Abstract：
:1,2-diolato ligands, such as carbohydrates and glycoproteins, tend to stabilize chromium(V), thus forming important intermediates that have been implicated in the genotoxicity of Cr(VI). Since many years, room-temperature continuous-wave electron paramagnetic resonance (EPR) at X-band microwave frequencies has been used as a standard characterization tool to study chromium(V) intermediates formed during the reduction of Cr(VI) in the presence of biomolecules. In this work, the added value is tested of using a combination of pulsed and high-field EPR techniques with density functional theory computations to unravel the nature of Cr(V) complexes with biologically relevant chelators, such as carbohydrates. The study focuses on the oxidochromium(V) complexes formed during reduction of potassium dichromate with glutathione in the presence of the monosaccharide d-glucose or the polyalcohol d-glucitol. It is shown that although the presence of a multitude of Cr(V) intermediates may hamper a complete structural determination, the combined EPR and DFT approach reveals unambiguously the effect of freezing on the location of the counterions, the gradual replacement of water ligands by the diols, and the preference of Cr(V) to bind certain conformers.
journal_name
J Inorg Biochemjournal_title
Journal of inorganic biochemistryauthors
Van Doorslaer S,Beirinckx Q,Nys K,Mangiameli MF,Cuypers B,Callens F,Vrielinck H,González JCdoi
10.1016/j.jinorgbio.2016.07.012subject
Has Abstractpub_date
2016-09-01 00:00:00pages
216-226eissn
0162-0134issn
1873-3344pii
S0162-0134(16)30213-6journal_volume
162pub_type
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