MECANISMOS DE NITROSILAÇÃO DE FERRO PORFIRINAS POR SNAP: CINÉTICA DE REAÇÃO E ESTABILIDADE EM AMBIENTE AERÓBICO / MECHANISMS OF NITROSYLATION OF IRON PORPHYRINS BY SNPA: KINETICS OF THE REACTION AND STABILITY UNDER AEROBIC ENVIRONMENT

AUTOR(ES)
DATA DE PUBLICAÇÃO

2006

RESUMO

Serveal metalic complexes have been identified as tergets for the binding of nitric oxide. In order that these complexes can be efficiently and safely used in medical applications, it is important to understand their kinetic and structural properties in realistic models. In this work, the optical absorption and electron paramagnetic resonance techniques were used to study the nitrosylation of two water soluble ferric porphyrins, FeTMPyP, cationic, and FeTPPS4, anionic, by the NO donor S-nitrous- Nacetylpenecillamine (SNAP). For both porphyrins, nitrosylation rates as a function of SNAP concentration were obtained, and the second order rate constants were found. The similarity between these constants, KTMPYP = 0.84 x 10(3) M(-1)s(-1) and KTPPS4 = 0.97 x 10(3) M(-1)s(-1), suggests a mechanism independent of the nature of the porphyrin meso-substituents. It was demonstrated tha the nitrosylation by SNAP is different from that by NO gas, and a reaction mechanism was proposed. The reaction was also studied in aerobic environment. In contrast to NO gas, SNAP was able to produce nitrosylated iron porphyrins even in the presence of oxygen. The influence of ionic micelles on the stability of nitrosylated complexes was evaluated. The association of iron porphyrins with BSA and its influence on nitrosylation by SNAP were studied. The results demonstrated strong electrostatic influence on the binding of iron porphyrins to BSA. The interaction with BSA influenced the nitrosylation rates. The nitrosylated porphyrins were characterized by EPR spectroscopy.

ASSUNTO(S)

micelas espectroscopia otica micelles biofisica oxido nitrico spectroscopy otica biophysics nitric oxide ferro-porfirinas iron porphyrins

ACESSO AO ARTIGO

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