On the effect of intramolecular H-bonding in the configurational assessment of polyhydroxylated compounds with computational methods : The hyacinthacines case

Autores
Zanardi, María Marta; Sortino, Maximiliano A.; Sarotti, Ariel M.
Año de publicación
2019
Idioma
inglés
Tipo de recurso
artículo
Estado
versión aceptada
Descripción
Fil: Zanardi, María Marta. Pontificia Universidad Católica Argentina. Facultad de Química e Ingeniería del Rosario; Argentina
Fil: Zanardi, María Marta. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Área Farmacognosia; Argentina
Fil: Sortino, Maximiliano A. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Área Farmacognosia; Argentina
Fil: Sarotti, Ariel M. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química de Rosario; Argentina
Fil: Sarotti, Ariel M. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Abstract: Hyacinthacines are important members of the pyrrolizidine family, with several compounds having ambiguous, revised or unverified structures. Herein we thoroughly explored the performance DP4 and DP4+ for the in silico stereoassignment of hyacinthacines A1, A2 and five synthetic isomers. The results suggested that the quality of the predictions strongly depended on the conformational landscape provided by DFT energies, with five compounds correctly assigned. In the two cases incorrectly classified we found that the source of the problem was conformational in nature, with spurious conformations being considerably over-stabilized by intramolecular H-bondings. We showed that neglecting such shapes resulted in a noteworthy improvement, with all compounds correctly assigned in high confidence (>99.9%).
Fuente
Carbohydrate Research. Vol. 474, 2019
Materia
ISOMEROS
METODO COMPUTACIONAL
QUIMICA
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/4.0/
Repositorio
Repositorio Institucional (UCA)
Institución
Pontificia Universidad Católica Argentina
OAI Identificador
oai:ucacris:123456789/9025
Acceder
id RIUCA_4ed3181511acea802e94e44d755c349a
oai_identifier_str oai:ucacris:123456789/9025
network_acronym_str RIUCA
repository_id_str 2585
network_name_str Repositorio Institucional (UCA)
spelling On the effect of intramolecular H-bonding in the configurational assessment of polyhydroxylated compounds with computational methods : The hyacinthacines caseZanardi, María MartaSortino, Maximiliano A.Sarotti, Ariel M.ISOMEROSMETODO COMPUTACIONALQUIMICAFil: Zanardi, María Marta. Pontificia Universidad Católica Argentina. Facultad de Química e Ingeniería del Rosario; ArgentinaFil: Zanardi, María Marta. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Área Farmacognosia; ArgentinaFil: Sortino, Maximiliano A. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Área Farmacognosia; ArgentinaFil: Sarotti, Ariel M. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química de Rosario; ArgentinaFil: Sarotti, Ariel M. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaAbstract: Hyacinthacines are important members of the pyrrolizidine family, with several compounds having ambiguous, revised or unverified structures. Herein we thoroughly explored the performance DP4 and DP4+ for the in silico stereoassignment of hyacinthacines A1, A2 and five synthetic isomers. The results suggested that the quality of the predictions strongly depended on the conformational landscape provided by DFT energies, with five compounds correctly assigned. In the two cases incorrectly classified we found that the source of the problem was conformational in nature, with spurious conformations being considerably over-stabilized by intramolecular H-bondings. We showed that neglecting such shapes resulted in a noteworthy improvement, with all compounds correctly assigned in high confidence (>99.9%).Elsevier2019info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfhttps://repositorio.uca.edu.ar/handle/123456789/90250008-6215https://doi.org/10.1016/j.carres.2019.01.011Zanardi, M. M., Sortino, M. A., Sarotti, A. M. On the effect of intramolecular H-bonding in the configurational assessment of polyhydroxylated compounds with computational methods : The hyacinthacines case [en línea]. Carbohydrate Research. 2019, 474. doy: https://doi.org/10.1016/j.carres.2019.01.011. Disponible en: https://repositorio.uca.edu.ar/handle/123456789/9025Carbohydrate Research. Vol. 474, 2019reponame:Repositorio Institucional (UCA)instname:Pontificia Universidad Católica Argentinaenginfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/4.0/2025-07-03T10:57:00Zoai:ucacris:123456789/9025instacron:UCAInstitucionalhttps://repositorio.uca.edu.ar/Universidad privadaNo correspondehttps://repositorio.uca.edu.ar/oaiclaudia_fernandez@uca.edu.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:25852025-07-03 10:57:00.778Repositorio Institucional (UCA) - Pontificia Universidad Católica Argentinafalse
dc.title.none.fl_str_mv On the effect of intramolecular H-bonding in the configurational assessment of polyhydroxylated compounds with computational methods : The hyacinthacines case
title On the effect of intramolecular H-bonding in the configurational assessment of polyhydroxylated compounds with computational methods : The hyacinthacines case
spellingShingle On the effect of intramolecular H-bonding in the configurational assessment of polyhydroxylated compounds with computational methods : The hyacinthacines case
Zanardi, María Marta
ISOMEROS
METODO COMPUTACIONAL
QUIMICA
title_short On the effect of intramolecular H-bonding in the configurational assessment of polyhydroxylated compounds with computational methods : The hyacinthacines case
title_full On the effect of intramolecular H-bonding in the configurational assessment of polyhydroxylated compounds with computational methods : The hyacinthacines case
title_fullStr On the effect of intramolecular H-bonding in the configurational assessment of polyhydroxylated compounds with computational methods : The hyacinthacines case
title_full_unstemmed On the effect of intramolecular H-bonding in the configurational assessment of polyhydroxylated compounds with computational methods : The hyacinthacines case
title_sort On the effect of intramolecular H-bonding in the configurational assessment of polyhydroxylated compounds with computational methods : The hyacinthacines case
dc.creator.none.fl_str_mv Zanardi, María Marta
Sortino, Maximiliano A.
Sarotti, Ariel M.
author Zanardi, María Marta
author_facet Zanardi, María Marta
Sortino, Maximiliano A.
Sarotti, Ariel M.
author_role author
author2 Sortino, Maximiliano A.
Sarotti, Ariel M.
author2_role author
author
dc.subject.none.fl_str_mv ISOMEROS
METODO COMPUTACIONAL
QUIMICA
topic ISOMEROS
METODO COMPUTACIONAL
QUIMICA
dc.description.none.fl_txt_mv Fil: Zanardi, María Marta. Pontificia Universidad Católica Argentina. Facultad de Química e Ingeniería del Rosario; Argentina
Fil: Zanardi, María Marta. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Área Farmacognosia; Argentina
Fil: Sortino, Maximiliano A. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Área Farmacognosia; Argentina
Fil: Sarotti, Ariel M. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química de Rosario; Argentina
Fil: Sarotti, Ariel M. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Abstract: Hyacinthacines are important members of the pyrrolizidine family, with several compounds having ambiguous, revised or unverified structures. Herein we thoroughly explored the performance DP4 and DP4+ for the in silico stereoassignment of hyacinthacines A1, A2 and five synthetic isomers. The results suggested that the quality of the predictions strongly depended on the conformational landscape provided by DFT energies, with five compounds correctly assigned. In the two cases incorrectly classified we found that the source of the problem was conformational in nature, with spurious conformations being considerably over-stabilized by intramolecular H-bondings. We showed that neglecting such shapes resulted in a noteworthy improvement, with all compounds correctly assigned in high confidence (>99.9%).
description Fil: Zanardi, María Marta. Pontificia Universidad Católica Argentina. Facultad de Química e Ingeniería del Rosario; Argentina
publishDate 2019
dc.date.none.fl_str_mv 2019
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv https://repositorio.uca.edu.ar/handle/123456789/9025
0008-6215
https://doi.org/10.1016/j.carres.2019.01.011
Zanardi, M. M., Sortino, M. A., Sarotti, A. M. On the effect of intramolecular H-bonding in the configurational assessment of polyhydroxylated compounds with computational methods : The hyacinthacines case [en línea]. Carbohydrate Research. 2019, 474. doy: https://doi.org/10.1016/j.carres.2019.01.011. Disponible en: https://repositorio.uca.edu.ar/handle/123456789/9025
url https://repositorio.uca.edu.ar/handle/123456789/9025
https://doi.org/10.1016/j.carres.2019.01.011
identifier_str_mv 0008-6215
Zanardi, M. M., Sortino, M. A., Sarotti, A. M. On the effect of intramolecular H-bonding in the configurational assessment of polyhydroxylated compounds with computational methods : The hyacinthacines case [en línea]. Carbohydrate Research. 2019, 474. doy: https://doi.org/10.1016/j.carres.2019.01.011. Disponible en: https://repositorio.uca.edu.ar/handle/123456789/9025
dc.language.none.fl_str_mv eng
language eng
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/4.0/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/4.0/
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Elsevier
publisher.none.fl_str_mv Elsevier
dc.source.none.fl_str_mv Carbohydrate Research. Vol. 474, 2019
reponame:Repositorio Institucional (UCA)
instname:Pontificia Universidad Católica Argentina
reponame_str Repositorio Institucional (UCA)
collection Repositorio Institucional (UCA)
instname_str Pontificia Universidad Católica Argentina
repository.name.fl_str_mv Repositorio Institucional (UCA) - Pontificia Universidad Católica Argentina
repository.mail.fl_str_mv claudia_fernandez@uca.edu.ar
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score 12.982451

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