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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
Colaborador(es): SONIA RENAUX WANDERLEY LOURO - Orientador
Catalogação: 07/NOV/2006 Língua(s): PORTUGUESE - BRAZIL
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.
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
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.
Descrição: Arquivo:   
COVER, ACKNOWLEDGEMENTS, RESUMO, ABSTRACT, SUMMARY AND LISTS PDF    
CHAPTER 1 PDF    
CHAPTER 2 PDF    
CHAPTER 3 PDF    
CHAPTER 4 PDF    
CHAPTER 5 PDF    
CHAPTER 6 PDF    
REFERENCES PDF