Theoretical and experimental study of the diastereoisomers (2S) and (2R)-naringenin-6-C-β-D-glucopyranoside obtained from Clitoria guianensis
Autor(a) principal: | |
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Data de Publicação: | 2023 |
Outros Autores: | , , , , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Institucional da UNESP |
Texto Completo: | http://dx.doi.org/10.1007/s00894-023-05482-y http://hdl.handle.net/11449/249705 |
Resumo: | Abstract: In this work the diastereoisomers (2S) and (2R)-naringenin-6-C-β-D-glucopyroside, isolated for the first time from Clitoria guianensis, were studied using the density functional theory. The frontier molecular orbitals and structural properties showed that the diastereoisomers exhibit the same energy gap 166.61 kcal mol−1 and structural properties different, where in the S diastereoisomer, the bond length between the chiral carbon and the phenolic group is greater (difference of 0.0126 Å). The HPLC data showed that the retention time of the S-diastereoisomer (16.7 min) is shorter than that of R, suggesting that the S compound is more polar than R. The HPLC results corroborates with the molecular electrostatic potential which showed that in the S configuration, the electronegative density was more intense overall, particularly in the glucose molecule. The reactivity indices showed that the diastereoisomers are good electrophiles and reactive species. Finally, the absolute configuration of the diastereoisomers were determined using electronic circular dichroism (ECD) spectroscopy and the theoretical spectra were similar to the experimental. Methods: All calculations of Density Functional Theory (DFT) and Time-Dependent Density Functional Theory (TDDFT) were performed using the program Gaussian 09 and the structures of the diastereoisomers were generated and analyzed using the GaussView program. The optimization and vibrational frequency calculations were performed using the functional CAM-B3LYP and 6–311 + + G(2d,2p) basis set. Conformational searches were performed for R configuration, by molecular mechanics using the MM + , MMFF, and OPLS05 force fields; the entire molecular mechanics simulation was performed using the Maestro/MacroModel software. The calculations for the simulations of the ECD spectra were performed for the eight lowest energy conformers obtained in the geometric optimization step, and the TDDFT at the CAM-B3LYP/6–311 + + G(2d,2p) theory level used. The effects of methanol and chloroform were calculated using the SMD implicit solvent model. |
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Theoretical and experimental study of the diastereoisomers (2S) and (2R)-naringenin-6-C-β-D-glucopyranoside obtained from Clitoria guianensisAbsolute configurationCircular DichroismConformational searchTDDFTAbstract: In this work the diastereoisomers (2S) and (2R)-naringenin-6-C-β-D-glucopyroside, isolated for the first time from Clitoria guianensis, were studied using the density functional theory. The frontier molecular orbitals and structural properties showed that the diastereoisomers exhibit the same energy gap 166.61 kcal mol−1 and structural properties different, where in the S diastereoisomer, the bond length between the chiral carbon and the phenolic group is greater (difference of 0.0126 Å). The HPLC data showed that the retention time of the S-diastereoisomer (16.7 min) is shorter than that of R, suggesting that the S compound is more polar than R. The HPLC results corroborates with the molecular electrostatic potential which showed that in the S configuration, the electronegative density was more intense overall, particularly in the glucose molecule. The reactivity indices showed that the diastereoisomers are good electrophiles and reactive species. Finally, the absolute configuration of the diastereoisomers were determined using electronic circular dichroism (ECD) spectroscopy and the theoretical spectra were similar to the experimental. Methods: All calculations of Density Functional Theory (DFT) and Time-Dependent Density Functional Theory (TDDFT) were performed using the program Gaussian 09 and the structures of the diastereoisomers were generated and analyzed using the GaussView program. The optimization and vibrational frequency calculations were performed using the functional CAM-B3LYP and 6–311 + + G(2d,2p) basis set. Conformational searches were performed for R configuration, by molecular mechanics using the MM + , MMFF, and OPLS05 force fields; the entire molecular mechanics simulation was performed using the Maestro/MacroModel software. The calculations for the simulations of the ECD spectra were performed for the eight lowest energy conformers obtained in the geometric optimization step, and the TDDFT at the CAM-B3LYP/6–311 + + G(2d,2p) theory level used. The effects of methanol and chloroform were calculated using the SMD implicit solvent model.Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Collegiate of Exact Sciences and Biotechnology Universidade Federal do Tocantins, 77 402-970, TocantinsGraduate Program in Chemistry Universidade Federal do Tocantins, 77 402-970, TocantinsInstitute of Chemistry Universidade Estadual Paulista (Unesp), SPInstitute of Chemistry Universidade Estadual Paulista (Unesp), SPCAPES: 001FAPESP: 2013/08293-7FAPESP: Grant 2017/11485-6Universidade Federal do TocantinsUniversidade Estadual Paulista (UNESP)Cruz, Állefe BarbosaCiribelli, Nicolas NascimentoCunha, Camila Luiza [UNESP]Nascimento, Isabele Rodrigues [UNESP]Holzbach, Juliana CristinaPereira, Douglas Henrique2023-07-29T16:07:02Z2023-07-29T16:07:02Z2023-03-01info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articlehttp://dx.doi.org/10.1007/s00894-023-05482-yJournal of Molecular Modeling, v. 29, n. 3, 2023.0948-50231610-2940http://hdl.handle.net/11449/24970510.1007/s00894-023-05482-y2-s2.0-85149048707Scopusreponame:Repositório Institucional da UNESPinstname:Universidade Estadual Paulista (UNESP)instacron:UNESPengJournal of Molecular Modelinginfo:eu-repo/semantics/openAccess2024-05-03T17:28:26Zoai:repositorio.unesp.br:11449/249705Repositório InstitucionalPUBhttp://repositorio.unesp.br/oai/requestopendoar:29462024-05-03T17:28:26Repositório Institucional da UNESP - Universidade Estadual Paulista (UNESP)false |
dc.title.none.fl_str_mv |
Theoretical and experimental study of the diastereoisomers (2S) and (2R)-naringenin-6-C-β-D-glucopyranoside obtained from Clitoria guianensis |
title |
Theoretical and experimental study of the diastereoisomers (2S) and (2R)-naringenin-6-C-β-D-glucopyranoside obtained from Clitoria guianensis |
spellingShingle |
Theoretical and experimental study of the diastereoisomers (2S) and (2R)-naringenin-6-C-β-D-glucopyranoside obtained from Clitoria guianensis Cruz, Állefe Barbosa Absolute configuration Circular Dichroism Conformational search TDDFT |
title_short |
Theoretical and experimental study of the diastereoisomers (2S) and (2R)-naringenin-6-C-β-D-glucopyranoside obtained from Clitoria guianensis |
title_full |
Theoretical and experimental study of the diastereoisomers (2S) and (2R)-naringenin-6-C-β-D-glucopyranoside obtained from Clitoria guianensis |
title_fullStr |
Theoretical and experimental study of the diastereoisomers (2S) and (2R)-naringenin-6-C-β-D-glucopyranoside obtained from Clitoria guianensis |
title_full_unstemmed |
Theoretical and experimental study of the diastereoisomers (2S) and (2R)-naringenin-6-C-β-D-glucopyranoside obtained from Clitoria guianensis |
title_sort |
Theoretical and experimental study of the diastereoisomers (2S) and (2R)-naringenin-6-C-β-D-glucopyranoside obtained from Clitoria guianensis |
author |
Cruz, Állefe Barbosa |
author_facet |
Cruz, Állefe Barbosa Ciribelli, Nicolas Nascimento Cunha, Camila Luiza [UNESP] Nascimento, Isabele Rodrigues [UNESP] Holzbach, Juliana Cristina Pereira, Douglas Henrique |
author_role |
author |
author2 |
Ciribelli, Nicolas Nascimento Cunha, Camila Luiza [UNESP] Nascimento, Isabele Rodrigues [UNESP] Holzbach, Juliana Cristina Pereira, Douglas Henrique |
author2_role |
author author author author author |
dc.contributor.none.fl_str_mv |
Universidade Federal do Tocantins Universidade Estadual Paulista (UNESP) |
dc.contributor.author.fl_str_mv |
Cruz, Állefe Barbosa Ciribelli, Nicolas Nascimento Cunha, Camila Luiza [UNESP] Nascimento, Isabele Rodrigues [UNESP] Holzbach, Juliana Cristina Pereira, Douglas Henrique |
dc.subject.por.fl_str_mv |
Absolute configuration Circular Dichroism Conformational search TDDFT |
topic |
Absolute configuration Circular Dichroism Conformational search TDDFT |
description |
Abstract: In this work the diastereoisomers (2S) and (2R)-naringenin-6-C-β-D-glucopyroside, isolated for the first time from Clitoria guianensis, were studied using the density functional theory. The frontier molecular orbitals and structural properties showed that the diastereoisomers exhibit the same energy gap 166.61 kcal mol−1 and structural properties different, where in the S diastereoisomer, the bond length between the chiral carbon and the phenolic group is greater (difference of 0.0126 Å). The HPLC data showed that the retention time of the S-diastereoisomer (16.7 min) is shorter than that of R, suggesting that the S compound is more polar than R. The HPLC results corroborates with the molecular electrostatic potential which showed that in the S configuration, the electronegative density was more intense overall, particularly in the glucose molecule. The reactivity indices showed that the diastereoisomers are good electrophiles and reactive species. Finally, the absolute configuration of the diastereoisomers were determined using electronic circular dichroism (ECD) spectroscopy and the theoretical spectra were similar to the experimental. Methods: All calculations of Density Functional Theory (DFT) and Time-Dependent Density Functional Theory (TDDFT) were performed using the program Gaussian 09 and the structures of the diastereoisomers were generated and analyzed using the GaussView program. The optimization and vibrational frequency calculations were performed using the functional CAM-B3LYP and 6–311 + + G(2d,2p) basis set. Conformational searches were performed for R configuration, by molecular mechanics using the MM + , MMFF, and OPLS05 force fields; the entire molecular mechanics simulation was performed using the Maestro/MacroModel software. The calculations for the simulations of the ECD spectra were performed for the eight lowest energy conformers obtained in the geometric optimization step, and the TDDFT at the CAM-B3LYP/6–311 + + G(2d,2p) theory level used. The effects of methanol and chloroform were calculated using the SMD implicit solvent model. |
publishDate |
2023 |
dc.date.none.fl_str_mv |
2023-07-29T16:07:02Z 2023-07-29T16:07:02Z 2023-03-01 |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/article |
format |
article |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://dx.doi.org/10.1007/s00894-023-05482-y Journal of Molecular Modeling, v. 29, n. 3, 2023. 0948-5023 1610-2940 http://hdl.handle.net/11449/249705 10.1007/s00894-023-05482-y 2-s2.0-85149048707 |
url |
http://dx.doi.org/10.1007/s00894-023-05482-y http://hdl.handle.net/11449/249705 |
identifier_str_mv |
Journal of Molecular Modeling, v. 29, n. 3, 2023. 0948-5023 1610-2940 10.1007/s00894-023-05482-y 2-s2.0-85149048707 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
Journal of Molecular Modeling |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.source.none.fl_str_mv |
Scopus reponame:Repositório Institucional da UNESP instname:Universidade Estadual Paulista (UNESP) instacron:UNESP |
instname_str |
Universidade Estadual Paulista (UNESP) |
instacron_str |
UNESP |
institution |
UNESP |
reponame_str |
Repositório Institucional da UNESP |
collection |
Repositório Institucional da UNESP |
repository.name.fl_str_mv |
Repositório Institucional da UNESP - Universidade Estadual Paulista (UNESP) |
repository.mail.fl_str_mv |
|
_version_ |
1799965169131978752 |