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Title: V-51 NMR chemical shifts calculated from QM/MM models of peroxo forms of vanadium haloperoxidases
Authors: Geethalakshmi, K. R.
Waller, Mark P.
Thiel, Walter
Buehl, Michael
Keywords: Fungus curvularia-inaequalis
Active-site mutants
Dependent haloperoxidase
Catalytic mechanism
QD Chemistry
Issue Date: 2-Apr-2009
Citation: Geethalakshmi , K R , Waller , M P , Thiel , W & Buehl , M 2009 , ' V-51 NMR chemical shifts calculated from QM/MM models of peroxo forms of vanadium haloperoxidases ' Journal of Physical Chemistry B , vol 113 , no. 13 , pp. 4456-4465 . , 10.1021/jp8109308
Abstract: QM/MM models of the peroxo forms of vanadium-containing haloperoxidases (VHPOs) are critically assessed in terms of active site geometries, hydrogen bonds within the active site, isotropic and anisotropic V-51 NMR chemical shifts, and TD-DFT excitation energies. The geometric stability within the active site of the protein is comparable to the respective native forms, as indicated by low standard deviations in bond lengths across a number of local minima sampled along MID trajectories. There is a significant calculated upfield shift in delta(V-51) upon formation of the peroxo from the respective native forms for both the vanadium-containing chloroperoxidase (VCPO) and vanadium-containing bromoperoxidase (VBPO) models, which is in qualitative agreement with V-51 NMR experiments of VBPO in solution. The models show appreciable differences between the anisotropic chemical shifts of the different protonation states of the peroxo form of VHPO. The most likely candidates for the peroxo forms of the VHPO enzymes appear to be unprotonated or have a single proton on either of the equatorial oxygen ligands, based on QM/MM modeling in combination with X-ray, V-51 NMR, and UV-vis data.
Version: Postprint
Status: Peer reviewed
ISSN: 1520-6106
Type: Journal article
Rights: This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry B, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see DOI: 10.1021/jp8109308
Appears in Collections:University of St Andrews Research
Chemistry Research

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