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  • Title: Extensive NMRD studies of Ni(II) salt solutions in water and water-glycerol mixtures.
    Author: Kowalewski J, Egorov A, Kruk D, Laaksonen A, Nikkhou Aski S, Parigi G, Westlund PO.
    Journal: J Magn Reson; 2008 Nov; 195(1):103-11. PubMed ID: 18809345.
    Abstract:
    Aqueous solutions of simple nickel(II) salts are a classical test case for theories of the paramagnetic relaxation enhancement (PRE) and its dependence on the magnetic field (nuclear magnetic relaxation dispersion, NMRD), going back to late fifties. We present here new experimental data, extending the NMRD range up to 21T (900 MHz). In addition to salt solutions in (acidified) water, we have also measured on solutions containing glycerol. The aqueous solution data do not show any significant changes compared to the earlier experiments. The interpretation, based on the general ("slow-motion") theory is also similar to the earlier work from our laboratory. The NMRD-data in mixed solvents are qualitatively different, indicating that the glycerol not only changes the solution viscosity, but may also enter the first coordination sphere of the metal ion, resulting in lower symmetry complexes, characterized by non-vanishing averaged zero-field splitting. This hypothesis is corroborated by molecular dynamics simulations. A strategy appropriate for interpreting the NMRD-data for the chemically complicated systems of this type is proposed.
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