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The low-frequency limit of the electrical conductivity (dc conductivity) of differently flexible polyions in aqueous solutions has been measured over an extended polyion concentration range, covering both the dilute and semidilute (entangled and unentangled) regime, up to the concentrated regime. The data have been analyzed taking into account the different flexibility of the polymer chains according to the scaling theory of polyion solutions, in the case of flexible polyions, and according to the Manning model, in the case of rigid polyions. In both cases, the fraction f of free counterions, released into the aqueous phase from the ionizable polyion groups, has been evaluated and its dependence on the polyion concentration determined. Our results show that the counterion condensation follows at least three different regimes in dependence on the polyion concentration. The fraction f of free counterions remains constant only in the semidilute regime (a region that we have named the Manning regime), while there is a marked dependence on the polyion concentration both in the dilute and in the concentrated regime. These results are briefly discussed in the light of the scaling theory of polyelectrolyte aqueous solutions.

Charged colloidal particles whose interacting potential is governed by a short-range attraction and a long-range screened electrostatic repulsion contributions form aggregates whose shape, size, and overall charge are sensitively dependent on the balance between attraction and repulsion. In some cases, this class of colloidal systems shows an equilibrium cluster phase, where particles associate and dissociate reversibly into clusters. When the aggregation of the charged particles is induced by adding an oppositely charged polyion, very close to the isoelectric condition, the interaggregate interactions become very strong and a dynamical arrested state seems to occur. We provide some experimental evidences of this structural arrest in a colloid system composed by vesicles built up by a cationic lipid stuck together by an oppositely charged linear polyion, by means of the combined use of static and dynamic light scattering technique complemented by laser Doppler electrophoretic measurements. Our results show that the second virial coefficient, which is related to the potential of mean force between two adjacent aggregates, markedly increases in the vicinity of the isoelectric point. We interpret this increase as a print of strong interparticle interactions, yielding to a dynamical arrested state via cluster growth.

Interaction of DNA with oppositely charged objects, such as multivalent ions, cationic surfactants, cationic liposomes, basic proteins, and alcohols, up to nano- or mesoscopic particles, gives rise to a very interesting and fascinating phenomenology, where the shape, size, and stability of the resulting aggregates depend on a delicate balance between different driving forces, mainly of electrostatic origin. We have studied the cationic liposome-DNA complexes during the whole complexation process, below, close to, and above the isoelectric condition, where the number of cationic lipids equals the number of phosphate groups on the DNA chain. We took advantage of the combined use of dynamic light scattering, laser Doppler electrophoretic mobility, and radio-wave dielectric relaxation measurements in order to characterize both the structural parameters (hydrodynamic radius) and the electrical parameters (charge and counterion concentration) of the resulting structures. These structures are fundamentally of two types, clusters of liposomes stuck together by DNA chains (cluster phase in low-density colloidal suspension) and coexisting DNA coils and DNA globules, according to the procedure through which interactions occur (liposomes in excess DNA solution or DNA in excess liposome suspension).

We present a set of electrical conductivity measurements of a mesoscopic equilibrium cluster phase in the aggregation process of charged particles induced by oppositely charged polyions. These measurements supply strong experimental evidence that correlated adsorption of polyions is driven by the counterion release. This phenomenon, known to occur in DNA-liposome mixtures in lamellar phase, i.e., when liposomes fuse together to form a sandwichlike structure encompassing DNA chains, was not previously observed in aqueous suspension of clusters of intact liposomes stuck together by polyions to form reversible aggregates. A simple statistical model of the lateral correlation of polyions at the particle surface justifies quantitatively the observed behavior of the counterion release, as shown by electrical conductivity measurements.

Lanthanide ions such as La3+ and Gd3+ are well known to have large effects on the structure of phospholipid membranes. Unilamellar vesicles of dipalmitoylphosphatidylcholine (DPPC) were prepared by sonication method and confirmed by transmission electron microscopy. The effects of concentration of gadolinium ions Gd3+ on DPPC unilamellar vesicles in aqueous media were studied by different techniques. As physical techniques, photon correlation spectroscopy, electrophoretic mobility, and differential scanning calorimetry were used. The theoretical predictions of the colloidal stability of liposomes were followed using the Derjaguin-Landau-Verwey-Overbeek theory. Changes in the size of liposomes and high polydispersities values were observed as Gd3+ concentration increases, suggesting that this cation induces the aggregation of vesicles. Electrophoretic mobility measurements on unilamellar vesicles as a function of Gd3+ ion concentration show that the vesicles adsorb Gd3+ ions. Above Gd3+ concentrations of 0.1 mol dm-3, the zeta potential and light scattering measurements indicate the beginning of aggregation process. For comparison with similar phospholipids, the zeta potential of phosphatidylcholine interacting with Gd3+ was measured, showing an analogous behavior. Differential scanning calorimetry has been used to determine the effect of Gd3+ on the transition temperature (Tc) and on the enthalpy (DeltaHc) associated with the process.

The dielectric properties of polyelectrolytes in solvent of different quality have been measured in an extended frequency range and the dielectric parameters associated with the polarization induced by counterion fluctuation over some peculiar polyion lengths have been evaluated. Following the scaling theory of polyelectrolyte solutions and the recent models developed by Dobrynin and Rubinstein that explicitly take into account the quality of the solvent on the polyion chain conformation, we have reviewed and summarized a set of scaling laws that describe the dielectric behavior of these systems in the dilute and semidilute regime. Moreover, for poorer solvents, where theory of hydrophobic polyelectrolytes predicts, and computer simulation confirms, a particular chain structure consisting of partially collapsed monomers (beads) connected by monomer strings, we derived a scaling law. These predictions are compared with the results obtained from the dielectric parameters (the dielectric increment delta epsilon and the relaxation time tau(ion)) of the "intermediate" frequency relaxation of two partially charged polymers, which possess a carbon-based backbone for which water is a poor solvent and ethylene glycol is a good solvent. By varying the solvent composition (a water-ethylene glycol mixture), we have tuned the quality of the solvent, passing from poor to good condition and have observed the predicted scaling for all the systems investigated. These findings give a further support to the scaling theory of polyelectrolyte solutions and to the necklace model for hydrophobic polyelectrolytes in poor solvents.

In this paper, we revisit some of our previous results together with further experimental evidences for the existence of large equilibrium clusters in low-density aqueous colloidal suspensions, resulting from the screening of charged spherical macroions by oppositely charged linear polyelectrolytes. The aggregation process is described by a simple phenomenological model where aggregates interact via a long-range repulsion Yukawa potential and some supports to the equilibrium properties of the resulting aggregates, on the basis of dynamic light scattering, zeta potential, and transmission electron microscopy techniques, have been provided.