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. doi:10.1016/j.jinorgbio.2009.04.012. https://resolver.caltech.edu/CaltechAUTHORS:20180612-155638279
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Abstract
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.
Item Type: | Article | ||||||
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Additional Information: | © 2009 Elsevier. Received 27 January 2009, Revised 20 March 2009, Accepted 24 April 2009, Available online 7 May 2009. his research was supported by NSF Grant CHE 0446304 (E.I.S.). X. X. is grateful for William S. Johnson fellowship. | ||||||
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Subject Keywords: | Blue copper; Axial ligand; Protein constraint; Coupled distortion; Temperature dependence | ||||||
Issue or Number: | 10 | ||||||
DOI: | 10.1016/j.jinorgbio.2009.04.012 | ||||||
Record Number: | CaltechAUTHORS:20180612-155638279 | ||||||
Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20180612-155638279 | ||||||
Official Citation: | Xiangjin Xie, Ryan G. Hadt, Sofia R. Pauleta, Pablo J. González, Sun Un, Isabel Moura, Edward I. Solomon, A variable temperature spectroscopic study on Paracoccus pantotrophus pseudoazurin: Protein constraints on the blue Cu site, Journal of Inorganic Biochemistry, Volume 103, Issue 10, 2009, Pages 1307-1313, ISSN 0162-0134, https://doi.org/10.1016/j.jinorgbio.2009.04.012. (http://www.sciencedirect.com/science/article/pii/S0162013409000907) | ||||||
Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | ||||||
ID Code: | 87038 | ||||||
Collection: | CaltechAUTHORS | ||||||
Deposited By: | George Porter | ||||||
Deposited On: | 12 Jun 2018 23:16 | ||||||
Last Modified: | 15 Nov 2021 20:44 |
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