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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-π-cation radical and oxoperferryl species of hematin, as analogues of Compounds 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 vs. 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 flow-injection modes and analytical columns applications. © 2015 Elsevier Ltd.

Registro:

Documento: Artículo
Título:Mechanistic evaluation of hematin action as a horseradish peroxidase biomimetic on the 4-aminoantipyrine/phenol oxidation reaction
Autor:Córdoba, A.; Alasino, N.; Asteasuain, M.; Magario, I.; Ferreira, M.L.
Filiación:Investigación y Desarrollo en Tecnología Química (IDTQ), Grupo Vinculado PLAPIQUI-CONICET, Facultad de Ciencias Exactas, Físicas y Naturales, Universidad Nacional de Córdoba, Córdoba, Argentina
Planta Piloto de Ingeniería Química (PLAPIQUI), PLAPIQUI-UNS-CONICET, Universidad Nacional del Sur, Bahía Blanca, Argentina
Ciudad Universitaria, Av.Velez Sarsfield 1611, X5016GCA, Córdoba, Argentina
Camino La Carrindanga Km 7, CC 717, Bahía Blanca, Provinciade Buenos Aires, Argentina
Palabras clave:4-Aminoantipyrine; Biomimetics; Bioprocess monitoring; Dynamic simulation; Kinetic parameters; Peroxidase; Biomimetics; Computer simulation; Enzymes; Food products; Kinetic parameters; Oxidation; Peroxides; Phenols; Rate constants; 4-aminoantipyrine; Bioprocess monitoring; Catalytic performance; Flow injection modes; Horseradish peroxidase; Oxidation reactions; Peroxidase; Peroxide decomposition; Condensation reactions
Año:2015
Volumen:129
Página de inicio:249
Página de fin:259
DOI: http://dx.doi.org/10.1016/j.ces.2015.02.031
Título revista:Chemical Engineering Science
Título revista abreviado:Chem. Eng. Sci.
ISSN:00092509
CODEN:CESCA
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00092509_v129_n_p249_Cordoba

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Citas:

---------- APA ----------
Córdoba, A., Alasino, N., Asteasuain, M., Magario, I. & Ferreira, M.L. (2015) . Mechanistic evaluation of hematin action as a horseradish peroxidase biomimetic on the 4-aminoantipyrine/phenol oxidation reaction. Chemical Engineering Science, 129, 249-259.
http://dx.doi.org/10.1016/j.ces.2015.02.031
---------- CHICAGO ----------
Córdoba, A., Alasino, N., Asteasuain, M., Magario, I., Ferreira, M.L. "Mechanistic evaluation of hematin action as a horseradish peroxidase biomimetic on the 4-aminoantipyrine/phenol oxidation reaction" . Chemical Engineering Science 129 (2015) : 249-259.
http://dx.doi.org/10.1016/j.ces.2015.02.031
---------- MLA ----------
Córdoba, A., Alasino, N., Asteasuain, M., Magario, I., Ferreira, M.L. "Mechanistic evaluation of hematin action as a horseradish peroxidase biomimetic on the 4-aminoantipyrine/phenol oxidation reaction" . Chemical Engineering Science, vol. 129, 2015, pp. 249-259.
http://dx.doi.org/10.1016/j.ces.2015.02.031
---------- VANCOUVER ----------
Córdoba, A., Alasino, N., Asteasuain, M., Magario, I., Ferreira, M.L. Mechanistic evaluation of hematin action as a horseradish peroxidase biomimetic on the 4-aminoantipyrine/phenol oxidation reaction. Chem. Eng. Sci. 2015;129:249-259.
http://dx.doi.org/10.1016/j.ces.2015.02.031