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  • Title: Pulsed EPR studies of the exchangeable proton at the molybdenum center of dimethyl sulfoxide reductase.
    Author: Raitsimring AM, Astashkin AV, Feng C, Enemark JH, Nelson KJ, Rajagopalan KV.
    Journal: J Biol Inorg Chem; 2003 Jan; 8(1-2):95-104. PubMed ID: 12459903.
    Abstract:
    Electron spin echo envelope modulation (ESEEM) spectroscopy has been used to determine the hyperfine ( hfi) and quadrupole ( nqi) interactions of the exchangeable deuteron (proton) at the Mo(V) site of DMSO reductase. The data obtained have been translated into structure-related parameters. It was found that isotropic hfi constant of the proton is not unique, but is distributed within a range of 26-36 MHz. From this hfi distribution, a 30 degrees -wide distribution of the OH bond orientations due to a rotation around the Mo-O bond was estimated. The angle between the axes of the nqi and anisotropic hfi tensors was found to be anomalously small in comparison with that expected from the Mo-O-D bond geometry. This peculiarity was attributed to the effect of spin density on the hydroxyl oxygen atom. The orientation of the Mo-OH fragment with respect to the g-frame was determined from the experimental orientations of the nqi and hfi tensor axes and a theoretical evaluation of the anisotropic hfi axis direction.
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