25Mg NMR in DNA solutions: Dominance of site binding effects

  1. D. Murk Rose*,
  2. M. L. Bleam,
  3. M. T. Record, Jr., and
  4. R. G. Bryant*
  1. Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53706
  2. *Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455

Abstract

25Mg NMR spectroscopy is applied to a study of magnesium ion interactions with DNA, which is considered as a model for a linear polyelectrolyte. It is demonstrated that the magnesium ion spectrum is complicated by a non-Lorent-zian line shape and is dominated by the effects of chemical exchange with macromolecule binding sites. A distinction is made between specific-site interactions in which the magnesium ion loses a water molecule from the first coordination sphere on binding and those interactions, referred to as territorial binding, in which the ion maintains its first coordination sphere complement of solvent. The first type of site-binding interactions are shown to dominate the magnesium ion NMR spectrum, based on a consideration of the magnitudes of the observed 25Mg relaxation rates compared with 23Na relaxation rates, the clear contributions of chemical exchange-limited relaxation, and an ion displacement experiment employing sodium.

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