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

Authors
Córdoba, Agostina; Alasino, Noelia Pia Ximena; Asteasuain, Mariano; Magario, Ivana; Ferreira, Maria Lujan
Publication Year
2015
Language
English
Format
article
Status
Published version
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.
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
Subject
biomimetics
peroxidase
bioprocess monitoring
dynamic simulation
4-aminoantipyrine
kinetic parameters
Ingeniería de Procesos Químicos
Ingeniería Química
INGENIERÍAS Y TECNOLOGÍAS
Access level
Restricted access
License
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
Repository
CONICET Digital (CONICET)
Institution
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identifier
oai:ri.conicet.gov.ar:11336/15320