Application of metal complexes as biomimetic catalysts on glycerol oxidation

Two biomimetic complexes were evaluated as catalysts in the H2O2 mediated oxidation of glycerol, namely a peroxidase mimetic Fe(III) protoporphyrin complex (hematin) and the superoxide-dismutase mimetic complex of Mn(III) with 1,3-bis(5-sulphonatesalycilidenamino) propane (MnL−). Catalysis was targe...

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Autores principales: Parodi, Adrián Rodrigo, Merlo, Carolina, Córdoba, Agostina, Palopoli, Claudia, Ferreyra, Joaquín, Signorella, Sandra, Ferreira, María Luján, Magario, Ivana
Formato: article
Lenguaje:Inglés
Publicado: 2022
Materias:
Oxidación
Reacciones químicas
Catalizador
Glicerol
Acceso en línea:http://hdl.handle.net/11086/29028
https://doi.org/10.1016/j.mcat.2018.11.007
https://www.sciencedirect.com/journal/molecular-catalysis
Aporte de:
Repositorio Digital Universitario (UNC) de Universidad Nacional de Córdoba
id I10-R141-11086-29028
record_format dspace
institution Universidad Nacional de Córdoba
institution_str I-10
repository_str R-141
collection Repositorio Digital Universitario (UNC)
language Inglés
topic Oxidación
Reacciones químicas
Catalizador
Glicerol
spellingShingle Oxidación
Reacciones químicas
Catalizador
Glicerol
Parodi, Adrián Rodrigo
Merlo, Carolina
Córdoba, Agostina
Palopoli, Claudia
Ferreyra, Joaquín
Signorella, Sandra
Ferreira, María Luján
Magario, Ivana
Application of metal complexes as biomimetic catalysts on glycerol oxidation
topic_facet Oxidación
Reacciones químicas
Catalizador
Glicerol
description Two biomimetic complexes were evaluated as catalysts in the H2O2 mediated oxidation of glycerol, namely a peroxidase mimetic Fe(III) protoporphyrin complex (hematin) and the superoxide-dismutase mimetic complex of Mn(III) with 1,3-bis(5-sulphonatesalycilidenamino) propane (MnL−). Catalysis was targeted to glyceraldehyde since antimicrobial power was proved for it. Glyceraldehyde evolved at a higher rate than the uncatalyzed reaction only with hematin acid treated solutions and kinetics were typical of a radical mechanism. Nonetheless, glycerol conversions were low. H2O2 bleached hematin and the immobilization on a porous matrix could not prevent this. Meanwhile, the catalatic activity of hematin was high but its peroxidatic activity was inhibited at pH > 8. Thus, the coordination of hematin compound I to H2O2 over glycerol may be the preferred route with the accumulation of peroxy radicals, able to degrade the porphyrinic ring -with probable iron releasing- but also contributing to glycerol oxidation. On the other hand, a prompt decay with time of the catalatic and peroxidatic activities of MnL− was observed, which was improved by the addition of dimethylsulfoxide (DMSO), dimethylformamide (DMF) or acetone to the basic buffer system. Finally, EPR spectroscopy of MnL− supported the hypothesis of the formation of an inactive bis-oxo-bridged Mn(IV)Mn(IV) dimer upon addition of H2O2.
format article
author Parodi, Adrián Rodrigo
Merlo, Carolina
Córdoba, Agostina
Palopoli, Claudia
Ferreyra, Joaquín
Signorella, Sandra
Ferreira, María Luján
Magario, Ivana
author_facet Parodi, Adrián Rodrigo
Merlo, Carolina
Córdoba, Agostina
Palopoli, Claudia
Ferreyra, Joaquín
Signorella, Sandra
Ferreira, María Luján
Magario, Ivana
author_sort Parodi, Adrián Rodrigo
title Application of metal complexes as biomimetic catalysts on glycerol oxidation
title_short Application of metal complexes as biomimetic catalysts on glycerol oxidation
title_full Application of metal complexes as biomimetic catalysts on glycerol oxidation
title_fullStr Application of metal complexes as biomimetic catalysts on glycerol oxidation
title_full_unstemmed Application of metal complexes as biomimetic catalysts on glycerol oxidation
title_sort application of metal complexes as biomimetic catalysts on glycerol oxidation
publishDate 2022
url http://hdl.handle.net/11086/29028
https://doi.org/10.1016/j.mcat.2018.11.007
https://www.sciencedirect.com/journal/molecular-catalysis
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