Abstract
The deuterohemin complex carrying a deca-L-alanine peptide residue covalently linked to one of the propionic acid side chain of the porphyrin has been synthesized and its catalytic behaviour in biomimetic oxidations has been investigated by kinetic measurements. In the catalytic oxidation of a series of para-substituted thioanisoles by hydrogen peroxide a correlation has been found between the reaction rates and the Hammettσp parameter suggesting that a direct oxygen transfer from an iron-oxo species to the substrate sulfur atom takes place. This trend is similar to that found for chloroperoxidase whereas for normal peroxidases the rate of oxidation of the same substrates correlates with Hammett σ+ values. The catalytic oxidation of L- and D-tyrosine by hydrogen peroxide exhibit substrate saturation kinetics mimicking the enzymic reactions catalyzed by peroxidases. The reaction shows stereoselective effects, the oxidation of D-tyrosine being favoured with respect to that of the L isomer.
Riassunto
È stato sintetizzato il complesso della deuteroemina recante un residuo peptidico di deca-L-alanina legato covalentemente ad una delle catene propioniche della porfirina e ne è stato investigato il comportamento catalitico in ossidazioni biomimetiche. Nell’ossidazione catalitica di una serie di tioanisoli para-sostituiti da parte del perossido di idrogeno si è trovata una correlazione tra la velocità di reazione ed il paramtroσp di Hammett; ciò indicherebbe un meccanismo di trasferimento diretto di ossigeno da parte di una specie ferro-osso all’atomo di zolfo del substrato. Questo andamento è simile a quello trovato per la catalisi da parte della cloroperossidasi nelle stesse reazioni, mentre per le perossidasi comuni le velocità di reazione correlano con i parametri π+ di Hammett. Le ossidazioni catalitiche della L- e D-tirosina da parte del perossido di idrogeno mostrano delle cinetiche di saturazione del substrato caratteristiche delle reazioni enzimatiche catalizzate dalle perossidasi. La reazione mostra effetti di stereoselettività, in quanto I’ossidazione della D-tirosina risulta favorita rispetto a quella dell’isomero L.
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Nella seduta del 9 febbraio 1991.
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Casella, L., Gullotti, M., Monzani, E. et al. Biomimetic oxidation catalysis by iron (III) deuteroporpbyrin carrying a deca-L-alanine peptide chain. Rend. Fis. Acc. Lincei 2, 201–212 (1991). https://doi.org/10.1007/BF03002947
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DOI: https://doi.org/10.1007/BF03002947