Abstract:
The multiheme enzyme nitrite reductase catalyzes a 6-electron reduction of nitrite to ammonia. The reaction is initiated by substrate binding to the free axial position of the high spin penta-coordinated heme active site. The spin configuration of the resulting complex is crucial for discrimination between the heterolytic vs homolytic character of the cleavage of the N-O bond and, therefore, subsequent steps of the catalytic cycle. Here, we report the first experimental evidence, based on resonance Raman spectroscopy, that nitrite binding to the enzyme from D. vulgaris induces a transition from the high spin to the low spin configuration in the catalytic heme, thereby favoring the heterolytic route. © 2010 American Chemical Society.
Registro:
Documento: |
Artículo
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Título: | Substrate binding to a nitrite reductase induces a spin transition |
Autor: | Martins, G.; Rodrigues, L.; Cunha, F.M.; Matos, D.; Hildebrandt, P.; Murgida, D.H.; Pereira, I.A.C.; Todorovic, S. |
Filiación: | Instituto de Tecnologia Química e Biologica, Universidade Nova de Lisboa, Av Republica (EAN), 2780-157 Oeiras, Portugal Technische Universität Berlin, Institut für Chemie, Sekr. PC14, Strae des 17. Juni 135, D-10623 Berlin, Germany Departamento de Quimica Inorganica, Analitica y Quimica Fisica/INQUIMAE, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Pab. 2, piso 1, C1428EHA Buenos Aires, Argentina Instituto Gulbenkian de Ciência, Apartado 14, P-2781- 901 Oeiras, Portugal
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Palabras clave: | Coordination reactions; Enzymes; Hemoglobin; Porphyrins; Raman spectroscopy; Spin dynamics; Active site; Axial positions; Catalytic cycles; Electron reduction; Experimental evidence; High spins; Nitrite reductase; Resonance Raman spectroscopy; Spin configurations; Spin transition; Substrate binding; Vulgaris; Electron spin resonance spectroscopy |
Año: | 2010
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Volumen: | 114
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Número: | 16
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Página de inicio: | 5563
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Página de fin: | 5566
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DOI: |
http://dx.doi.org/10.1021/jp9118502 |
Título revista: | Journal of Physical Chemistry B
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Título revista abreviado: | J Phys Chem B
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ISSN: | 15206106
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CODEN: | JPCBF
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Registro: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_15206106_v114_n16_p5563_Martins |
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Citas:
---------- APA ----------
Martins, G., Rodrigues, L., Cunha, F.M., Matos, D., Hildebrandt, P., Murgida, D.H., Pereira, I.A.C.,..., Todorovic, S.
(2010)
. Substrate binding to a nitrite reductase induces a spin transition. Journal of Physical Chemistry B, 114(16), 5563-5566.
http://dx.doi.org/10.1021/jp9118502---------- CHICAGO ----------
Martins, G., Rodrigues, L., Cunha, F.M., Matos, D., Hildebrandt, P., Murgida, D.H., et al.
"Substrate binding to a nitrite reductase induces a spin transition"
. Journal of Physical Chemistry B 114, no. 16
(2010) : 5563-5566.
http://dx.doi.org/10.1021/jp9118502---------- MLA ----------
Martins, G., Rodrigues, L., Cunha, F.M., Matos, D., Hildebrandt, P., Murgida, D.H., et al.
"Substrate binding to a nitrite reductase induces a spin transition"
. Journal of Physical Chemistry B, vol. 114, no. 16, 2010, pp. 5563-5566.
http://dx.doi.org/10.1021/jp9118502---------- VANCOUVER ----------
Martins, G., Rodrigues, L., Cunha, F.M., Matos, D., Hildebrandt, P., Murgida, D.H., et al. Substrate binding to a nitrite reductase induces a spin transition. J Phys Chem B. 2010;114(16):5563-5566.
http://dx.doi.org/10.1021/jp9118502