Document Detail

Electron paramagnetic resonance spectroscopic study of copper hopping in doped bis(L-histidinato)cadmium dihydrate.
MedLine Citation:
PMID:  23530765     Owner:  NLM     Status:  MEDLINE    
Electron paramagnetic resonance (EPR) spectroscopy was used to study Cu(II) dynamic behavior in a doped biological model crystal, bis(L-histidinato)cadmium dihydrate, in order to gain better insight into copper site stability in metalloproteins. Temperature-dependent changes in the low temperature X-band EPR spectra became visible around 100 K and continued up to room temperature. The measured 298 K g-tensor (principal values: 2.17, 2.16, 2.07) and copper hyperfine coupling tensor (principal values: -260, -190, -37 MHz) were similar to the average of the 77 K tensor values pertaining to two neighboring histidine binding sites. The observed temperature dependence was interpreted using Anderson's theory of motional narrowing, where the magnetic parameters for the different states are averaged as the copper rapidly hops between sites. The EPR pattern was also found to undergo a sharp sigmoidal-shaped, temperature-dependent conversion between two species with a critical temperature T(c) ≈ 160 K. The species below T(c) hops between the two low temperature site patterns, and the one above T(c) represents an average of the molecular spin Hamiltonian coupling tensors of the two 77 K sites. In addition, the low and high temperature species hop between one another, contributing to the dynamic averaging. Spectral simulations using this 4-state model determined a hop rate between the two low temperature sites ν(h4) = 4.5 × 10(8) s(-1) and between the low and high temperature states ν(h2) = 1.7 × 10(8) s(-1) at 160 K. An Arrhenius relationship of hop rate and temperature gave energy barriers of ΔE4 = 389 cm(-1) and ΔE2 = 656 cm(-1) between the two low temperature sites and between the low and high temperature states, respectively.
Michael J Colaneri; Jacqueline Vitali; Kristin Kirschbaum
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Publication Detail:
Type:  Journal Article; Research Support, N.I.H., Extramural     Date:  2013-04-12
Journal Detail:
Title:  The journal of physical chemistry. A     Volume:  117     ISSN:  1520-5215     ISO Abbreviation:  J Phys Chem A     Publication Date:  2013 Apr 
Date Detail:
Created Date:  2013-04-25     Completed Date:  2013-10-29     Revised Date:  2014-05-07    
Medline Journal Info:
Nlm Unique ID:  9890903     Medline TA:  J Phys Chem A     Country:  United States    
Other Details:
Languages:  eng     Pagination:  3414-27     Citation Subset:  IM    
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MeSH Terms
Binding Sites
Cadmium / chemistry
Coordination Complexes / chemistry*
Copper / chemistry*
Electron Spin Resonance Spectroscopy
Histidine / chemistry
Metalloproteins / chemistry
Molecular Mimicry
Water / chemistry*
Grant Support
Reg. No./Substance:
0/Coordination Complexes; 0/Metalloproteins; 00BH33GNGH/Cadmium; 059QF0KO0R/Water; 4QD397987E/Histidine; 789U1901C5/Copper

From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine

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