Exploiting orientation-selective DEER: determining molecular structure in systems containing Cu(II) centres

Bowen, Alice M., Jones, Michael W., Lovett, Janet E., Gaule, Thembanikosi G., McPherson, Michael J., Dilworth, Jonathan R., Timmel, Christiane R. and Harmer, Jeffrey R. (2016) Exploiting orientation-selective DEER: determining molecular structure in systems containing Cu(II) centres. Physical Chemistry Chemical Physics, 18 8: 5981-5994. doi:10.1039/c5cp06096f


Author Bowen, Alice M.
Jones, Michael W.
Lovett, Janet E.
Gaule, Thembanikosi G.
McPherson, Michael J.
Dilworth, Jonathan R.
Timmel, Christiane R.
Harmer, Jeffrey R.
Title Exploiting orientation-selective DEER: determining molecular structure in systems containing Cu(II) centres
Journal name Physical Chemistry Chemical Physics   Check publisher's open access policy
ISSN 1463-9076
1463-9084
Publication date 2016-02-28
Year available 2016
Sub-type Article (original research)
DOI 10.1039/c5cp06096f
Open Access Status DOI
Volume 18
Issue 8
Start page 5981
End page 5994
Total pages 14
Place of publication Cambridge, United Kingdom
Publisher Royal Society of Chemistry
Language eng
Formatted abstract
Orientation-selective DEER (Double Electron-Electron Resonance) measurements were conducted on a series of rigid and flexible molecules containing Cu(II) ions. A system with two rigidly held Cu(II) ions was afforded by the protein homo-dimer of copper amine oxidase from Arthrobacter globiformis. This system provided experimental DEER data between two Cu(II) ions with a well-defined distance and relative orientation to assess the accuracy of the methodology. Evaluation of orientation-selective DEER (os DEER) on systems with limited flexibility was probed using a series of porphyrin-based Cu(II)–nitroxide and Cu(II)–Cu(II) model systems of well-defined lengths synthesized for this project. Density functional theory was employed to generate molecular models of the conformers for each porphyrin-based Cu(II) dimer studied. Excellent agreement was found between DEER traces simulated using these computed conformers and the experimental data. The performance of different parameterised structural models in simulating the experimental DEER data was also investigated. The results of this analysis demonstrate the degree to which the DEER data define the relative orientation of the two Cu(II) ions and highlight the need to choose a parameterised model that captures the essential features of the flexibility (rotational freedom) of the system being studied.
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: HERDC Pre-Audit
Centre for Advanced Imaging Publications
 
Versions
Version Filter Type
Citation counts: TR Web of Science Citation Count  Cited 4 times in Thomson Reuters Web of Science Article | Citations
Scopus Citation Count Cited 4 times in Scopus Article | Citations
Google Scholar Search Google Scholar
Created: Tue, 15 Mar 2016, 11:27:15 EST by System User on behalf of Centre for Advanced Imaging