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El ensamblaje hemo-cobre mediado por el acoplamiento reductor del monóxido de nitrógeno (*NO)
Jun Wang1, Mark P Schopfer, Amy A N Sarjeant
1Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218, USA.
Journal of the American Chemical Society
|December 23, 2008
Resumen
Este estudio demuestra un nuevo complejo de hierro-dinitrosilo que, con cobre y ácido, acopla óxido nítrico (NO) para formar óxido nitroso (N2O). Este sistema sirve como un modelo funcional para las enzimas reductasa de óxido nítrico.
Área de la Ciencia:
- Química bioorgánica Química bioorgánica.
- Coordinación Química de la Coordinación
- El mimetismo de la enzima.
Sus antecedentes:
- El óxido nítrico (NO) juega un papel crucial en los sistemas biológicos.
- Las enzimas reductasa de óxido nítrico (NOR) son vitales para las vías de desnitrificación.
- Comprender los mecanismos del metabolismo del NO es esencial para las aplicaciones biológicas y químicas.
Objetivo del estudio:
- Desarrollar un modelo funcional para la actividad de la reductasa de óxido nítrico hemo/cobre.
- Para investigar el mecanismo de acoplamiento y reducción del óxido nítrico (NO).
- Para explorar el papel de los iones de cobre en la transformación de NO.
Principales métodos:
- Síntesis de un complejo hierro-dinitrosilo ((6) L) Fe (((NO) 2.
- Investigó la reacción del complejo con iones de cobre (I) y ácido.
- Se utilizó espectroscopia UV-vis para monitorear el progreso de la reacción.
- Los productos gaseosos analizados, incluido el óxido nitroso (N2O).
Principales resultados:
- El complejo hierro-dinitrosilo acopla eficientemente dos moléculas de NO para liberar N2O en presencia de Cu+ y ácido.
- El ión cobre dentro del marco del ligando es esencial para la química de acoplamiento de NO.
- Un mecanismo propuesto implica la desproporción de NO promovida por el cobre.
- La reacción produce un producto hemo/cobre, [((6) L) Fe (((III)...Cu (((II) ((D) ]3+.
Conclusiones:
- El sistema químico descrito sirve como un modelo funcional estequiométrico para el óxido nítrico hemo/cobre reductasa.
- Este trabajo proporciona información sobre los mecanismos catalíticos de la reducción de NO.
- Destaca la importancia de la cooperación entre metales y ligandos en los procesos redox que involucran NO.
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