Application of metal complexes as biomimetic catalysts on glycerol oxidation

MERLO, CAROLINA; FERREYRA, JOAQUÍN; MAGARIO, IVANA; CÓRDOBA, AGOSTINA; SIGNORELLA, SANDRA; PARODI, ADRIÁN RODRIGO; PALOPOLI, CLAUDIA; CÓRDOBA, AGOSTINA; FERREIRA, MARÍA LUJÁN; SIGNORELLA, SANDRA; MERLO, CAROLINA; PARODI, ADRIÁN RODRIGO; FERREYRA, JOAQUÍN; PALOPOLI, CLAUDIA; MAGARIO, IVANA; FERREIRA, MARÍA LUJÁN

Molecular Catalysis

Elsevier B.V.

Año: 2018

2468-8231

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.