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Theoretical study of Z isomers of A-type dimeric proanthocyanidins substituted with R=H, OH and OCH3: stability and reactivity properties

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Abstract

The stereochemistry of A-type dimeric proanthocyanidins was studied, focusing on the factors that determine it, and the changes that occur with R = OCH3, R′ = H, and R = OH, R′ = H as substituents, starting with the study of the conformational space of each species. Using molecular dynamics at a semiempirical level, and complementing with functional density calculations, two conformers of lowest energy were characterized for R = H, eight conformers for R = OH, and three conformers for R = OCH3. Electronic distributions were analyzed at a higher calculation level, thus improving the basis set. Intramolecular interactions were examined and characterized by the theory of atoms in molecules (AIM). Detailed natural bond orbitals (NBO) analysis allowed the description of subtle stereoelectronic aspects of fundamental importance for understanding the stabilization and antioxidant function of these structures. The study was enriched by a deep analysis of maps of molecular electrostatic potential (MEP). The coordinated analysis of MEP, together with the NBO and AIM results, allowed us to rationalize novel distribution aspects of the potential created in the space around a molecule.

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Acknowledgments

Thanks are due to Agencia de Promoción Científica y Tecnológica Argentina (MINCYT), CONICET, Universidad Nacional de La Plata and Universidad de Buenos Aires (Argentina) for financial support. A.B.P. is a Senior Research Member of the National Research Council of Argentina (CONICET). A.H.J. is Member of the Scientific Research Career (CIC, Provincia de Buenos Aires). E.N.B. acknowledges a fellowship (IP-PRH No 54) from Agencia de Promoción Científica y Tecnológica Argentina and Universidad de la Cuenca del Plata (Corrientes, Argentina). R.M.L. acknowledges Universidad de la Cuenca del Plata for facilities provided during the course of this work.

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Authors and Affiliations

  1. Facultad de Ingeniería, Universidad de la Cuenca del Plata, Lavalle 50, 3400, Corrientes, Argentina

    Erika N. Bentz & Rosana M. Lobayan

  2. CEQUINOR Facultad de Ciencias Exactas y Facultad de Ingeniería, Universidad Nacional de La Plata, CC 962, 1900, La Plata, Argentina

    Alicia H. Jubert

  3. PRALIB (UBA, CONICET), Facultad de Farmacia y Bioquímica, Universidad de Buenos Aires, Junín 956, C1113AAD, Buenos Aires, Argentina

    Alicia B. Pomilio

Authors
  1. Erika N. Bentz
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  2. Alicia H. Jubert
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  3. Alicia B. Pomilio
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  4. Rosana M. Lobayan
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Correspondence to Rosana M. Lobayan.

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ESM Fig. S1a–d

Maps of molecular electrostatic potential (MEP) for Z1 rotamers, substituted with R = OCH3 (a), R = H (b) and R = OH (c) and for Z2 rotamers substituted with R = OH (d) of A-type dimeric proanthocyanidins, in a.u. Oblique lines indicate the decreasing reactivity towards electrophilic attack OCH3 (a) >H (b) >OH (c). Horizontal lines show higher reactivity of Z1 (c) rotamers than that of Z2 rotamers (d). (PDF 797 kb)

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Bentz, E.N., Jubert, A.H., Pomilio, A.B. et al. Theoretical study of Z isomers of A-type dimeric proanthocyanidins substituted with R=H, OH and OCH3: stability and reactivity properties. J Mol Model 16, 1895–1909 (2010). https://doi.org/10.1007/s00894-010-0682-z

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