Mechanistic evaluation of hematin action as a horseradish peroxidase biomimetic on the 4-aminoantipyrine/phenol oxidation reaction

Autores
Córdoba, Agostina; Alasino, Noelia Pia Ximena; Asteasuain, Mariano; Magario, Ivana; Ferreira, Maria Lujan
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Abstract: Hematin, a mimetic structure of heme peroxidases, was successfully applied for H2O2- mediated condensation reaction between phenol and 4-aminoantipyrine.The catalytic action was evaluated in comparison to horseradish peroxidase (HRP) by kinetic modelling and parametrization procedure. Expected side reactions were checked and discarded as model-relevant routes. The existence of the oxoperferryl-pi-cation radical and oxoperferryl species of hematin, as analogues of Compound I and II of HRP, can be postulated because simulated product formation fitted experimental data. However, in light of the optimized rate constants encountered, hematin was less active to peroxide activation and less specific to the coordination of phenol versus H2O2 than HRP. The model indicated that hematin bleaching from key intermediate oxoperferryl was induced rather than regenerated via Compound III formation. In contrast to the enzyme, the faster oxygen evolvement and the lack of precipitating polyphenol production observed with hematin after 4-aminoantipyrine depletion were interpreted as accumulation of oxidising HOO* radicals through the peroxide decomposition pathway. This study may be of interest for interpreting the catalytic performance of hematin. Moreover, the replacement of the enzyme by the less-expensive and non-polyphenol-forming hematin for this versatile colorimetric assay may provide convenient results, especially in flowinjection modes and analytical columns applications.
Fil: Córdoba, Agostina. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnológico Bahia Blanca. Planta Piloto de Ingenieria Quimica (i). Grupo Vinculado Al Plapiqui - Investigación y Desarrollo En Tecnologia Quimica; Argentina. Universidad Nacional de Córdoba; Argentina
Fil: Alasino, Noelia Pia Ximena. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnológico Bahia Blanca. Planta Piloto de Ingenieria Quimica (i). Grupo Vinculado Al Plapiqui - Investigación y Desarrollo En Tecnologia Quimica; Argentina. Universidad Nacional de Córdoba; Argentina
Fil: Asteasuain, Mariano. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Bahía Blanca. Planta Piloto de Ingeniería Química (i); Argentina; Argentina. Universidad Nacional del Sur; Argentina
Fil: Magario, Ivana. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnológico Bahia Blanca. Planta Piloto de Ingenieria Quimica (i). Grupo Vinculado Al Plapiqui - Investigación y Desarrollo En Tecnologia Quimica; Argentina. Universidad Nacional de Córdoba; Argentina
Fil: Ferreira, Maria Lujan. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Bahía Blanca. Planta Piloto de Ingeniería Química (i); Argentina; Argentina. Universidad Nacional del Sur; Argentina
Materia
Biomimetics
Peroxidase
Bioprocess Monitoring
Dynamic Simulation
4-Aminoantipyrine
Kinetic Parameters
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/15320
Acceder
id CONICETDig_3c45d9e07af333058f2bf81addc3c5bf
oai_identifier_str oai:ri.conicet.gov.ar:11336/15320
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Mechanistic evaluation of hematin action as a horseradish peroxidase biomimetic on the 4-aminoantipyrine/phenol oxidation reactionCórdoba, AgostinaAlasino, Noelia Pia XimenaAsteasuain, MarianoMagario, IvanaFerreira, Maria LujanBiomimeticsPeroxidaseBioprocess MonitoringDynamic Simulation4-AminoantipyrineKinetic Parametershttps://purl.org/becyt/ford/2.4https://purl.org/becyt/ford/2Abstract: Hematin, a mimetic structure of heme peroxidases, was successfully applied for H2O2- mediated condensation reaction between phenol and 4-aminoantipyrine.The catalytic action was evaluated in comparison to horseradish peroxidase (HRP) by kinetic modelling and parametrization procedure. Expected side reactions were checked and discarded as model-relevant routes. The existence of the oxoperferryl-pi-cation radical and oxoperferryl species of hematin, as analogues of Compound I and II of HRP, can be postulated because simulated product formation fitted experimental data. However, in light of the optimized rate constants encountered, hematin was less active to peroxide activation and less specific to the coordination of phenol versus H2O2 than HRP. The model indicated that hematin bleaching from key intermediate oxoperferryl was induced rather than regenerated via Compound III formation. In contrast to the enzyme, the faster oxygen evolvement and the lack of precipitating polyphenol production observed with hematin after 4-aminoantipyrine depletion were interpreted as accumulation of oxidising HOO* radicals through the peroxide decomposition pathway. This study may be of interest for interpreting the catalytic performance of hematin. Moreover, the replacement of the enzyme by the less-expensive and non-polyphenol-forming hematin for this versatile colorimetric assay may provide convenient results, especially in flowinjection modes and analytical columns applications.Fil: Córdoba, Agostina. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnológico Bahia Blanca. Planta Piloto de Ingenieria Quimica (i). Grupo Vinculado Al Plapiqui - Investigación y Desarrollo En Tecnologia Quimica; Argentina. Universidad Nacional de Córdoba; ArgentinaFil: Alasino, Noelia Pia Ximena. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnológico Bahia Blanca. Planta Piloto de Ingenieria Quimica (i). Grupo Vinculado Al Plapiqui - Investigación y Desarrollo En Tecnologia Quimica; Argentina. Universidad Nacional de Córdoba; ArgentinaFil: Asteasuain, Mariano. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Bahía Blanca. Planta Piloto de Ingeniería Química (i); Argentina; Argentina. Universidad Nacional del Sur; ArgentinaFil: Magario, Ivana. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnológico Bahia Blanca. Planta Piloto de Ingenieria Quimica (i). Grupo Vinculado Al Plapiqui - Investigación y Desarrollo En Tecnologia Quimica; Argentina. Universidad Nacional de Córdoba; ArgentinaFil: Ferreira, Maria Lujan. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Bahía Blanca. Planta Piloto de Ingeniería Química (i); Argentina; Argentina. Universidad Nacional del Sur; ArgentinaElsevier2015-06info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/15320Córdoba, Agostina; Alasino, Noelia Pia Ximena; Asteasuain, Mariano; Magario, Ivana; Ferreira, Maria Lujan; Mechanistic evaluation of hematin action as a horseradish peroxidase biomimetic on the 4-aminoantipyrine/phenol oxidation reaction; Elsevier; Chemical Engineering Science; 129; 6-2015; 249-2590009-2509enginfo:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0009250915001463info:eu-repo/semantics/altIdentifier/doi/10.1016/j.ces.2015.02.031info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-nd/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:37:24Zoai:ri.conicet.gov.ar:11336/15320instacron: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:34982025-09-29 09:37:24.777CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Mechanistic evaluation of hematin action as a horseradish peroxidase biomimetic on the 4-aminoantipyrine/phenol oxidation reaction
title Mechanistic evaluation of hematin action as a horseradish peroxidase biomimetic on the 4-aminoantipyrine/phenol oxidation reaction
spellingShingle Mechanistic evaluation of hematin action as a horseradish peroxidase biomimetic on the 4-aminoantipyrine/phenol oxidation reaction
Córdoba, Agostina
Biomimetics
Peroxidase
Bioprocess Monitoring
Dynamic Simulation
4-Aminoantipyrine
Kinetic Parameters
title_short Mechanistic evaluation of hematin action as a horseradish peroxidase biomimetic on the 4-aminoantipyrine/phenol oxidation reaction
title_full Mechanistic evaluation of hematin action as a horseradish peroxidase biomimetic on the 4-aminoantipyrine/phenol oxidation reaction
title_fullStr Mechanistic evaluation of hematin action as a horseradish peroxidase biomimetic on the 4-aminoantipyrine/phenol oxidation reaction
title_full_unstemmed Mechanistic evaluation of hematin action as a horseradish peroxidase biomimetic on the 4-aminoantipyrine/phenol oxidation reaction
title_sort Mechanistic evaluation of hematin action as a horseradish peroxidase biomimetic on the 4-aminoantipyrine/phenol oxidation reaction
dc.creator.none.fl_str_mv Córdoba, Agostina
Alasino, Noelia Pia Ximena
Asteasuain, Mariano
Magario, Ivana
Ferreira, Maria Lujan
author Córdoba, Agostina
author_facet Córdoba, Agostina
Alasino, Noelia Pia Ximena
Asteasuain, Mariano
Magario, Ivana
Ferreira, Maria Lujan
author_role author
author2 Alasino, Noelia Pia Ximena
Asteasuain, Mariano
Magario, Ivana
Ferreira, Maria Lujan
author2_role author
author
author
author
dc.subject.none.fl_str_mv Biomimetics
Peroxidase
Bioprocess Monitoring
Dynamic Simulation
4-Aminoantipyrine
Kinetic Parameters
topic Biomimetics
Peroxidase
Bioprocess Monitoring
Dynamic Simulation
4-Aminoantipyrine
Kinetic Parameters
purl_subject.fl_str_mv https://purl.org/becyt/ford/2.4
https://purl.org/becyt/ford/2
dc.description.none.fl_txt_mv Abstract: Hematin, a mimetic structure of heme peroxidases, was successfully applied for H2O2- mediated condensation reaction between phenol and 4-aminoantipyrine.The catalytic action was evaluated in comparison to horseradish peroxidase (HRP) by kinetic modelling and parametrization procedure. Expected side reactions were checked and discarded as model-relevant routes. The existence of the oxoperferryl-pi-cation radical and oxoperferryl species of hematin, as analogues of Compound I and II of HRP, can be postulated because simulated product formation fitted experimental data. However, in light of the optimized rate constants encountered, hematin was less active to peroxide activation and less specific to the coordination of phenol versus H2O2 than HRP. The model indicated that hematin bleaching from key intermediate oxoperferryl was induced rather than regenerated via Compound III formation. In contrast to the enzyme, the faster oxygen evolvement and the lack of precipitating polyphenol production observed with hematin after 4-aminoantipyrine depletion were interpreted as accumulation of oxidising HOO* radicals through the peroxide decomposition pathway. This study may be of interest for interpreting the catalytic performance of hematin. Moreover, the replacement of the enzyme by the less-expensive and non-polyphenol-forming hematin for this versatile colorimetric assay may provide convenient results, especially in flowinjection modes and analytical columns applications.
Fil: Córdoba, Agostina. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnológico Bahia Blanca. Planta Piloto de Ingenieria Quimica (i). Grupo Vinculado Al Plapiqui - Investigación y Desarrollo En Tecnologia Quimica; Argentina. Universidad Nacional de Córdoba; Argentina
Fil: Alasino, Noelia Pia Ximena. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnológico Bahia Blanca. Planta Piloto de Ingenieria Quimica (i). Grupo Vinculado Al Plapiqui - Investigación y Desarrollo En Tecnologia Quimica; Argentina. Universidad Nacional de Córdoba; Argentina
Fil: Asteasuain, Mariano. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Bahía Blanca. Planta Piloto de Ingeniería Química (i); Argentina; Argentina. Universidad Nacional del Sur; Argentina
Fil: Magario, Ivana. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnológico Bahia Blanca. Planta Piloto de Ingenieria Quimica (i). Grupo Vinculado Al Plapiqui - Investigación y Desarrollo En Tecnologia Quimica; Argentina. Universidad Nacional de Córdoba; Argentina
Fil: Ferreira, Maria Lujan. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Bahía Blanca. Planta Piloto de Ingeniería Química (i); Argentina; Argentina. Universidad Nacional del Sur; Argentina
description Abstract: Hematin, a mimetic structure of heme peroxidases, was successfully applied for H2O2- mediated condensation reaction between phenol and 4-aminoantipyrine.The catalytic action was evaluated in comparison to horseradish peroxidase (HRP) by kinetic modelling and parametrization procedure. Expected side reactions were checked and discarded as model-relevant routes. The existence of the oxoperferryl-pi-cation radical and oxoperferryl species of hematin, as analogues of Compound I and II of HRP, can be postulated because simulated product formation fitted experimental data. However, in light of the optimized rate constants encountered, hematin was less active to peroxide activation and less specific to the coordination of phenol versus H2O2 than HRP. The model indicated that hematin bleaching from key intermediate oxoperferryl was induced rather than regenerated via Compound III formation. In contrast to the enzyme, the faster oxygen evolvement and the lack of precipitating polyphenol production observed with hematin after 4-aminoantipyrine depletion were interpreted as accumulation of oxidising HOO* radicals through the peroxide decomposition pathway. This study may be of interest for interpreting the catalytic performance of hematin. Moreover, the replacement of the enzyme by the less-expensive and non-polyphenol-forming hematin for this versatile colorimetric assay may provide convenient results, especially in flowinjection modes and analytical columns applications.
publishDate 2015
dc.date.none.fl_str_mv 2015-06
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/11336/15320
Córdoba, Agostina; Alasino, Noelia Pia Ximena; Asteasuain, Mariano; Magario, Ivana; Ferreira, Maria Lujan; Mechanistic evaluation of hematin action as a horseradish peroxidase biomimetic on the 4-aminoantipyrine/phenol oxidation reaction; Elsevier; Chemical Engineering Science; 129; 6-2015; 249-259
0009-2509
url http://hdl.handle.net/11336/15320
identifier_str_mv Córdoba, Agostina; Alasino, Noelia Pia Ximena; Asteasuain, Mariano; Magario, Ivana; Ferreira, Maria Lujan; Mechanistic evaluation of hematin action as a horseradish peroxidase biomimetic on the 4-aminoantipyrine/phenol oxidation reaction; Elsevier; Chemical Engineering Science; 129; 6-2015; 249-259
0009-2509
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0009250915001463
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.ces.2015.02.031
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv Elsevier
publisher.none.fl_str_mv Elsevier
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 13.070432

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