Título: | MECHANISMS OF NITROSYLATION OF IRON PORPHYRINS BY SNPA: KINETICS OF THE REACTION AND STABILITY UNDER AEROBIC ENVIRONMENT | ||||||||||||||||||||||||||||||||||||||||
Autor: |
FERNANDO DE SOUZA DIAS DOS SANTOS VILHENA |
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Colaborador(es): |
SONIA RENAUX WANDERLEY LOURO - Orientador |
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Catalogação: | 07/NOV/2006 | Língua(s): | PORTUGUESE - BRAZIL |
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Tipo: | TEXT | Subtipo: | THESIS | ||||||||||||||||||||||||||||||||||||||
Notas: |
[pt] Todos os dados constantes dos documentos são de inteira responsabilidade de seus autores. Os dados utilizados nas descrições dos documentos estão em conformidade com os sistemas da administração da PUC-Rio. [en] All data contained in the documents are the sole responsibility of the authors. The data used in the descriptions of the documents are in conformity with the systems of the administration of PUC-Rio. |
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Referência(s): |
[pt] https://www.maxwell.vrac.puc-rio.br/projetosEspeciais/ETDs/consultas/conteudo.php?strSecao=resultado&nrSeq=9242&idi=1 [en] https://www.maxwell.vrac.puc-rio.br/projetosEspeciais/ETDs/consultas/conteudo.php?strSecao=resultado&nrSeq=9242&idi=2 |
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DOI: | https://doi.org/10.17771/PUCRio.acad.9242 | ||||||||||||||||||||||||||||||||||||||||
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.
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