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.
Fil: Vega Hissi, Esteban Gabriel. Universidad Nacional de San Luis. Facultad de Quimica, Bioquimica y Farmacia. Departamento de Quimica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico San Luis. Instituto Multidisciplinario de Investigaciones Biológicas de San Luis; Argentina
Fil: Estrada, Mario Rinaldo. Universidad Nacional de San Luis. Facultad de Quimica, Bioquimica y Farmacia. Departamento de Quimica; Argentina
Fil: Lavecchia, Martín José. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico La Plata. Centro de Química Inorgánica; Argentina
Fil: Pis Diez, Reinaldo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico La Plata. Centro de Química Inorgánica; Argentina
Materia
COMPUTATIONAL ANALYSIS
UNCONJUGATED BILIRRUBIN
PKA
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/4389
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/4389
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Computational chemical analysis of unconjugated bilirubin anions and insights into pKa values clarificationVega Hissi, Esteban GabrielEstrada, Mario RinaldoLavecchia, Martín JoséPis Diez, ReinaldoCOMPUTATIONAL ANALYSISUNCONJUGATED BILIRRUBINPKAhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The 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.Fil: Vega Hissi, Esteban Gabriel. Universidad Nacional de San Luis. Facultad de Quimica, Bioquimica y Farmacia. Departamento de Quimica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico San Luis. Instituto Multidisciplinario de Investigaciones Biológicas de San Luis; ArgentinaFil: Estrada, Mario Rinaldo. Universidad Nacional de San Luis. Facultad de Quimica, Bioquimica y Farmacia. Departamento de Quimica; ArgentinaFil: Lavecchia, Martín José. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico La Plata. Centro de Química Inorgánica; ArgentinaFil: Pis Diez, Reinaldo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico La Plata. Centro de Química Inorgánica; ArgentinaAmerican Institute of Physics2013-11info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/4389Vega Hissi, Esteban Gabriel; Estrada, Mario Rinaldo; Lavecchia, Martín José; Pis Diez, Reinaldo; Computational chemical analysis of unconjugated bilirubin anions and insights into pKa values clarification; American Institute of Physics; Journal of Chemical Physics; 138; 11-2013; 035101-1-035101-100021-9606enginfo:eu-repo/semantics/altIdentifier/doi/10.1063/1.4773586info:eu-repo/semantics/altIdentifier/url/http://scitation.aip.org/content/aip/journal/jcp/138/3/10.1063/1.4773586info:eu-repo/semantics/altIdentifier/issn/0021-9606info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T12:10:54Zoai:ri.conicet.gov.ar:11336/4389instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-10-22 12:10:54.361CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
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
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 COMPUTATIONAL ANALYSIS
UNCONJUGATED BILIRRUBIN
PKA
topic COMPUTATIONAL ANALYSIS
UNCONJUGATED BILIRRUBIN
PKA
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
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.
Fil: Vega Hissi, Esteban Gabriel. Universidad Nacional de San Luis. Facultad de Quimica, Bioquimica y Farmacia. Departamento de Quimica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico San Luis. Instituto Multidisciplinario de Investigaciones Biológicas de San Luis; Argentina
Fil: Estrada, Mario Rinaldo. Universidad Nacional de San Luis. Facultad de Quimica, Bioquimica y Farmacia. Departamento de Quimica; Argentina
Fil: Lavecchia, Martín José. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico La Plata. Centro de Química Inorgánica; Argentina
Fil: Pis Diez, Reinaldo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico La Plata. Centro de Química Inorgánica; Argentina
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
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://hdl.handle.net/11336/4389
Vega Hissi, Esteban Gabriel; Estrada, Mario Rinaldo; Lavecchia, Martín José; Pis Diez, Reinaldo; Computational chemical analysis of unconjugated bilirubin anions and insights into pKa values clarification; American Institute of Physics; Journal of Chemical Physics; 138; 11-2013; 035101-1-035101-10
0021-9606
url http://hdl.handle.net/11336/4389
identifier_str_mv Vega Hissi, Esteban Gabriel; Estrada, Mario Rinaldo; Lavecchia, Martín José; Pis Diez, Reinaldo; Computational chemical analysis of unconjugated bilirubin anions and insights into pKa values clarification; American Institute of Physics; Journal of Chemical Physics; 138; 11-2013; 035101-1-035101-10
0021-9606
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1063/1.4773586
info:eu-repo/semantics/altIdentifier/url/http://scitation.aip.org/content/aip/journal/jcp/138/3/10.1063/1.4773586
info:eu-repo/semantics/altIdentifier/issn/0021-9606
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv American Institute of Physics
publisher.none.fl_str_mv American Institute of Physics
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 12.982451

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