The structure of ions and zwitterionic lipids regulates the charge of dipolar membranes

In pure water, zwitterionic lipids form lamellar phases with an equilibrium water gap on the order of 2 to 3 nm as a result of the dominating van der Waals attraction between dipolar bilayers. Monovalent ions can swell those neutral lamellae by a small amount. Divalent ions can adsorb onto dipolar membranes and charge them. Using solution X-ray scattering, we studied how the structure of ions and zwitterionic lipids regulates the charge of dipolar membranes. We found that unlike monovalent ions that weakly interact with all of the examined dipolar membranes, divalent and trivalent ions adsorb onto membranes containing lipids with saturated tails, with an association constant on the order of ～10 M(-1). One double bond in the lipid tail is sufficient to prevent divalent ion adsorption. We suggest that this behavior is due to the relatively loose packing of lipids with unsaturated tails that increases the area per lipid headgroup, enabling their free rotation. Divalent ion adsorption links two lipids and limits their free rotation. The ion-dipole interaction gained by the adsorption of the ions onto unsaturated membranes is insufficient to compensate for the loss of headgroup free-rotational entropy. The ion-dipole interaction is stronger for cations with a higher valence. Nevertheless, polyamines behave as monovalent ions near dipolar interfaces in the sense that they interact weakly with the membrane surface, whereas in the bulk their behavior is similar to that of multivalent cations. Advanced data analysis and comparison with theory provide insight into the structure and interactions between ion-induced regulated charged interfaces. This study models biologically relevant interactions between cell membranes and various ions and the manner in which the lipid structure governs those interactions. The ability to monitor these interactions creates a tool for probing systems that are more complex and forms the basis for controlling the interactions between dipolar membranes and charged proteins or biopolymers for encapsulation and delivery applications.     

IR-Untersuchungen an wäßrigen Lösungen von Metallchloriden

IR Spectra of Aqueous Solutions of Metal Chlorides Aqueous solutions of the chlorides of some monovalent and divalent metals have been investigated by IR-Spectroscopy. The spectra are registered as a function of the concentration of these solutions. The solutions of monovalent metal chlorides show no variations of the deformation band and the valence band to pure water. In solutions of divalent metal chlorides the positions of the bands are dependent on the concentration of solution.     

Theory of competitive counterion adsorption on flexible polyelectrolytes: divalent salts

The counterion distribution around an isolated flexible polyelectrolyte in the presence of a divalent salt is evaluated using the adsorption model [M. Muthukumar, J. Chem. Phys. 120, 9343 (2004)] that considers the Bjerrum length, salt concentration, and local dielectric heterogeneity as physical variables in the system. Self-consistent calculations of effective charge and size of the polymer show that divalent counterions replace condensed monovalent counterions in competitive adsorption. The theory further predicts that at modest physical conditions for a flexible polyelectrolytes such as sodium polystyrene sulfonate in aqueous solutions polymer charge is compensated and reversed with increasing divalent salt. Consequently, the polyelectrolyte shrinks and reswells. Lower temperatures and higher degrees of dielectric heterogeneity between chain backbone and solvent enhance condensation of all species of ions. Complete diagrams of states for the effective charge calculated as functions of the Coulomb strength and salt concentration suggest that (a) overcharging requires a minimum Coulomb strength and (b) progressively higher presence of salt recharges the polymer due to either electrostatic screening (for low Coulomb strengths) or coion condensation (for high Coulomb strengths). Consideration of ion-bridging by divalent counterions leads to a first-order collapse of polyelectrolytes in modest presence of divalent salts and at higher Coulomb strengths. The authors' theoretical predictions are in agreement with the generic results from experiments and simulations.     

Repulsion between oppositely charged macromolecules or particles

The interaction of two oppositely charged surfaces has been investigated using Monte Carlo simulations and approximate analytical methods. When immersed in an aqueous electrolyte containing only monovalent ions, two such surfaces will generally show an attraction at large and intermediate separations. However, if the electrolyte solution contains divalent or multivalent ions, then a repulsion can appear at intermediate separations. The repulsion increases with increasing concentration of the multivalent salt as well as with the valency of the multivalent ion. The addition of a second salt with only monovalent ions magnifies the effect. The repulsion between oppositely charged surfaces is an effect of ion-ion correlations, and it increases with increasing electrostatic coupling and, for example, a lowering of the dielectric permittivity enhances the effect. An apparent charge reversal of the surface neutralized by the multivalent ion is always observed together with a repulsion at large separation, whereas at intermediate separations a repulsion can appear without charge reversal. The effect is hardly observable for a symmetric multivalent salt (e.g., 2:2 or 3:3).     

Studies on the interaction of poly(4-vinylpyridiniumchloride) with poly(sodiumphosphate) in an aqueous solution by conductometry

A reaction between poly(4-vinylpyridiniumchloride) and poly(sodiumphosphate) in the presence and absence of NaCl and NaBr salts was studied in aqueous solution by conductometry. The interaction of polycation and polyanion gave insoluble polyelectrolyte complex which contained polycation and polyanion in unit mole ratio in a salt-free solution. A deviation from stoichiometry was observed at high polyion concentration and in the presence of NaCl and NaBr salts. The resultant complex showed swelling property in different solvent mixtures. A maximum degree of swelling was obtained in the solvent mixture of NaBr + water and NaBr + water + acetone. Furthermore, polyelectrolyte complex sorbed salts from aqueous electrolyte solutions. The sorption of salts increased with increasing salt concentration. © 1996 John Wiley & Sons, Inc.     

A salt-free zero-charged aqueous onion-phase enhances the solubility of fullerene C60 in water

An onion-phase (multilamellar vesicular phase or Lalpha-phase) was prepared from salt-free zero-charged cationic and anionic (catanionic) surfactant mixtures of tetradecyltrimethylammonium hydroxide (TTAOH)/lauric acid (LA)/H2O. The H+ and OH- counterions form water (TTAOH + LA --> TTAL + H2O), leaving the solution salt free. The onion-phase solution has novel properties including low conductivity, low osmotic pressure and unscreened electrostatic repulsions between cationic and anionic surfactants because of the absence of salt. The spherical multilamellar vesicles have an average 250 nm radius as measured by freeze-fracture transmission electron microscopy (FF-TEM) and the maximum interlayer distance, i.e., the thickness of the hydrophobic bilayer and the water layer, was calculated to be around 52 nm by small-angle X-ray scattering (SAXS). Extremely hydrophobic C60 fullerene can be solubilized in this salt-free zero-charged aqueous onion-phase. As a typical result, 0.588 mg.mL(-1) (approximately 0.82 mmol.L(-1)) C60 has been successfully solubilized into a 50 mmol.L(-1) catanionic surfactant onion-phase aqueous solution. The weight ratio of fullerene to TTAL is calculated to be around 1:40. Solubilization of C60 in the salt-free catanionic onion-phase solution was investigated by using different sample preparation routes, and a variety of techniques were used to characterize these vesicular systems with or without encapsulated C60. The onion-phase solution changed color from slightly bluish to yellow or brown after C60 was solubilized. 1H and 13C NMR measurements indicated that the C60 molecules are located in the hydrophobic layers, i.e., in the central positions [omega-CH3 and delta-(CH2)x] of the hydrophobic layers of the TTAL onion-phase. Salt-free zero-charged catanionic vesicular aqueous solutions are good candidates for enhancing the solubility of C60 in aqueous solutions and may broaden the functionality of fullerenes to new potential applications in biology, medicine, and materials. Hopefully, our method can also be extended to solubilize functionalized carbon nanotubes in aqueous solutions.     

Monte Carlo simulations of a charged dendrimer with explicit counterions and salt ions

Static properties of a dendrimer with generation g = 5 with positively charged terminal groups in an athermal solvent are studied by lattice Monte Carlo simulations using the cooperative motion algorithm as the tossing scheme. The calculations are performed both for a salt-free system with neutralizing counterions and for a small amount of added monovalent and divalent salt. The full Coulomb potential and the excluded volume interactions between ions and beads are taken explicitly into account with the reduced temperature tau, the number of salt cations (anions) n(s), and salt valence z(s) as the simulation parameters. The bahaviour of the systems is analyzed by the mean effective charge per end-bead , Coulomb mean energy , mean-square radius of gyration , pair correlation functions g(alphabeta), and charge density rho(ch). The simulations show that for n(s)> or = 0 and decreasing tau: (a) there is encapsulation in the dendrimer and condensation onto the terminal groups of anions accompanied by a monotonic decrease in and and by subsequent swelling and shrinking of the molecule; (b) encapsulation, condensation and shrinking are the most significant and swelling weaker for |z(s)| = 2; (c) penetration of salt cations into the dendrimer is minor when compared to that of anions; (d) rho(ch) is reduced and becomes negative close to the center of mass of the dendrimer and on its periphery; (e) for the considered n(s) > 0, unlike divalent salt ions the monovalent ones cause slight effects when compared to the salt-free case.     

Investigation of the salting out of methane from aqueous electrolyte solutions using computer simulations

We calculate the excess chemical potential of methane in aqueous electrolyte solutions of NaCl using Monte Carlo computer simulations. In a recent work [Docherty et al. J. Chem. Phys. 2006, 125, 074510], we presented a new potential model for methane in water which is capable of describing accurately the excess chemical potential of methane in pure water over a range of temperatures, a quantity that can be related to the solubility and which is commonly used to study the hydrophobic effect. Here, we use the same potential model for the water-methane interactions and investigate the effect of added salt on the chemical potential of methane in the solution. The methane molecules are modeled as single Lennard-Jones (LJ) interaction sites, and the water molecules are modeled with the TIP4P/2005 model. A correcting factor of chi = 1.07 for the energetic Berthelot (geometric) combining rule of the methane-water interaction is also used, which mimics the polarization of methane in water. We consider NaCl as the salt and treat the ions with the Smith and Dang model (i.e., as charged LJ interaction sites). Ion-water, ion-ion, and ion-methane interactions are treated using Lorentz-Berthelot combining rules. In addition, the Coulombic potential is used to model charge-charge interactions which are calculated using the Ewald sum. We have carried out isobaric-isothermal (NpT) simulations to determine the equilibrium densities of the solutions. The simulation data is in excellent agreement with experimental densities of aqueous NaCl solutions of different concentration. Hydration numbers are also obtained and found to be in agreement with reported data. Canonical (NVT) simulations at the averaged densities are then performed using the Widom test-particle insertion method to obtain the excess chemical potential of methane in the saline solutions. An increase in the chemical potential of methane, corresponding to a salting out effect, is observed when salt is added to the solution. We investigate different concentrations and ion sizes. An overprediction of the salting out effect as compared with experimental data is observed, which we believe is due to the polarizing effect of the ions in the solution, which is not taken into account by the model. We also find a direct correlation between the increase in the chemical potential and the packing fraction of the solution and argue that the main cause of the observed salting out effect (as represented by an increase in the excess chemical potential) is the increase in the packing fraction of the solutions due to the added salt. Together, with this, we put forward an argument toward explaining the anomalous Hofmeister effect of Li(+).     

Effect of exchangeable cation on the swelling property of 2:1 dioctahedral smectite--a periodic first principle study

We used both localized and periodic calculations on a series of monovalent (Li+, Na+, K+, Rb+, Cs+) and divalent (Mg2+, Ca2+, Sr2+, Ba2+) cations to monitor their effect on the swelling of clays. The activity order obtained for the exchangeable cations among all the monovalent and divalent series studied: Ca2+ > Sr2+ > Mg2+ > Rb+ > Ba2+ > Na+ > Li+ > Cs+ > K+. We have shown that, in case of dioctahedral smectite, the hydroxyl groups play a major role in their interaction with water and other polar molecules in the presence of an interlayer cation. We studied both type of clays, with a different surface structure and with/without water using a periodic calculation. Interlayer cations and charged 2:1 clay surfaces interact strongly with polar solvents; when it is in an aqueous medium, clay expands and the phenomenon is known as crystalline swelling. The extent of swelling is controlled by a balance between relatively strong swelling forces and electrostatic forces of attraction between the negatively charged phyllosilicate layer and the positively charged interlayer cation. We have calculated the solvation energy at the first hydration shell of an exchangeable cation, but the results do not correspond directly to the experimental d-spacing values. A novel quantitative scale is proposed with the numbers generated by the relative nucleophilicity of the active cation sites in their hydrated state through Fukui functions within the helm of the hard soft acid base principle. The solvation effect thus measured show a perfect match with experiment, which proposes that the reactivity index calculation with a first hydration shell could rationalize the swelling mechanism for exchangeable cations. The conformers after electron donation or acceptance propose the swelling mechanism for monovalent and divalent cations.     

Aqueous solutions of divalent chlorides: ions hydration shell and water structure

By combining neutron diffraction and Monte Carlo simulations, we have determined the microscopic structure of the hydration ions shell in aqueous solutions of MgCl(2) and CaCl(2), along with the radial distribution functions of the solvent. In particular the hydration shell of the cations, show cation specific symmetry, due to the strong and directional interaction of ions and water oxygens. The ions and their hydration shells likely form molecular moieties and bring clear signatures in the water-water radial distribution functions. Apart from these signatures, the influence of divalent salts on the microscopic structure of water is similar to that of previously investigated monovalent solutes, and it is visible as a shift of the second peak of the oxygen-oxygen radial distribution function, caused by distortion of the hydrogen bond network of water.     

Effects of cations on the hydrogen bond network of liquid water: new results from X-ray absorption spectroscopy of liquid microjets

Oxygen K-edge X-ray absorption spectra (XAS) of aqueous chloride solutions have been measured for Li(+), Na(+), K(+), NH(4)(+), C(NH(2))(3)(+), Mg(2+), and Ca(2+) at 2 and 4 M cation concentrations. Marked changes in the liquid water XAS are observed upon addition of the various monovalent cation chlorides that are nearly independent of the identity of the cation. This indicates that interactions with the dissolved monovalent cations do not significantly perturb the unoccupied molecular orbitals of water molecules in the vicinity of the cations and that water-chloride interactions are primarily responsible for the observed spectral changes. In contrast, the addition of the divalent cations engenders changes unique from the case of the monovalent cations, as well as from each other. Density functional theory calculations suggest that the ion-specific spectral variations arise primarily from direct electronic perturbation of the unoccupied orbitals due to the presence of the ions, probably as a result of differences in charge transfer from the water molecules onto the divalent cations.     

All-atom molecular dynamics analysis of kinetic and structural properties of ionic micellar solutions

All-atom molecular dynamics simulation results regarding aqueous sodium dodecyl sulfate (SDS) solutions have been presented. Both salt-free solutions with different SDS concentrations and those containing calcium chloride additives have been studied. The simulation has shown that surface-active SDS ions form stable premicellar aggregates. The obtained molecular dynamics trajectories have been used to describe both the kinetic and structural properties of solutions containing SDS molecular aggregates and the properties of individual aggregates. Aggregation kinetics has been investigated, and the characteristic sizes of the aggregates have been calculated by different methods. It has been found that the size of a premicellar aggregate with aggregation number n = 16 in a salt-free solution virtually does not depend on surfactant concentration. Radial distribution functions (RDFs) of hydrogen and oxygen atoms of water molecules relative to the center of mass of an aggregate have no local maxima near the aggregate surface; i.e., the surface is incompletely wetted with water. Corresponding RDFs of carbon atoms have one, two or three maxima depending on the surfactant concentration and the serial number of a carbon atom in the hydrocarbon radical of the surface- active ion. The study of the potentials of mean force for the interaction of sodium and calcium ions with an aggregate having aggregation number n = 32 shows that only calcium ions can be strongly bound to such an aggregate.     

Effect of cation size and charge on the interaction between silica surfaces in 1:1, 2:1, and 3:1 aqueous electrolytes

Application of two complementary AFM measurements, force vs separation and adhesion force, reveals the combined effects of cation size and charge (valency) on the interaction between silica surfaces in three 1:1, three 2:1, and three 3:1 metal chloride aqueous solutions of different concentrations. The interaction between the silica surfaces in 1:1 and 2:1 salt solutions is fully accounted for by ion-independent van der Waals (vdW) attraction and electric double-layer repulsion modified by cation specific adsorption to the silica surfaces. The deduced ranking of mono- and divalent cation adsorption capacity (adsorbability) to silica, Mg(2+) < Ca(2+) < Na(+) < Sr(2+) < K(+) < Cs(+), follows cation bare size as well as cation solvation energy but does not correlate with hydrated ionic radius or with volume or surface ionic charge density. In the presence of 3:1 salts, the coarse phenomenology of the force between the silica surfaces as a function of salt concentration resembles that in 1:1 and 2:1 electrolytes. Nevertheless, two fundamental differences should be noticed. First, the attraction between the silica surfaces is too large to be attributed solely to vdW force, hence implying an additional attraction mechanism or gross modification of the conventional vdW attraction. Second, neutralization of the silica surfaces occurs at trivalent cation concentrations that are 3 orders of magnitude smaller than those characterizing surface neutralization by mono- and divalent cations. Consequently, when trivalent cations are added to our cation adsorbability series the correlation with bare ion size breaks down abruptly. The strong adsorbability of trivalent cations to silica contrasts straightforward expectations based on ranking of the cationic solvation energies, thus suggesting a different adsorption mechanism which is inoperative or weak for mono- and divalent cations.     

Effect of borax additives on the rheological properties of sodium hyaluronate aqueous solutions

The rheological properties of sodium hyaluronate aqueous solutions are studied, and the effect of borax additives on them is investigated. It is shown that, at low concentrations, sodium hyaluronate behaves as a typical linear polyelectrolyte in the limit of a high concentration of the salt in both a 0.1 M NaCl aqueous solution and a salt-free solvent. The addition of 1 mole of borax per base-mole of the polymer to the solution of sodium hyaluronate significantly decreases the specific viscosity of the solution if no salt is added and has practically no effect on the viscosity of the solution in 0.1 M NaCl. The viscosity of a semidilute solution of sodium hyaluronate without the added salt decreases as the shear rate is increased in the range 1.5–656 s^?1. With an increase in temperature, viscosity decreases and its dependence on shear rate becomes less pronounced. The same effect is exerted by small amounts of borax. The properties of salt-free solutions are explained by the presence of admixtures of low-molecular-mass ions in them that screen the Coulomb repulsion of charges linked to sodium hyaluronate chains, and the effect of borax may be rationalized by the screening effect of ions resulting from the hydrolysis of borax.     

Rod-like polyelectrolyte adsorption onto charged surfaces in monovalent and divalent salt solutions

We analyze the adsorption of strongly charged polyelectrolytes onto weakly charged surfaces in divalent salt solutions. We include short-range attractions between the monomers and the surface and between condensed ions and monomers, as well correlations among the condensed ions. Our results are compared with the adsorption in monovalent salt solutions. Different surface charge densities (σ), and divalent (m) and monovalent (s) salt concentrations are considered. When the Wigner-Seitz cells diameter (2R) is larger than the length of the rod, the maximum amount of adsorption scales like n_max ∼ σ^4/3 in both monovalent and divalent solutions. For homogeneously charged surfaces, the maximum adsorption occurs at s* ∼ σ² when s* > ϕ, where ϕ is the monomer concentration, the counterpart for divalent salt solution, m* roughly scales as σ^2.2 when m* > ϕ. The effective surface charge density has a maximum absolute value at m′ < m*. A discrete surface charge distribution and short-range attractions between monomers and surface charge groups can greatly enhance surface charge inversion especially for high salt concentration. The critical salt concentration for adsorption in divalent salt solution roughly scales as m_c ∼ bσ^1.9, where b is the distance between two neighboring charged monomers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3642–3653, 2004     

Attraction between like-charged monovalent ions

Ions with like-charges repel each other with a magnitude given by the Coulomb law. The repulsion is also known to persist in aqueous solutions albeit factored by the medium's dielectric constant. In this paper, we report results from molecular dynamics simulations of alkali halides salt solutions indicating an effective attraction between some of the like-charged monovalent ions. The attraction is observed between anions, as well as between cations, leading to the formation of dimers with lifetimes on the order of few picoseconds. Two mechanisms have been identified to drive this counterintuitive attraction. The first is exhibited by high-charge density ions, such as fluoride, at low salt concentrations, yielding effective attractions with magnitude up to the order of 1-2 kT. In this case, the stronger local electric field generated when the two ions are in contact augments the alignment of neighboring waters toward the ions. This results in a gain of substantial favorable ion-water interaction energy. For fluorides, this interaction constitutes the major change among the different energy components compensating for the anion-anion repulsion, and therefore, rendering like-charge association possible. The second mechanism involves mediation by counterions, the attractions increase with salt concentration and are characterized by small magnitudes. In particular, clusters of ion triplets, in which a counterion is either bridging the two like-charged ions or is paired to only one of them, are formed. Although these two mechanisms may not yield net attractions in many cases, they might still be operational and significant, explaining effective repulsions between like-charged ions with magnitudes much smaller than expected based on continuum electrostatics.     

Ionic effects in collapse of polyelectrolyte brushes

We investigated the effect of counterion valence on the structure and swelling behavior of polyelectrolyte brushes using a nonlocal density functional theory that accounts for the excluded-volume effects of all ionic species and intrachain and electrostatic correlations. It was shown that charge correlation in the presence of multivalent counterions results in collapse of a polyelectrolyte brush at an intermediate polyion grafting density. At high grafting density, the brush reswells in a way similar to that in a monovalent ionic solution. In the presence of multivalent counterions, the nonmonotonic swelling of a polyelectrolyte brush in response to the increase of the grafting density can be attributed to a competition of the counterion-mediated electrostatic attraction between polyions with the excluded-volume effect of all ionic species. While a polyelectrolyte brush exhibits an "osmotic brush" regime at low salt concentration and a "salted brush" regime at high salt concentration regardless of the counterion valence, we found a smoother transition as the valence of the counterions increases. As observed in recent experiments, a quasi-power-law dependence of the brush thickness on the concentration ratio can be identified when the monovalent counterions are replaced with trivalent counterions at a fixed ionic strength.     

Protein interactions studied by SAXS: effect of ionic strength and protein concentration for BSA in aqueous solutions

We have studied a series of samples of bovine serum albumin (BSA) solutions with protein concentration, c, ranging from 2 to 500 mg/mL and ionic strength, I, from 0 to 2 M by small-angle X-ray scattering (SAXS). The scattering intensity distribution was compared to simulations using an oblate ellipsoid form factor with radii of 17 x 42 x 42 A, combined with either a screened Coulomb, repulsive structure factor, SSC(q), or an attractive square-well structure factor, SSW(q). At pH = 7, BSA is negatively charged. At low ionic strength, I < 0.3 M, the total interaction exhibits a decrease of the repulsive interaction when compared to the salt-free solution, as the net surface charge is screened, and the data can be fitted by assuming an ellipsoid form factor and screened Coulomb interaction. At moderate ionic strength (0.3-0.5 M), the interaction is rather weak, and a hard-sphere structure factor has been used to simulate the data with a higher volume fraction. Upon further increase of the ionic strength (I >or= 1.0 M), the overall interaction potential was dominated by an additional attractive potential, and the data could be successfully fitted by an ellipsoid form factor and a square-well potential model. The fit parameters, well depth and well width, indicate that the attractive potential caused by a high salt concentration is weak and long-ranged. Although the long-range, attractive potential dominated the protein interaction, no gelation or precipitation was observed in any of the samples. This is explained by the increase of a short-range, repulsive interaction between protein molecules by forming a hydration layer with increasing salt concentration. The competition between long-range, attractive and short-range, repulsive interactions accounted for the stability of concentrated BSA solution at high ionic strength.