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Paramagnetic NMR Spectroscopy of Cobalt(II) and Copper(II) Derivatives of Pseudomonas aeruginosa His46Asp Azurin

Vila, A. J. and Ramirez, B. E. and Di Bilio, A. J. and Mizoguchi, T. J. and Richards, J. H. and Gray, H. B. (1997) Paramagnetic NMR Spectroscopy of Cobalt(II) and Copper(II) Derivatives of Pseudomonas aeruginosa His46Asp Azurin. Inorganic Chemistry, 36 (20). pp. 4567-4570. ISSN 0020-1669. https://resolver.caltech.edu/CaltechAUTHORS:20150428-132741371

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Abstract

NMR spectra of paramagnetic Co(II) and Cu(II) derivatives of Pseudomonas aeruginosa His46Asp azurin have been investigated. In each derivative, assignment of hyperfine-shifted resonances outside the diamagnetic envelope of spectra recorded at 200 and 500 MHz confirms that the Asp carboxylate is coordinated to the paramagnetic metal center. The reduced paramagnetic shifts of the Cys112 proton resonances in Cu(II) and Co(II) His46Asp azurins compared to those of the corresponding wild type proteins indicate that metal-S(Cys) bonding is weakened in this mutant. The downfield shifts of the γ-CH_2 of Met121 suggest a stronger interaction between the metal and the Met thioether group than is present in the wild type protein. Molecular modeling of the metal site structure indicates a distorted tetrahedral geometry with Asp46 (monodentate carboxylate), Cys112, and His117 equatorial ligands. In this structure, the metal ion is shifted 0.3 Å out of the O(Asp)S(Cys)N(His) trigonal plane toward Met121.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ic9703282 DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ic9703282PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ic9703282PublisherSupporting Information
ORCID:
AuthorORCID
Gray, H. B.0000-0002-7937-7876
Additional Information:© 1997 American Chemical Society. Received March 19, 1997. A.J.V. thanks the Fundacion Antorchas and TWAS for research funds, ACS for a travel grant, and IQUIOS for use of an ACE 200 spectrometer. This research was supported by the NIH (DK19038 to H.B.G.; GM16424 to J.H.R.).
Funders:
Funding AgencyGrant Number
Fundacion AntorchasUNSPECIFIED
TWASUNSPECIFIED
American Chemical SocietyUNSPECIFIED
NIHDK19038
NIHGM16424
Issue or Number:20
Record Number:CaltechAUTHORS:20150428-132741371
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20150428-132741371
Official Citation:Paramagnetic NMR Spectroscopy of Cobalt(II) and Copper(II) Derivatives of Pseudomonas aeruginosa His46Asp Azurin A. J. Vila, B. E. Ramirez, A. J. Di Bilio, T. J. Mizoguchi, J. H. Richards, and H. B. Gray Inorganic Chemistry 1997 36 (20), 4567-4570 DOI: 10.1021/ic9703282
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:57051
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:28 Apr 2015 20:49
Last Modified:22 Nov 2019 09:58

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