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The blue or Type 1 (T1) copper site of Paracoccuspantotrophus pseudoazurin exhibits significant absorption intensity in both the 450 and 600 nm regions. These are sigma and π S_(Cys) to Cu^(2+) charge transfer (CT) transitions. The temperature dependent absorption, EPR, and resonance Raman (rR) vibrations enhanced by these bands indicate that a single species is present at all temperatures. This contrasts the temperature dependent behavior of the T1 center in nitrite reductase [S. Ghosh, X. Xie, A. Dey, Y. Sun, C. Scholes, E. Solomon, Proc. Natl. Acad. Sci. 106 (2009) 4969-4974] which has a thioether ligand that is unconstrained by the protein. The lack of temperature dependence in the T1 site in pseudoazurin indicates the presence of a protein constraint similar to the blue Cu site in plastocyanin where the thioether ligand is constrained at 2.8 A. However, plastocyanin exhibits only π CT. This spectral difference between pseudoazurin and plastocyanin reflects a coupled distortion of the site where the axial thioether in pseudoazurin is also constrained, but at a shorter Cu-S_(Met) bond length. This leads to an increase in the Cu^(2+)-S_(Cys) bond length, and the site undergoes a partial tetragonal distortion in pseudoazurin. Thus, its ground state wavefunction has both sigma and pi character in the Cu^(2+)-S(Cys) bond.

Pertenece a

Caltech Authors  


Xie, Xiangjin -  Hadt, Ryan G. -  Pauleta, Sofia R. -  González, Pablo J. -  Un, Sun -  Moura, Isabel -  Solomon, Edward I. - 

Id.: 71396362

Versión: 1.0

Estado: Final

Tipo de recurso: Article  -  PeerReviewed  - 

Tipo de Interactividad: Expositivo

Nivel de Interactividad: muy bajo

Audiencia: Estudiante  -  Profesor  -  Autor  - 

Estructura: Atomic

Coste: no

Copyright: sí

Requerimientos técnicos:  Browser: Any - 

Relación: [References] http://resolver.caltech.edu/CaltechAUTHORS:20180612-155638279
[References] https://authors.library.caltech.edu/87038/

Fecha de contribución: 13-jun-2018


* Xie, Xiangjin and Hadt, Ryan G. and Pauleta, Sofia R. and González, Pablo J. and Un, Sun and Moura, Isabel and Solomon, Edward I. (2009) A variable temperature spectroscopic study on Paracoccus pantotrophus pseudoazurin: protein constraints on the blue Cu site. Journal of Inorganic Biochemistry, 103 (10). pp. 1307-1313. ISSN 0162-0134. http://resolver.caltech.edu/CaltechAUTHORS:20180612-155638279

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