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Z-Isomers of (4α→6″, 2α→O→1″)-phenylflavan substituted with R′=R=OH. Conformational properties, electronic structure and aqueous solvent effects

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Abstract

Procyanidins are highly hydroxylated polymers known as antioxidant compounds, thereby exhibiting beneficial effects. These compounds are protective agents against oxidative stress and the damage induced by free radicals in membranes and nucleic acids. This paper describes a study of the conformational space of (4α→6″, 2α→O→1″)-phenylflavan substituted with R′=R=OH as part of a larger study of similar structures with different substitutions. The relationships between aqueous solution–vacuum variations of some properties were studied, as well as the stabilization and reactivity of (4α→6″, 2α→O→1″)-phenylflavan substituted with R′=R=H, R′=H, R=OH, R′=R=OH, and (+)-catechin. The variations in geometric parameters and electronic properties due to conformational changes, as well as the effects of substituents and polar solvents, were evaluated and analyzed. Bader’s theory of atoms in molecules was applied to characterize intramolecular interactions, along with a natural bond orbital analysis for each conformer described. The molecular electrostatic potential was rationalized by charge delocalization mechanisms and interatomic intramolecular interactions, relating them to the structural changes and topological properties of the electron charge density. Molecular polarizability and permanent electric dipole moment values were estimated. The results show the importance of a knowledge of the conformational space, and values for each conformer. Based on our previous results, we showed the existence of electron charge delocalization mechanisms acting cooperatively as “delocalization routes”, showing interactions between different rings not even sharing the same plane. These “delocalization routes” were more effective for (4α→6″, 2α→O→1″)-phenylflavan substituted with R′=R=OH than for (+)-catechin, and are proposed as adding insight into the structure–antioxidant activity relationship of flavans.

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Acknowledgments

Thanks are due to National Council of Scientific and Technical Researches of Argentina (CONICET) and Universidad de Buenos Aires (Argentina) for financial support. A.B.P. is a Senior Research Member of CONICET. E.N.B. acknowledges a fellowship of CONICET and Universidad Nacional del Nordeste (Corrientes, Argentina). R.M.L. acknowledges Centro de Cómputos de Alto Desempeño de la Universidad Nacional del Nordeste (CADUNNE) for computational facilities, and financial support of the Secretaria General de Ciencia y Técnica de la Universidad Nacional del Nordeste (Corrientes, Argentina).

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Authors and Affiliations

  1. Departamento de Física, Facultad de Ciencias Exactas y Naturales y Agrimensura, Universidad Nacional del Nordeste, Avda. Libertad 5300, 3400, Corrientes, Argentina

    Erika N. Bentz & Rosana M. Lobayan

  2. Instituto de Bioquímica y Medicina Molecular [IBIMOL (ex PRALIB), UBA-CONICET], Facultad de Farmacia y Bioquímica, Universidad de Buenos Aires, Junín 956, C1113AAD, Buenos Aires, Argentina

    Alicia B. Pomilio

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  1. Erika N. Bentz
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  2. Alicia B. Pomilio
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  3. Rosana M. Lobayan
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Correspondence to Rosana M. Lobayan.

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Bentz, E.N., Pomilio, A.B. & Lobayan, R.M. Z-Isomers of (4α→6″, 2α→O→1″)-phenylflavan substituted with R′=R=OH. Conformational properties, electronic structure and aqueous solvent effects. J Mol Model 22, 187 (2016). https://doi.org/10.1007/s00894-016-3034-9

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