Title
A multifrequency HYSCORE study of weakly coupled nuclei in frozen solutions of high-spin aquometmyoglobin A multifrequency HYSCORE study of weakly coupled nuclei in frozen solutions of high-spin aquometmyoglobin
Author
Faculty/Department
Faculty of Sciences. Physics
Publication type
article
Publication
Easton, Pa ,
Subject
Physics
Chemistry
Source (journal)
Inorganic chemistry / American Chemical Society. - Easton, Pa
Volume/pages
47(2008) :23 , p. 11294-11304
ISSN
0020-1669
ISI
000261142900058
Carrier
E
Target language
English (eng)
Full text (Publishers DOI)
Affiliation
University of Antwerp
Abstract
In this work, we show the extreme power of multifrequency HYSCORE (hyperfine sublevel correlation spectroscopy) techniques to unravel the hyperfine interactions of the electron spin with the remote nuclei in the heme site of high-spin ferric heme proteins. Horse heart aquo-metmyoglobin was used as a model system to demonstrate the power of these techniques. Experimental evidence was collected and assigned to protons of the proximal histidine ligand, to the mesoprotons of the heme ligand, and to two different protons of the distal water ligand. The latter difference relates to the stabilization of the water ligand by the E7His residue. Furthermore, HYSCORE signals of the remote Nä of the proximal (F8) and Nå of the distal (E7) histidine were detected. Finally, correlation peaks from the lesser-abundant 13C nuclei of the heme ligand could be detected. These novel results allow dissection of the hyperfine couplings into individual contributions and calculation of the spin density in the ð and ó orbitals, thus completing earlier electron paramagnetic resonance and liquid-state NMR data.
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