  The electrostatic complexation between DOTAP-DOPC unilamellar liposomes and
an oppositely charged polyelectrolyte (NaPA) has been investigated in a wide
range of the liposome surface charge density. We systematically characterized
the "reentrant condensation" and the charge inversion of
polyelectrolyte-decorated liposomes by means of dynamic light scattering and
electrophoresis. We explored the stability of this model
polyelectrolyte/colloid system by fixing each time the charge of the bare
liposomes and by changing two independent control parameters of the
suspensions: the polyelectrolyte/colloid charge ratio and the ionic strength of
the aqueous suspending medium. The progressive addition of neutral DOPC lipid
within the liposome membrane gave rise to a new intriguing phenomenon: the
stability diagram of the suspensions showed a novel reentrance due to the
crossing of the desorption threshold of the polyelectrolyte. Indeed, at fixed
charge density of the bare DOTAP/DOPC liposomes and for a wide range of polyion
concentrations, we showed that the simple electrolyte addition first (low salt
regime) destabilizes the suspensions because of the enhanced screening of the
residual repulsion between the complexes, and then (high salt regime)
determines the onset of a new stable phase, originated by the absence of
polyelectrolyte adsorption on the particle surfaces. We show that the observed
phenomenology can be rationalized within the Velegol-Thwar model for
heterogeneously charged particles and that the polyelectrolyte desorption fits
well the predictions of the adsorption theory of Winkler and Cherstvy. Our
findings unambiguously support the picture of the reentrant condensation as
driven by the correlated adsorption of the polyelectrolyte chains on the
particle surface, providing interesting insights into possible mechanisms for
tailoring complex colloids via salt-induced effects.
