Dressed polyions, counterion condensation, and adsorption excess in polyelectrolyte solutions

Proc Natl Acad Sci U S A. 1996 Apr 30;93(9):4342-4. doi: 10.1073/pnas.93.9.4342.

Abstract

The phenomenon of Manning-Oosawa counterion condensation is given an explicit statistical mechanical and qualitative basis via a dressed polyelectrolyte formalism in connection with the topology of the electrostatic free-energy surface and is derived explicitly in terms of the adsorption excess of ions about the polyion via the nonlinear Poisson-Boltzmann equation. The approach is closely analogous to the theory of ion binding in micelles. Our results not only elucidate a Poisson-Boltzmann analysis, which shows that a fraction of the counterions lie within a finite volume around the polyion even if the volume of the system tends towards infinity, but also provide a direct link between Manning's theta-the number of condensed counterions for each polyion site-and a statistical thermodynamic quantity, namely, the adsorption excess per monomer.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Adsorption
  • DNA / chemistry*
  • Electrochemistry
  • Electrolytes
  • Ions
  • Mathematics
  • Models, Theoretical
  • Oligodeoxyribonucleotides / chemistry
  • Polymers*
  • Solutions

Substances

  • Electrolytes
  • Ions
  • Oligodeoxyribonucleotides
  • Polymers
  • Solutions
  • DNA