English
 
User Manual Privacy Policy Disclaimer Contact us
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT
  Thiolate spin population of type I copper in azurin derived from 33S hyperfine coupling

Cohen, M. R., Mendelman, N., Radoul, M., Wilson, T. D., Savelieff, M. G., Zimmermann, H., et al. (2017). Thiolate spin population of type I copper in azurin derived from 33S hyperfine coupling. Inorganic Chemistry, 56(11), 6163-6174. doi:10.1021/acs.inorgchem.7b00167.

Item is

Basic

show hide
Item Permalink: http://hdl.handle.net/11858/00-001M-0000-002D-499C-0 Version Permalink: http://hdl.handle.net/21.11116/0000-0000-0298-2
Genre: Journal Article

Files

show Files
hide Files
:
InorgChem_56_2017_6163.pdf (Any fulltext), 4MB
 
File Permalink:
-
Name:
InorgChem_56_2017_6163.pdf
Description:
-
Visibility:
Restricted (Max Planck Institute for Medical Research, Heidelberg; )
MIME-Type / Checksum:
application/pdf
Technical Metadata:
Copyright Date:
-
Copyright Info:
-
License:
-
:
InorgChem_56_2017_6163_Suppl.pdf (Any fulltext), 3MB
 
File Permalink:
-
Name:
InorgChem_56_2017_6163_Suppl.pdf
Description:
-
Visibility:
Restricted (Max Planck Institute for Medical Research, Heidelberg; )
MIME-Type / Checksum:
application/pdf
Technical Metadata:
Copyright Date:
-
Copyright Info:
-
License:
-

Locators

show
hide
Description:
-
Description:
-

Creators

show
hide
 Creators:
Cohen, Marie Ramirez, Author
Mendelman, Netanel, Author
Radoul, Marina, Author
Wilson, Tiffany D., Author
Savelieff, Masha G., Author
Zimmermann, Herbert1, Author              
Kaminker, Ilia, Author
Feintuch, Akiva, Author
Lu, Yi, Author
Goldfarb, Daniella, Author
Affiliations:
1Department of Biomolecular Mechanisms, Max Planck Institute for Medical Research, Max Planck Society, ou_1497700              

Content

show
hide
Free keywords: -
 Abstract: The electron transfer mediating properties of type I copper proteins stem from the intricate ligand coordination sphere of the Cu ion in their active site. These redox properties are in part due to unusual cysteine thiol coordination, which forms a highly covalent copper–sulfur (Cu–S) bond. The structure and electronic properties of type I copper have been the subject of many experimental and theoretical studies. The measurement of spin delocalization of the Cu(II) unpaired electron to neighboring ligands provides an elegant experimental way to probe the fine details of the electronic structure of type I copper. To date, the crucial parameter of electron delocalization to the sulfur atom of the cysteine ligand has not been directly determined experimentally. We have prepared 33S-enriched azurin and carried out W-band (95 GHz) electron paramagnetic resonance (EPR) and electron–electron double resonance detected NMR (EDNMR) measurements and, for the first time, recorded the 33S nuclear frequencies, from which the hyperfine coupling and the spin population on the sulfur of the thiolate ligand were derived. The overlapping 33S and 14N EDNMR signals were resolved using a recently introduced two-dimensional correlation technique, 2D-EDNMR. The 33S hyperfine tensor was determined by simulations of the EDNMR spectra using 33S hyperfine and quadrupolar tensors predicted by QM/MM DFT calculations as starting points for a manual spectral fit procedure. To reach a reasonable agreement with the experimental spectra, the 33S hyperfine principal value, Az, and one of the corresponding Euler angles had to be modified. The final values obtained gave an experimentally determined sulfur spin population of 29.8 ± 0.7%, significantly improving the wide range of 29–62% reported in the literature. Our direct, experimentally derived value now provides an important constraint for further theoretical work aimed at unravelling the unique electronic properties of this site.

Details

show
hide
Language(s): eng - English
 Dates: 2017-01-182017-05-162017-06-05
 Publication Status: Published in print
 Pages: 12
 Publishing info: -
 Table of Contents: -
 Rev. Method: Peer
 Degree: -

Event

show

Legal Case

show

Project information

show

Source 1

show
hide
Title: Inorganic Chemistry
  Abbreviation : Inorg. Chem.
Source Genre: Journal
 Creator(s):
Affiliations:
Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 56 (11) Sequence Number: - Start / End Page: 6163 - 6174 Identifier: ISSN: 0020-1669
CoNE: /journals/resource/0020-1669