In this communication we illustrate the occurrence of a recently reported new phenomenon of surface-charge amplification, SCA, (originally dubbed overcharging, OC), [Jimenez-Angeles F. and Lozada-Cassou M., J. Phys. Chem. B, 2004, 108, 7286] by means of molecular dynamics simulation of aqueous electrolytes solutions involving multivalent cations in contact with charged graphene walls and the presence of short-chain lithium polystyrene sulfonates where the solvent water is described explicitly with a realistic molecular model. We show that the occurrence of SCA in these systems, in contrast to that observed in primitive models, involves neither contact co-adsorption of the negatively charged macroions nor divalent cations with a large size and charge asymmetry as required in the case of implicit solvents. In fact the SCA phenomenon hinges around the preferential adsorption of water (over the hydrated ions) with an average dipolar orientation such that the charges of the water's hydrogen and oxygen sites induce magnification rather than screening of the positive-charged graphene surface, within a limited range of surface-charge density.
We use the recently developed soft-potential-enhanced Poisson-Boltzmann (SPB) theory to study the interaction between two parallel polyelectrolytes (PEs) in monovalent ionic solutions in the weak-coupling regime. The SPB theory is fitted to ion distributions from coarse-grained molecular dynamics (MD) simulations and benchmarked against all-atom MD modelling for poly(diallyldimethylammonium) (PDADMA). We show that the SPB theory is able to accurately capture the interactions between two PEs at distances beyond the PE radius. For PDADMA positional correlations between the charged groups lead to…
The low-frequency limit of the electrical conductivity (d.c. 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…
The structure of polyelectrolytes is highly sensitive to small changes in the interactions between its monomers. In particular, interactions mediated by counterions play a significant role, and are affected by both specific molecular effects and generic concentration effects. The ability of coarse-grained models to reproduce the structural properties of an atomic model is thus a challenging task. Our present study compares the ability of different kinds of coarse-grained models: (i)~to reproduce the structure of an atomistic model of a polyelectrolyte (the sodium polyacrylate), (ii)~to reprodu…
A series of well-defined hydrophilic and hydrophobic polyelectrolytes of various chain lengths $N$ and effective charge fractions $f_{eff}$ have been adsorbed onto oppositely charged solid surfaces immersed in aqueous solutions. \emph{In situ} high energy X-ray reflectivity has provided the thickness $h$, the electron density and the roughness of the adsorbed layer in its aqueous environment. In the case of hydrophobic polyelectrolytes, we have found $h\propto N^0 f_{eff}^{-2/3}$, in agreement with a pearl-necklace conformation for the chains induced by a Rayleigh-like instability.
We demonstrate in this paper the influence of solvent quality on the structure of the semi-dilute solution of a hydrophobic polyelectrolyte, partially sulfonated Poly-Styrene Sulfonate. Two solvents are used: (i) one mixture of water and an organic solvent: THF, which is also slightly polar; (ii) DMSO, a polar organic solvent. In case (i), it is shown by SAXS study that the structure - namely the scattering from all chains, characterised by a maximum ("polyelectrolyte peak"), of the aqueous hydrophobic polyelectrolyte solutions (PSS) depends on the solvent quality through the added amount of o…
We theoretically investigate electrostatic properties between two charged surfaces with a grafted polyelectrolyte layer in an aqueous electrolyte solution by using the Poisson-Boltzmann approach accounting for ion partitioning. In order to consider the ion partitioning effect, we focus on changes of electrostatic properties due to the difference in dielectric permittivity of the polyelectrolyte layer and the aqueous electrolyte solution. We find that ion partitioning enhances electrostatic potential in the region between two charged soft surfaces and hence increases the electrostatic interacti…
Using extensive Molecular Dynamics simulations we study the behavior of polyelectrolytes with hydrophobic side chains, which are known to form cylindrical micelles in aqueous solution. We investigate the stability of such bundles with respect to hydrophobicity, the strength of the electrostatic interaction, and the bundle size. We show that for the parameter range relevant for sulfonated poly-para-phenylenes (PPP) one finds a stable finite bundle size. In a more generic model we also show the influence of the length of the precursor oligomer on the stability of the bundles. We also point out t…
The combination of two techniques (Small Angle X-ray Scattering and Atomic Force Microscopy) has allowed us to measure in reciprocal and real space the correlation length $ξ$ of salt-free aqueous solutions of highly charged hydrophobic polyelectrolyte as a function of the polymer concentration $C_p$, charge fraction $f$ and chain length $N$. Contrary to the classical behaviour of hydrophilic polyelectrolytes in the strong coupling limit, $ξ$ is strongly dependent on $f$. In particular a continuous transition has been observed from $ξ\sim C_p^{-1/2}$ to $ξ\sim C_p^{-1/3}$ when $f$ decreased fro…
We investigate electro-osmosis in aqueous solutions of polyelectrolytes using mean-field equations. A solution of positively charged polyelectrolytes is confined between two negatively charged planar surfaces, and an electric field is applied parallel to the surfaces. When electrostatic attraction between the polymer and the surface is strong, the polymers adhere to the surface, forming a highly viscous adsorption layer that greatly suppresses the electro-osmosis. Conversely, electro-osmosis is enhanced by depleting the polymers from the surfaces. We also found that the electro-osmotic flow is…
Macromolecules based on dendritic or hyperbranched polyelectrolytes have been emerging as high potential candidates for biomedical applications. Here we study the charge and solvation structure of dendritic polyglycerol sulphate (dPGS) of generations 0 to 3 in aqueous sodium chloride solution by explicit-solvent molecular dynamics computer simulations. We characterize dPGS by calculating several important properties such as relevant dPGS radii, molecular distributions, the solvent accessible surface area, and the partial molecular volume. In particular, as the dPGS exhibits high charge renorma…
Structural and thermodynamic properties of the model solution containing charged oligomers and the equivalent number of counterions were studied by means of the canonical Monte Carlo simulation technique. The oligomers are represented as (flexible) freely jointed chains or as a linear (rigid) array of charged hard spheres. In accordance with the primitive model of electrolyte solutions, the counterions are modeled as charged hard spheres and the solvent as dielectric continuum. Significant differences in the pair distribution functions, obtained for the rigid (rod-like) and flexible model are …
Hydrophobic polyelectrolytes have been predicted to adopt an unique pearl-necklace conformation in aqueous solvents. We present in this Letter an attempt to characterise quantitatively this conformation with a focus on $D_p$, the pearl size. For this purpose polystyrenesulfonate (PSS) of various effective charge fractions $f_{eff}$ and chain lengths $N$ has been adsorbed onto oppositely charged surfaces immersed in water in condition where the bulk structure is expected to persist in the adsorbed state. \emph{In situ} ellipsometry has provided an apparent thickness $h_{app}$ of the PSS layer. …
We consider conformations and intra-molecular conformational transitions in amphiphilic starlike polymers formed by diblock copolymer arms with inner hydrophobic and outer polyelectrolyte blocks. A combination of an analytical mean-field theory with the assumption-free numerical self-consistent field (SCF) modeling approach is applied. It is demonstrated that unimolecular micelles with collapsed hydrophobic cores and swollen polyelectrolyte coronae are formed in dilute aqueous solutions at high ionic strength or/and low degree of ionization of the outer hydrophilic block. An intra-molecular co…
Polyelectrolyte multilayers (PEM) in combination with good electrolyte solvents, e.g., ionic liquids (ILs) are potential candidates for the new generation of electrochemical separators. Swelling PEM with aqueous IL solutions is one way to incorporate IL in PEM. In addition to quantifying the IL uptake in PEM, physical characterization of the swollen PEM is essential for their potential applications and to uncover the underlying molecular process of the swelling. In this article, thickness and viscoelasticity of PEI(PSS/PADMAC)4PSS and PEI(PSS/PAH)4PSS multilayers were determined upon uptake of…
The role of electrostatics on the interfacial properties of polyelectrolyte microgels has been discussed controversially in the literature. It is not yet clear if, or how, Coulomb interactions affect their behavior under interfacial confinement. In this work, we combine compression isotherms, atomic force microscopy imaging, and computer simulations to further investigate the behavior of pH-responsive microgels at oil-water interfaces. At low compression, charged microgels can be compressed more than uncharged microgels. The in-plane effective area of charged microgels is found to be smaller i…
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/col…
We investigate the complexation of a highly charged sphere with a long flexible polyelectrolyte, \textit{both negatively charged} in salt free environment. Electroneutrality is insured by the presence of divalent counterions. Using molecular dynamics (MD) within the framework of the primitive model, we consider different Coulomb coupling regimes. At strong Coulomb coupling we find that the adsorbed chain is always confined to the colloidal surface but forms different conformations that depend on the linear charge density of the chain. A mechanism involving the polyelectrolyte \textit{overcharg…
When polyelectrolyte-neutral block copolymers are mixed in solutions to oppositely charged species (e.g. surfactant micelles, macromolecules, proteins etc), there is the formation of stable supermicellar aggregates combining both components. The resulting colloidal complexes exhibit a core-shell structure and the mechanism yielding to their formation is electrostatic self-assembly. In this contribution, we report on the structural properties of supermicellar aggregates made from yttrium-based inorganic nanoparticles (radius 2 nm) and polyelectrolyte-neutral block copolymers in aqueous solution…
Binding and phase behavior of oppositely charged polyelectrolytes and surfactants were studied in aqueous bulk solutions and at air-water interfaces. In particular, we have investigated the polyanion poly(sodium 4-styrenesulfonate) (NaPSS) and the cationic surfactants dodecyltrimethylammonium bromide (C$_{12}$TAB), tetradecyltrimethylammonium bromide (C$_{14}$TAB) and cetyltrimethylammonium bromide (C$_{16}$TAB). In order to reveal surfactant/polyelectrolyte binding, aggregation and phase separation of the mixtures, we have varied the NaPSS concentration systematically and have kept the surfac…
The interaction between charged objects in solution is generally expected to recapitulate two central principles of electromagnetics: (i) like-charged objects repel, and (ii) they do so regardless of the sign of their electrical charge. Here we demonstrate experimentally that the solvent plays a hitherto unforeseen but crucial role in interparticle interactions, and importantly, that interactions in the fluid phase can break charge-reversal symmetry. We show that in aqueous solution, negatively charged particles can attract at long range while positively charged particles repel. In solvents th…
