Modeling the influence of adsorbed DNA on the lateral pressure and tilt transition of a zwitterionic lipid monolayer

Phys Chem Chem Phys. 2012 Aug 14;14(30):10613-21. doi: 10.1039/c2cp40923b. Epub 2012 Jun 29.

Abstract

Certain lipid monolayers at the air-water interface undergo a second-order transition from a tilted to an untilted liquid-crystalline state of their lipid hydrocarbon chains at sufficiently large lateral pressure. Recent experimental observations demonstrate that in the presence of divalent cations DNA adsorbs onto a zwitterionic lipid monolayer and decreases the tilt transition pressure. Lowering of the tilt transition pressure indicates that the DNA condenses the lipid monolayer laterally. To rationalize this finding we analyze a theoretical model that combines a phenomenological Landau approach with an extension of the Poisson-Boltzmann model to zwitterionic lipids. Based on numerical calculations of the mean-field electrostatic free energy of a zwitterionic lipid monolayer-DNA complex in the presence of divalent cations, we analyze the thermodynamic equilibrium of DNA adsorption. We find that adsorbed DNA induces a 10% reduction of the electrostatic contribution to the lateral pressure exerted by the monolayer. This result implies a small but notable decrease in the tilt transition pressure. Additional mechanisms due to ion-ion correlations and headgroup reorientations are likely to further enhance this decrease.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Adsorption
  • Air
  • DNA / chemistry*
  • DNA / metabolism
  • Lipids / chemistry*
  • Models, Theoretical*
  • Static Electricity
  • Thermodynamics
  • Water / chemistry

Substances

  • Lipids
  • Water
  • DNA