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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. © 2016, Springer-Verlag Berlin Heidelberg.

Registro:

Documento: Artículo
Título:Z-Isomers of (4α→6″, 2α→O→1″)-phenylflavan substituted with R′=R=OH. Conformational properties, electronic structure and aqueous solvent effects
Autor:Bentz, E.N.; Pomilio, A.B.; Lobayan, R.M.
Filiación:Departamento de Física, Facultad de Ciencias Exactas y Naturales y Agrimensura, Universidad Nacional del Nordeste, Avda. Libertad 5300, Corrientes, Argentina
Instituto de Bioquímica y Medicina Molecular [IBIMOL (ex PRALIB), UBA-CONICET], Facultad de Farmacia y Bioquímica, Universidad de Buenos Aires, Junín 956, Buenos Aires, Argentina
Palabras clave:(4α→6″, 2α→O→1″)- phenylflavans; Antioxidants; Aqueous solvent effect; Atoms in molecules; Density functional theory; Molecular polarizability; Natural bond orbital analysis; PCM model
Año:2016
Volumen:22
Número:8
DOI: http://dx.doi.org/10.1007/s00894-016-3034-9
Título revista:Journal of Molecular Modeling
Título revista abreviado:J. Mol. Model.
ISSN:16102940
CODEN:JMMOF
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_16102940_v22_n8_p_Bentz

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Citas:

---------- APA ----------
Bentz, E.N., Pomilio, A.B. & Lobayan, R.M. (2016) . Z-Isomers of (4α→6″, 2α→O→1″)-phenylflavan substituted with R′=R=OH. Conformational properties, electronic structure and aqueous solvent effects. Journal of Molecular Modeling, 22(8).
http://dx.doi.org/10.1007/s00894-016-3034-9
---------- CHICAGO ----------
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" . Journal of Molecular Modeling 22, no. 8 (2016).
http://dx.doi.org/10.1007/s00894-016-3034-9
---------- MLA ----------
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" . Journal of Molecular Modeling, vol. 22, no. 8, 2016.
http://dx.doi.org/10.1007/s00894-016-3034-9
---------- VANCOUVER ----------
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. 2016;22(8).
http://dx.doi.org/10.1007/s00894-016-3034-9