Ettringite surface chemistry: Interplay of electrostatic and ion specificity

This paper presents a detailed experimental study combined with Monte Carlo (MC) simulations within the primitive model of the physical chemistry at the ettringite-water interface over a wide range of pH and bulk conditions for which ettringite exists thanks to its solubility in aqueous solutions. Ettringite, which is an important phase in hydrated cement-based systems, bears a permanent and positive structural charge. In contrast with previous studies, electrokinetic measurements together with the careful chemical analysis of the equilibrium solutions of the dispersions have brought strong support to designate sulfate as being the ion determining the potential. Simulations showed that electrostatics, through ion-ion correlations, are not strong enough to explain the charge reversal of ettringite immersed in sulfate salt solutions. However, an excellent agreement between simulated and experimental data was obtained including a short-range nonelectrostatic adsorption potential for the sulfate ion. This result strongly suggests the existence of a chemical specificity of sulfate ions for an ettringite surface.     

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).     

Determination of the Structure and Effective Dielectric Constant of Hydrated Ions

Abstract

Debye's equation for the salting in or out of nonpolar compounds, such as benzene, in aqueous salt solutions was expanded so as to determine the effective dielectric decrement and constant of the hydrated domain of an ion. For ions having an electrostatic charge per surface area less than or equal to that of the K⁺ or Cl^? ions, this domain consists of a single layer of water molecules loosely or negatively hydrated to the ion; i.e., the domain consists of a mono-molecular B region. For ions having an electrostatic charge per unit surface area approximately equal to that of the Na⁺ and F^? ions, there exists no B region and only one layer of tightly bound or positively hydrated water (a monomolecular A region). Since the electrostatic field does not appreciably influence water molecules beyond this A region, such ions have an effective dielectric constant that is near zero, as in relatively inert molecules such as hydrocarbons. For all other ions, such as H⁺, Li⁺, Mg²⁺⁰,Cr²⁺, Sr²⁺, Ba²⁺, and other multivalent ions, there exists only one monomolecular A region followed by one monomolecular B region. The effective value of the dielectric constant of such an ion is obtained from its B region, since its A region cannot be penetrated. The effective dielectric decrement or constant of any B region as measured by benzene solubility goes through a maximum as the electrostatic charge per unit surface area (C/A) is decreased because a large C/A restricts the orientation of the hydrated water molecules and a low value of C/A allows competitive interaction between surrounding water molecules. Thus both small and large values of C/A decrease the solubility of benzene, i.e., decrease i t s ability to penetrate into the medium. A decrease in the macroscopic dielectric constant of water upon the addition of salt is due to the destruction of the clusters of water by the ions, or to the addition of ions which have effective dielectric constants less than that of water, or both. All hydrated ions o r molecules which salt-in or salt -out benzene have, respectfully, effective dielectric constants greater or less than that of water.     

Hofmeister effects: interplay of hydration, nonelectrostatic potentials, and ion size

The classical Derjaguin-Landau-Verwey-Overbeek (DLVO) theory of colloids, and corresponding theories of electrolytes, are unable to explain ion specific forces between colloidal particles quantitatively. The same is true generally, for surfactant aggregates, lipids, proteins, for zeta and membrane potentials and in adsorption phenomena. Even with fitting parameters the theory is not predictive. The classical theories of interactions begin with continuum solvent electrostatic (double layer) forces. Extensions to include surface hydration are taken care of with concepts like inner and outer Helmholtz planes, and "dressed" ion sizes. The opposing quantum mechanical attractive forces (variously termed van der Waals, Hamaker, Lifshitz, dispersion, nonelectrostatic forces) are treated separately from electrostatic forces. The ansatz that separates electrostatic and quantum forces can be shown to be thermodynamically inconsistent. Hofmeister or specific ion effects usually show up above ≈10(-2) molar salt. Parameters to accommodate these in terms of hydration and ion size had to be invoked, specific to each case. Ionic dispersion forces, between ions and solvent, for ion-ion and ion-surface interactions are not explicit in classical theories that use "effective" potentials. It can be shown that the missing ionic quantum fluctuation forces have a large role to play in specific ion effects, and in hydration. In a consistent predictive theory they have to be included at the same level as the nonlinear electrostatic forces that form the skeletal framework of standard theory. This poses a challenge. The challenges go further than academic theory and have implications for the interpretation and meaning of concepts like pH, buffers and membrane potentials, and for their experimental interpretation. In this article we overview recent quantitative developments in our evolving understanding of the theoretical origins of specific ion, or Hofmeister effects. These are demonstrated through an analysis that incorporates nonelectrostatic ion-surface and ion-ion dispersion interactions. This is based on ab initio ionic polarisabilities, and finite ion sizes quantified through recent ab initio work. We underline the central role of ionic polarisabilities and of ion size in the nonelectrostatic interactions that involve ions, solvent molecules and interfaces. Examples of mechanisms through which they operate are discussed in detail. An ab initio hydration model that accounts for polarisabilities of the tightly held hydration shell of "cosmotropic" ions is introduced. It is shown how Hofmeister effects depend on an interplay between specific surface chemistry, surface charge density, pH, buffer, and counterion with polarisabilities and ion size. We also discuss how the most recent theories on surface hydration combined with hydrated nonelectrostatic potentials may predict experimental zeta potentials and hydration forces.     

Possible origin of the inverse and direct Hofmeister series for lysozyme at low and high salt concentrations

Protein solubility studies below the isoelectric point exhibit a direct Hofmeister series at high salt concentrations and an inverse Hofmeister series at low salt concentrations. The efficiencies of different anions measured by salt concentrations needed to effect precipitation at fixed cations are the usual Hofmeister series (Cl(-) > NO(3)(-) > Br(-) > ClO(4)(-) > I(-) > SCN(-)). The sequence is reversed at low concentrations. This has been known for over a century. Reversal of the Hofmeister series is not peculiar to proteins. Its origin poses a key test for any theoretical model. Such specific ion effects in the cloud points of lysozyme suspensions have recently been revisited. Here, a model for lysozymes is considered that takes into account forces acting on ions that are missing from classical theory. It is shown that both direct and reverse Hofmeister effects can be predicted quantitatively. The attractive/repulsive force between two protein molecules was calculated. To do this, a modification of Poisson-Boltzmann theory is used that accounts for the effects of ion polarizabilities and ion sizes obtained from ab initio calculations. At low salt concentrations, the adsorption of the more polarizable anions is enhanced by ion-surface dispersion interactions. The increased adsorption screens the protein surface charge, thus reducing the surface forces to give an inverse Hofmeister series. At high concentrations, enhanced adsorption of the more polarizable counterions (anions) leads to an effective reversal in surface charge. Consequently, an increase in co-ion (cations) adsorption occurs, resulting in an increase in surface forces. It will be demonstrated that among the different contributions determining the predicted specific ion effect the entropic term due to anions is the main responsible for the Hofmeister sequence at low salt concentrations. Conversely, the entropic term due to cations determines the Hofmeister sequence at high salt concentrations. This behavior is a remarkable example of the charge-reversal phenomenon.     

Ion-ion proton transfer reactions of bio-ions involving noncovalent interactions: Holomyoglobin

Multiply protonated horse skeletal muscle holomyoglobin and apomyoglobin have been subjected to ion-ion proton transfer reactions with anions derived from perfluoro-1,3-dimethylcyclohexane in a quadrupole ion trap operated with helium as a bath gas at 1 mtorr. Neither the apomyoglobin nor holomyoglobin ions show any sign of fragmentation associated with charge state reduction to the 1 + charge state. This is particularly noteworthy for the holomyoglobin ions, which retain the noncovalently bound heme group. For example, no sign of heme loss is associated with charge state reduction from the 9 + charge state of holomyoglobin to the 1 + charge state despite the eight consecutive highly exothermic proton transfer reactions required to bring about this charge change. This result is consistent with calculations that show the combination of long ion lifetime and the high ion-helium collision rate relative to the ion-ion collision rate makes fragmentation unlikely for high mass ions in the ion trap environment even for noncovalently bound complexes of moderate binding strength. The ion-ion proton transfer rates for holo- and apomyoglobin ions of the same charge state also were observed to be indistinguishable, which supports the expectation that ion-ion proton transfer rates are insensitive to ion structure and are determined primarily by the attractive Coulomb field.     

Corrected Debye-Hückel analysis of surface complexation; III. Spherical particle charging including ion condensation

Statistical mechanics has been used to derive a model for the charging of a spherical particle in a salt solution to complement our experimental studies and gain a deeper understanding of the processes involved in surface complexation. Our chosen model goes beyond the equilibrium constants and the Gouy-Chapmann theory currently used in surface complexation models. The proton adsorption is taken to occur at a harmonic potential well on the surface characterized by a frequency v and a well depth u(0). Outside the particle surface there is a capacitor layer of width w(c) which is impenetrable to the salt ions. The diffuse screening of the charged particle is described by a corrected Debye-Hückel analysis accounting for ion size in the ion-ion interactions. To account also for nonlinear electrostatic response a layer of condensed counterions has been introduced. The criterion for the onset of ion condensation is that the electrostatic field exceeds a linear response criterion. Ion size effects are accounted for in terms of hole-corrected electrostatic energies and excluded volume. The model has been applied to titrated surface charge data on goethite (alpha-FeOOH) at various background concentrations and good agreement between the experimental data and the model was obtained. Both the size of the screening ions and the central particle size were shown to be of importance for the surface charge.     

Entropic effects in the electric double layer of model colloids with size-asymmetric monovalent ions

The structure of the electric double layer of charged nanoparticles and colloids in monovalent salts is crucial to determine their thermodynamics, solubility, and polyion adsorption. In this work, we explore the double layer structure and the possibility of charge reversal in relation to the size of both counterions and coions. We examine systems with various size-ratios between counterions and coions (ion size asymmetries) as well as different total ion volume fractions. Using Monte Carlo simulations and integral equations of a primitive-model electric double layer, we determine the highest charge neutralization and electrostatic screening near the electrified surface. Specifically, for two binary monovalent electrolytes with the same counterion properties but differing only in the coion's size surrounding a charged nanoparticle, the one with largest coion size is found to have the largest charge neutralization and screening. That is, in size-asymmetric double layers with a given counterion's size the excluded volume of the coions dictates the adsorption of the ionic charge close to the colloidal surface for monovalent salts. Furthermore, we demonstrate that charge reversal can occur at low surface charge densities, given a large enough total ion concentration, for systems of monovalent salts in a wide range of ion size asymmetries. In addition, we find a non-monotonic behavior for the corresponding maximum charge reversal, as a function of the colloidal bare charge. We also find that the reversal effect disappears for binary salts with large-size counterions and small-size coions at high surface charge densities. Lastly, we observe a good agreement between results from both Monte Carlo simulations and the integral equation theory across different colloidal charge densities and 1:1-electrolytes with different ion sizes.     

Computer Simulation of Cation-Exchange Membrane Structure: An Elementary Act of Hydrated Ion Transport

A fragment of the structure of a sulfo cation exchanger, which is the basis of most cation-exchange membranes, is calculated by an ab initio method. An analysis of interatomic bonds in the structure shows that, to detach a mobile ion from a fixed ion, it is necessary to break the hydrogen bond between hydration water molecules of the counterion in addition to overcoming the electrostatic attraction. As the hydrogen bond cleavage work for simple hydrated ions is ten times the electrostatic attraction energy, an elementary act of ion transport in a cation-exchange membrane is considered mostly as the hydrogen bond transfer reaction.     

Counterion volume effects in mixed electrical double layers

When a monolayer of negatively charged surfactant molecules is brought in contact with an aqueous solution containing mixtures of counterions of different size and valency, very large deviations from Poisson-Boltzmann theory (PBT) develop at a high surface charge, with the smaller counterion outcompeting the larger one (even if divalent) near the interface, leading to counterion segregation [V.L. Shapovalov, G. Brezesinski, J. Phys. Chem. B 110 (2006) 10032]. We use a modified PBT that empirically includes an extended Carnahan-Starling equation-of-state to describe hard-sphere interactions in electrical double layers containing ions of different size and charge. Model calculations are made for ion concentration profiles, free energies, surface pressures, and differential capacities. At high surface charge, volume interactions become important, leading to significant deviations from PBT. In contrast to PBT, at high surface charge, contributions to energy and pressure are no longer mainly entropic, but instead volume and electrostatic field effects now dominate. When the hydrated size of the divalent ion is used as an adjustable parameter, the theory is in good agreement with the experimental data.     

Effects of multivalent salt addition on effective charge of dilute colloidal solutions

The effective charge Z* is often invoked to account for the accumulation of counterions near the colloid with intrinsic charge Z. Although the ion concentrations c(i) are not uniform in the solution due to the presence of the charged particle, their chemical potentials are uniform everywhere. Thus, on the basis of ion chemical potential, effective ion concentrations c(i)*, which can be experimentally measured by potentiometry, are defined with the pure salt solution as the reference state. The effective charge associated with the charged particle can then be determined by the global electroneutrality condition. Monte Carlo simulations are performed in a spherical Wigner-Seitz cell to obtain the effective charge of the colloid. In terms of the charge ratio alpha=Z*/Z, the effects of added salt concentration, counterion valency, and particle charge are examined. The effective charge declines with increasing salt concentration and the multivalent salt is much more efficient in reducing the effective charge of the colloidal solution. Moreover, the extent of effective charge reduction is decreased with increasing intrinsic charge for a given concentration of added salt. Those results are qualitatively consistent with experimental observations by electrophoresis.     

Binding of acetylcholine and tetramethylammonium to a cyclophane receptor: anion's contribution to the cation-pi interaction

The interaction of the lipophilic cyclophane 1 with several acetylcholine (ACh) and tetramethylammonium (TMA) salts has been investigated in deuteriochloroform to ascertain the influence of the counterion on the cation-pi interaction. Reliable association constants have been measured for 17 salts of commonly used anions; corresponding binding free energies -DeltaG degrees ranged from over 8 kJ mol(-1) down to the limit of detection. The dramatic dependence of the binding energy on the anion showed that the latter takes part in the process with a passive and adverse contribution, which inhibits cation binding even to complete suppression in unfavorable cases. Thermodynamic parameters for the association of 1 with TMA picrate demonstrate that binding is enthalpic in origin, showing a substantial enthalpy gain (DeltaH degrees = -16.7 kJ mol(-1)) and an adverse entropic contribution (DeltaS degrees = -27.9 J mol(-1) K(-1)). A correlation has been found between the "goodness" of anions as binding partners and the solubility of their salts. Conversion of the anion into a more charge-dispersed species, for example, conversion of chloride into dialkyltrichlorostannate, improves cation binding substantially, indicating that charge dispersion is a main factor determining the influence of the anion on the cation-pi interaction. DFT computational studies show that the variation of the binding free energy of TMA with the counterion is closely accounted for by the electrostatic potential (EP) of the ion pair: guest binding appears to respond to the cation's charge density exposed to the receptor, which is determined by the anion's charge density through a polarization mechanism. A value of -DeltaG degrees = 38.6 kJ mol(-1) has been extrapolated for the free energy of binding of TMA to 1 in chloroform but in the absence of a counterion. The transmission of electrostatic effects from the ion pair to the cation-pi interaction demonstrates that host-guest association is governed by Coulombic attraction, as long as factors (steric, entropic, solvation, etc.) other than pure electrostatics are not prevalent.     

Explanation of Ionic Sequences in Various Phenomena. III. Salting-in and -out of Amino Acids

Abstract

Previous developed theories were applied in explaining the mechanism for the salting-in and -out of various amino acids. Glycine is salted-in according to the cationic sequences Li⁺ > Na⁺ > K⁺ > Rb⁺ and Ca²⁺ > Ba²⁺ > Sr²⁺. The ability of a cation to increase the solubility of an amino acid therefore corresponds to the destruction of the ion-ion bond between the - CO-₂and the -NH_{+ 2}group of the amino acid by forming an insoluble ion-ion bond between the added cation and the - CO?² group. This insolubilizing effect produces a positive charge on the amino acid. If, however, the anion of the added salt forms a relatively insoluble ion-ion bond with the -NH₊₂ group of the amino acid, then the effect is minimized because now both charges on the amino acid are reduced. Consequently, the more insoluble the cation amino acid salt and the more soluble the anion amino acid salt (or vice versa), the greater will be the salting-in effect. Titration of either charged group on the amino acid zwitterion has the same effect, since now the ion-ion bond of the amino acid is again destroyed. Aliphatic and carboxylic acid groups also effect the salting-in sequence, since these groups are salted-out by addition of salt when D^± < D_H2o. These mechanisms explain how leucine is first salted-out, then salted-in (at 4 M) and finally salted-out again (at 9 M) in LiCl solutions. Urea salts-in hydrophobic amino acids by increasing the dielectric constant and salts-out polar amino acids by increasing the interaction between the two charge groups on the amino acid. Glycine reverses the salting-in effect of NaCl on asparagine by competing for the Na⁺ ion.     

Entropy and enthalpy of polyelectrolyte complexation: Langevin dynamics simulations

We report a systematic study by Langevin dynamics simulation on the energetics of complexation between two oppositely charged polyelectrolytes of same charge density in dilute solutions of a good solvent with counterions and salt ions explicitly included. The enthalpy of polyelectrolyte complexation is quantified by comparisons of the Coulomb energy before and after complexation. The entropy of polyelectrolyte complexation is determined directly from simulations and compared with that from a mean-field lattice model explicitly accounting for counterion adsorption. At weak Coulomb interaction strengths, e.g., in solvents of high dielectric constant or with weakly charged polyelectrolytes, complexation is driven by a negative enthalpy due to electrostatic attraction between two oppositely charged chains, with counterion release entropy playing only a subsidiary role. In the strong interaction regime, complexation is driven by a large counterion release entropy and opposed by a positive enthalpy change. The addition of salt reduces the enthalpy of polyelectrolyte complexation by screening electrostatic interaction at all Coulomb interaction strengths. The counterion release entropy also decreases in the presence of salt, but the reduction only becomes significant at higher Coulomb interaction strengths. More significantly, in the range of Coulomb interaction strengths appropriate for highly charged polymers in aqueous solutions, complexation enthalpy depends weakly on salt concentration and counterion release entropy exhibits a large variation as a function of salt concentration. Our study quantitatively establishes that polyelectrolyte complexation in highly charged Coulomb systems is of entropic origin.     

Thermodynamic linkage of ion binding and hydration in myofibrillar protein solutions determined from multinuclear spin relaxation studies

The mechanisms for the anionic and cationic interactions with myofibrillar proteins in aqueous solutions were investigated by nuclear magnetic resonance over a wide range of salt concentration. Markedly nonlinear dependeces of the ¹⁷O and ²³Na NMR transverse relaxation rates on salt concentration were analyzed with a thermodynamic linkage model of salt-dependent solubility and hydration (ligand-induced association model), according to Wyman's theory of linked functions. Nonlinear regression analysis of both ¹⁷O and ²³Na NMR data suggested cooperative, reversible binding of hydrated ions to myofibrillar proteins. Both ions and water were found to exchange fast, on the NMR timescale, between the binding sites of the myofibrillar proteins and the aqueous solution. At sodium chloride concentrations higher than about 0.1 grams salt/gram water, ion activities have marked effects upon the NMR relaxation rates of both ions and water. A salt activity model allowed quantitative fitting of the NMR data at high salt concentrations. The effect of neglecting the ion activity in solutions of myofibrillar proteins was also estimated and compared with the ligand-induced, cooperative association model for myofibrillar proteins. The comparison between the ¹⁷O and ²³Na results strongly suggests that water is exchanged as the hydrated ion species between the myofibrillar protein binding sites and the bulk, aqueous solution.     

Aqueous suspensions of charged spherical colloids: dependence of the surface charge on ionic strength, acidity, and colloid concentration

We theoretically investigate the dependence of the surface charge developed on charged spherical colloids upon several environmental parameters: the ionic strength of the monovalent added electrolyte, acidity (stabilized by a pH buffer solution), and colloid concentration. In the framework of the mean-field Poisson-Boltzmann spherical cell model, we include the charged colloid-microion correlations into the buffer equation, and we allow for the specific binding of ions to the ionizable groups on the colloid surface. Theoretical predictions are compared to the results obtained under the planar-symmetry Gouy-Chapman approximation and analyzed for the experimental conditions of an aqueous dispersion of the phospholipid dimyristoyl phosphatidylglycerol (DMPG). Experimental measurements of the partition ratio of an aqueous soluble cationic spin label on buffered dispersions of polyanionic unilamellar vesicles of DMPG in the presence of added monovalent salt are theoretically interpreted in terms of ion partition due to electrostatic interactions. We show that the specific binding of the probe must be admitted to explain the experimental results.     

Experimental study of electrostatically stabilized colloidal particles: colloidal stability and charge reversal

We consider the interaction of colloidal spheres in the presence of mono-, di-, and trivalent ions. The colloids are stabilized by electrostatic repulsion due to surface charges. The repulsive part of the interaction potential Ψ(d) is deduced from precise measurements of the rate of slow coagulation. These "microsurface potential measurements" allow us to determine a weak repulsion in which Ψ(d) is of the order of a few k(B)T. These data are compared to ζ potential measured under similar conditions. At higher concentrations both di- and trivalent counterions accumulate at the very proximity of the particle surface leading to charge reversal. The salt concentration c(cr) at which charge reversal occurs is found to be always above the critical coagulation concentration c(ccc). The analysis of Ψ(d) and of the ζ potential demonstrates, however, that adsorption of multivalent counterions starts far below c(cr). Hence, colloid stability in the presence of di- and trivalent ions cannot be described in terms of a DLVO ansatz assuming a surface charge that is constant with regard to the ionic strength.     

Structural study of the solutions of acidic polysaccharides

A study was made of the effect of NaCl on the counterion activity coefficient in solutions of acidic polysaccharide sodium salts. The counterion activity coefficient in the sodium salt solutions of polyuronic acids was shown to be determined by electrostatic interactions only. Consequently it can be supposed that the counterion-polyion interaction is also of an electrostatic nature. A method was proposed for determining the distribution patterns of nonionogenic groups along the polyelectrolyte chain. The structural transition ofχ-carrageenan, depending on NaCl concentration, was found to be accompanied by a nonelectrostatic binding of sodium ions by the polysaccharide.     

Electrostatic correlations and fluctuations for ion binding to a finite length polyelectrolyte

A statistical mechanical model is presented which explicitly accounts for the fluctuations, the electrostatic, and the excluded volume correlations for ions bound to a polyelectrolyte such as DNA. The method can be employed to treat a wide range of ionic conditions including multivalent ions. The microscopic framework of the theory permits the use of realistic finite length and grooved structural model for the polyelectrolyte and modeling of the finite size of the bound ions. Test against Monte Carlo simulations suggests that the theory can give accurate predictions for the ion distribution and the thermodynamic properties. For multivalent ions, the theory makes improved predictions as compared with the mean-field approach. Moreover, for long polyelectrolyte and dilute salt concentration, the theory predicts ion binding properties that agree with the counterion condensation theory.