volume 1208))

Abstract

Computational studies carried out at density functional theory levels are able to provide reliable chemical information about medium sized compounds as anthocyanins and their aglycons (anthocyanidins). Thus, they indicate that the most stable tautomers in aqueous solution for the main anthocyanidins (excluding pelargonidin) are deprotonated at C4′ in the neutral forms, while deprotonations at C5 and C4′ characterize the most stable anions in solution. QTAIM electron density analysis (overviewed in brief in the methods section) shows that Lewis structures usually employed give rise to unreliable atomic charges. Thus: (1) The positive charge spreads throughout the whole cation, and is not localized on any specific atom or set of atoms; (2) Neutral forms can be described as enolates where the negative charge is counterbalanced in a different way to that indicated by the typical resonance forms; and (3) The negative charge of anions is mainly spread among three regions of the molecule: the two deprotonated sites and the C9-O1-C2 area. The analysis of a group of complexes formed by a model of cyanin with four common metalic cations (Mg(II), Al(II), Cu(II), Zn(II)), shows: (1) the preference for tetracoordination in Zn(II) and Cu(II) complexes, (2) higher affinity for Cu(II) than for the other metals here studied, and (3) the distortion of electron density in the cyanin ligand affects the whole molecule. This distortion can be described as a continuous polarization where, even, in some cases, the atomic electron populations of those atoms of the ligand that are more directly involved in bonding to the metal increase.

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Acknowledgements

We thank “Centro de Supercomputación de Galicia” (CESGA) for free access to its computational facilities, and financial support from Spanish Ministry of Economy through research project CTQ2010-21500.

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Authors and Affiliations

  1. Department of Physical Chemistry, University of Vigo, Bloque E, Planta 2ª, Seminario 8, Lagoas-Marcosende s/n, Vigo, 36200, Spain

    Ricardo A. Mosquera & Laura Estévez

  2. Department of Inorganic Chemistry, University of Vigo, Vigo, 36310, Spain

    Mercedes García Bugarín

Authors
  1. Ricardo A. Mosquera
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  2. Laura Estévez
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  3. Mercedes García Bugarín
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Corresponding author

Correspondence to Ricardo A. Mosquera .

Editor information

Editors and Affiliations

  1. University of Florida, Gainsville, Florida, USA

    Donald Armstrong

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Mosquera, R.A., Estévez, L., Bugarín, M.G. (2015). Computational Studies on Conformation, Electron Density Distributions, and Antioxidant Properties of Anthocyanidins. In: Armstrong, D. (eds) Advanced Protocols in Oxidative Stress III. Methods in Molecular Biology, vol 1208. Humana Press, New York, NY. https://doi.org/10.1007/978-1-4939-1441-8_19

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  • DOI: https://doi.org/10.1007/978-1-4939-1441-8_19

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  • Publisher Name: Humana Press, New York, NY

  • Print ISBN: 978-1-4939-1440-1

  • Online ISBN: 978-1-4939-1441-8

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