A field-dissociation relation for polyelectrolytes with an application to field-induced conformational changes of polynucleotides

Biophys Chem. 1977 Nov;7(3):189-92. doi: 10.1016/0301-4622(77)87021-x.

Abstract

An extension to polyelectrolyte solutions of Onsager's field-dissociation relation for weak electrolytes can be derived in a simple way. It is found that, except in the limit of zero ionic strength, a strong applied electric field prevents counterion condensation from proceeding to completion. The extent of incompleteness initially varies linearly with the applied field. The field-dissociation relation can easily be incorporated into the theory of ionic effects on the stability of ordered polynucleotide structures, whereupon a dependence of the stability on field strength emerges. An explicit calculation for a co-operative transition of the DNA melting type is presented, and it is concluded that for sufficiently low ionic strengths, a field of the order of 10 kV/cm may be able to induce melting by lowering the Tm by a few degrees. The threshold effect found experimentally by Pörschke, and particularly the observed linear dependence of the threshold field on the logarithm of the ionic strength, appears here as a simple consequence of the linear increase of the stabilization free energy with the logarithm of ionic strength.

MeSH terms

  • Chemical Phenomena
  • Chemistry, Physical
  • DNA
  • Electrolytes*
  • Nucleic Acid Conformation
  • Polynucleotides*

Substances

  • Electrolytes
  • Polynucleotides
  • DNA