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Theoretical Characterization by Density Functional Theory (DFT) of Delphinidin 3-O-Sambubioside and Its Esters Obtained by Chemical Lipophilization

Anthocyanins are water-soluble phenolic pigments. However, their poor solubility in lipidic media limits their use. This hurdle can be overcome with the lipophilization of anthocyanins, which consists of adding an aliphatic chain to a hydrophilic compound, in order to increase its solubility in lipi...

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Autores principales: Márquez-Rodríguez, Ana Selene, Grajeda-Iglesias, Claudia, Sánchez-Bojorge, Nora-Aydeé, Figueroa-Espinoza, María-Cruz, Rodríguez-Valdez, Luz-María, Fuentes-Montero, María Elena, Salas, Erika
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2018
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6100018/
https://www.ncbi.nlm.nih.gov/pubmed/29966272
http://dx.doi.org/10.3390/molecules23071587
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author Márquez-Rodríguez, Ana Selene
Grajeda-Iglesias, Claudia
Sánchez-Bojorge, Nora-Aydeé
Figueroa-Espinoza, María-Cruz
Rodríguez-Valdez, Luz-María
Fuentes-Montero, María Elena
Salas, Erika
author_facet Márquez-Rodríguez, Ana Selene
Grajeda-Iglesias, Claudia
Sánchez-Bojorge, Nora-Aydeé
Figueroa-Espinoza, María-Cruz
Rodríguez-Valdez, Luz-María
Fuentes-Montero, María Elena
Salas, Erika
author_sort Márquez-Rodríguez, Ana Selene
collection PubMed
description Anthocyanins are water-soluble phenolic pigments. However, their poor solubility in lipidic media limits their use. This hurdle can be overcome with the lipophilization of anthocyanins, which consists of adding an aliphatic chain to a hydrophilic compound, in order to increase its solubility in lipids. Still, the unspecific chemical lipophilization of anthocyanin-esters produces molecules with different properties from their precursors. In this work, experimental changes of anthocyanin-esters obtained by chemical lipophilization are investigated in silico aiming specifically at observing their molecular behavior and comparing it with their anthocyanin precursor. Thus, the analysis of delphinidin 3-O-sambubioside and its esters employing Density Functional Theory (DFT) methods, such as the hybrid functional B3LYP in combination with the 6-31++G(d,p) Pople basis set, provides the ground state properties, the local reactivity and the molecular orbitals (MOs) of these compounds. Excited states properties were analyzed by TD-DFT with the B3LYP functional, and the M06 and M06-2X meta-GGA functionals. Local reactivity calculations showed that the electrophilic site for all the anthocyanin-esters was the same as the one for the anthocyanin precursor, however the nucleophilic site changed depending localization of the esterification. TD-DFT results indicate that the place of esterification could change the electronic transitions and the MOs spatial distribution.
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spelling pubmed-61000182018-11-13 Theoretical Characterization by Density Functional Theory (DFT) of Delphinidin 3-O-Sambubioside and Its Esters Obtained by Chemical Lipophilization Márquez-Rodríguez, Ana Selene Grajeda-Iglesias, Claudia Sánchez-Bojorge, Nora-Aydeé Figueroa-Espinoza, María-Cruz Rodríguez-Valdez, Luz-María Fuentes-Montero, María Elena Salas, Erika Molecules Article Anthocyanins are water-soluble phenolic pigments. However, their poor solubility in lipidic media limits their use. This hurdle can be overcome with the lipophilization of anthocyanins, which consists of adding an aliphatic chain to a hydrophilic compound, in order to increase its solubility in lipids. Still, the unspecific chemical lipophilization of anthocyanin-esters produces molecules with different properties from their precursors. In this work, experimental changes of anthocyanin-esters obtained by chemical lipophilization are investigated in silico aiming specifically at observing their molecular behavior and comparing it with their anthocyanin precursor. Thus, the analysis of delphinidin 3-O-sambubioside and its esters employing Density Functional Theory (DFT) methods, such as the hybrid functional B3LYP in combination with the 6-31++G(d,p) Pople basis set, provides the ground state properties, the local reactivity and the molecular orbitals (MOs) of these compounds. Excited states properties were analyzed by TD-DFT with the B3LYP functional, and the M06 and M06-2X meta-GGA functionals. Local reactivity calculations showed that the electrophilic site for all the anthocyanin-esters was the same as the one for the anthocyanin precursor, however the nucleophilic site changed depending localization of the esterification. TD-DFT results indicate that the place of esterification could change the electronic transitions and the MOs spatial distribution. MDPI 2018-06-29 /pmc/articles/PMC6100018/ /pubmed/29966272 http://dx.doi.org/10.3390/molecules23071587 Text en © 2018 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Márquez-Rodríguez, Ana Selene
Grajeda-Iglesias, Claudia
Sánchez-Bojorge, Nora-Aydeé
Figueroa-Espinoza, María-Cruz
Rodríguez-Valdez, Luz-María
Fuentes-Montero, María Elena
Salas, Erika
Theoretical Characterization by Density Functional Theory (DFT) of Delphinidin 3-O-Sambubioside and Its Esters Obtained by Chemical Lipophilization
title Theoretical Characterization by Density Functional Theory (DFT) of Delphinidin 3-O-Sambubioside and Its Esters Obtained by Chemical Lipophilization
title_full Theoretical Characterization by Density Functional Theory (DFT) of Delphinidin 3-O-Sambubioside and Its Esters Obtained by Chemical Lipophilization
title_fullStr Theoretical Characterization by Density Functional Theory (DFT) of Delphinidin 3-O-Sambubioside and Its Esters Obtained by Chemical Lipophilization
title_full_unstemmed Theoretical Characterization by Density Functional Theory (DFT) of Delphinidin 3-O-Sambubioside and Its Esters Obtained by Chemical Lipophilization
title_short Theoretical Characterization by Density Functional Theory (DFT) of Delphinidin 3-O-Sambubioside and Its Esters Obtained by Chemical Lipophilization
title_sort theoretical characterization by density functional theory (dft) of delphinidin 3-o-sambubioside and its esters obtained by chemical lipophilization
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6100018/
https://www.ncbi.nlm.nih.gov/pubmed/29966272
http://dx.doi.org/10.3390/molecules23071587
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