Computational chemical analysis of unconjugated bilirubin anions and insights into pKa values clarification

Autores
Vega Hissi, Esteban Gabriel; Estrada, Mario Rinaldo; Lavecchia, Martín José; Pis Diez, Reinaldo
Año de publicación
2013
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The pKa, the negative logarithm of the acid dissociation equilibrium constant, of the carboxylic acid groups of unconjugated bilirubin in water is a discussed issue because there are quite different experimental values reported. Using quantum mechanical calculations we have studied the conformational behavior of unconjugated bilirubin species (in gas phase and in solution modeled implicitly and explicitly) to provide evidence that may clarify pKa values because of its pathophysiological relevance. Our results show that rotation of carboxylate group, which is not restricted, settles it in a suitable place to establish stronger interactions that stabilizes the monoanion and the dianion to be properly solvated, demonstrating that the rationalization used to justify the high pKa values of unconjugated bilirubin is inappropriate. Furthermore, low unconjugated bilirubin (UCB) pKa values were estimated from a linear regression analysis.
Centro de Química Inorgánica
Materia
Química
Computational analysis
Unconjugated bilirrubin
Pka
Nivel de accesibilidad
acceso abierto
Condiciones de uso
http://creativecommons.org/licenses/by-nc-sa/4.0/
Repositorio
SEDICI (UNLP)
Institución
Universidad Nacional de La Plata
OAI Identificador
oai:sedici.unlp.edu.ar:10915/104345
Acceder
id SEDICI_734df493f9a40fe369dcd6f88bea1348
oai_identifier_str oai:sedici.unlp.edu.ar:10915/104345
network_acronym_str SEDICI
repository_id_str 1329
network_name_str SEDICI (UNLP)
spelling Computational chemical analysis of unconjugated bilirubin anions and insights into pKa values clarificationVega Hissi, Esteban GabrielEstrada, Mario RinaldoLavecchia, Martín JoséPis Diez, ReinaldoQuímicaComputational analysisUnconjugated bilirrubinPkaThe pKa, the negative logarithm of the acid dissociation equilibrium constant, of the carboxylic acid groups of unconjugated bilirubin in water is a discussed issue because there are quite different experimental values reported. Using quantum mechanical calculations we have studied the conformational behavior of unconjugated bilirubin species (in gas phase and in solution modeled implicitly and explicitly) to provide evidence that may clarify pKa values because of its pathophysiological relevance. Our results show that rotation of carboxylate group, which is not restricted, settles it in a suitable place to establish stronger interactions that stabilizes the monoanion and the dianion to be properly solvated, demonstrating that the rationalization used to justify the high pKa values of unconjugated bilirubin is inappropriate. Furthermore, low unconjugated bilirubin (UCB) pKa values were estimated from a linear regression analysis.Centro de Química Inorgánica2013-11info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionArticulohttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfhttp://sedici.unlp.edu.ar/handle/10915/104345enginfo:eu-repo/semantics/altIdentifier/url/http://hdl.handle.net/11336/4389info:eu-repo/semantics/altIdentifier/issn/0021-9606info:eu-repo/semantics/altIdentifier/doi/10.1063/1.4773586info:eu-repo/semantics/altIdentifier/hdl/11336/4389info:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by-nc-sa/4.0/Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)reponame:SEDICI (UNLP)instname:Universidad Nacional de La Platainstacron:UNLP2025-10-22T17:03:35Zoai:sedici.unlp.edu.ar:10915/104345Institucionalhttp://sedici.unlp.edu.ar/Universidad públicaNo correspondehttp://sedici.unlp.edu.ar/oai/snrdalira@sedici.unlp.edu.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:13292025-10-22 17:03:36.094SEDICI (UNLP) - Universidad Nacional de La Platafalse
dc.title.none.fl_str_mv Computational chemical analysis of unconjugated bilirubin anions and insights into pKa values clarification
title Computational chemical analysis of unconjugated bilirubin anions and insights into pKa values clarification
spellingShingle Computational chemical analysis of unconjugated bilirubin anions and insights into pKa values clarification
Vega Hissi, Esteban Gabriel
Química
Computational analysis
Unconjugated bilirrubin
Pka
title_short Computational chemical analysis of unconjugated bilirubin anions and insights into pKa values clarification
title_full Computational chemical analysis of unconjugated bilirubin anions and insights into pKa values clarification
title_fullStr Computational chemical analysis of unconjugated bilirubin anions and insights into pKa values clarification
title_full_unstemmed Computational chemical analysis of unconjugated bilirubin anions and insights into pKa values clarification
title_sort Computational chemical analysis of unconjugated bilirubin anions and insights into pKa values clarification
dc.creator.none.fl_str_mv Vega Hissi, Esteban Gabriel
Estrada, Mario Rinaldo
Lavecchia, Martín José
Pis Diez, Reinaldo
author Vega Hissi, Esteban Gabriel
author_facet Vega Hissi, Esteban Gabriel
Estrada, Mario Rinaldo
Lavecchia, Martín José
Pis Diez, Reinaldo
author_role author
author2 Estrada, Mario Rinaldo
Lavecchia, Martín José
Pis Diez, Reinaldo
author2_role author
author
author
dc.subject.none.fl_str_mv Química
Computational analysis
Unconjugated bilirrubin
Pka
topic Química
Computational analysis
Unconjugated bilirrubin
Pka
dc.description.none.fl_txt_mv The pKa, the negative logarithm of the acid dissociation equilibrium constant, of the carboxylic acid groups of unconjugated bilirubin in water is a discussed issue because there are quite different experimental values reported. Using quantum mechanical calculations we have studied the conformational behavior of unconjugated bilirubin species (in gas phase and in solution modeled implicitly and explicitly) to provide evidence that may clarify pKa values because of its pathophysiological relevance. Our results show that rotation of carboxylate group, which is not restricted, settles it in a suitable place to establish stronger interactions that stabilizes the monoanion and the dianion to be properly solvated, demonstrating that the rationalization used to justify the high pKa values of unconjugated bilirubin is inappropriate. Furthermore, low unconjugated bilirubin (UCB) pKa values were estimated from a linear regression analysis.
Centro de Química Inorgánica
description The pKa, the negative logarithm of the acid dissociation equilibrium constant, of the carboxylic acid groups of unconjugated bilirubin in water is a discussed issue because there are quite different experimental values reported. Using quantum mechanical calculations we have studied the conformational behavior of unconjugated bilirubin species (in gas phase and in solution modeled implicitly and explicitly) to provide evidence that may clarify pKa values because of its pathophysiological relevance. Our results show that rotation of carboxylate group, which is not restricted, settles it in a suitable place to establish stronger interactions that stabilizes the monoanion and the dianion to be properly solvated, demonstrating that the rationalization used to justify the high pKa values of unconjugated bilirubin is inappropriate. Furthermore, low unconjugated bilirubin (UCB) pKa values were estimated from a linear regression analysis.
publishDate 2013
dc.date.none.fl_str_mv 2013-11
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
Articulo
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://sedici.unlp.edu.ar/handle/10915/104345
url http://sedici.unlp.edu.ar/handle/10915/104345
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://hdl.handle.net/11336/4389
info:eu-repo/semantics/altIdentifier/issn/0021-9606
info:eu-repo/semantics/altIdentifier/doi/10.1063/1.4773586
info:eu-repo/semantics/altIdentifier/hdl/11336/4389
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by-nc-sa/4.0/
Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)
eu_rights_str_mv openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by-nc-sa/4.0/
Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)
dc.format.none.fl_str_mv application/pdf
dc.source.none.fl_str_mv reponame:SEDICI (UNLP)
instname:Universidad Nacional de La Plata
instacron:UNLP
reponame_str SEDICI (UNLP)
collection SEDICI (UNLP)
instname_str Universidad Nacional de La Plata
instacron_str UNLP
institution UNLP
repository.name.fl_str_mv SEDICI (UNLP) - Universidad Nacional de La Plata
repository.mail.fl_str_mv alira@sedici.unlp.edu.ar
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