Electrophoretic mobility of a cylindrical colloidal particle in a salt-free medium

Approximate expressions are derived for the electrophoretic mobility of dilute cylindrical colloidal particles in a salt-free medium containing only counterions. The cylinder is assumed to be infinitely long. It is shown that as in the case of a spherical particle, there is a certain critical value of the particle surface charge separating two cases. When the particle surface charge is lower than the critical value (case 1), the electrophoretic mobility increases with increasing particle surface charge per unit length. When the particle surface charge is higher than the critical value (case 2), the mobility becomes constant (for a cylinder in a transverse field) or the increase in the electrophoretic mobility with the particle surface charge becomes suppressed (for a cylinder in a tangential field). These phenomena are caused by the effect of counterion condensation in the vicinity of the particle surface. The critical value of the particle charge is essentially independent of the particle volume fraction phi for the dilute case, unlike the case of a sphere, in which case the critical charge value is proportional to ln(1/phi).     

Excluded volume driven counterion condensation inside nanotubes in a concave electrical double layer model

The physical properties of organic nanotubes attract increasing attention due to their potential benefit in technology, biology and medicine. We study the effect of ion size on the electrical properties of cylindrical nanotubes filled with electrolyte solution within a modified Poisson-Boltzmann (PB) approach. For comparison purposes, small hollow nanospheres filled with electrolyte solution are considered. The finite size of the particles in the inner electrolyte solution is described by the excluded volume effect within a lattice statistics approach. We found that an increased ion size reduces the number of counterions near the charged inner surface of the nanotube, leading to an enlarged electrostatic surface potential. The concentration of counterions close to the inner surface saturates for higher surface charge densities and larger ions. In the case of saturation, the closest counterion packing is achieved, all lattice sites near the surface are occupied and an actual counterion condensation is observed. By contrast, the counterion concentration at the axis of the nanotube steadily increases with increasing surface charge density. This growth is more pronounced for smaller nanotube radii and larger ions. At larger nanotube radii for small ion size counterion condensation may also be observed according to the Tsao criterion, i.e. the counterion concentration at the centre is independent of the number of counterions in the system. With decreasing radius the Tsao condensation effect is shifted towards physiologically unrealistic surface charge densities.     

Surface charge density/surface potential relationship for a spherical colloidal particle in a salt-free medium

On the basis of a theory of Imai and Oosawa (Busseiron Kenkyu52, 42 (1952); 59, 99 (1953)), approximate analytic expressions for the surface charge density/surface potential relationship for a spherical colloidal particle in a salt-free (aqueous or nonaqueous) medium containing only counterions are derived. There is a certain critical value of the surface charge density (or the total surface charge) separating two distinct cases: low surface charge density case and high surface charge density case. In the latter case counterion condensation occurs in the vicinity of the particle surface. The results are in excellent agreement with numerical calculations for the case of dilute suspensions.     

Monte Carlo simulation and molecular theory of tethered polyelectrolytes

We investigate the structure of end-tethered polyelectrolytes using Monte Carlo simulations and molecular theory. In the Monte Carlo calculations we explicitly take into account counterions and polymer configurations and calculate electrostatic interaction using Ewald summation. Rosenbluth biasing, distance biasing, and the use of a lattice are all used to speed up Monte Carlo calculation, enabling the efficient simulation of the polyelectrolyte layer. The molecular theory explicitly incorporates the chain conformations and the possibility of counterion condensation. Using both Monte Carlo simulation and theory, we examine the effect of grafting density, surface charge density, charge strength, and polymer chain length on the distribution of the polyelectrolyte monomers and counterions. For all grafting densities examined, a sharp decrease in brush height is observed in the strongly charged regime using both Monte Carlo simulation and theory. The decrease in layer thickness is due to counterion condensation within the layer. The height of the polymer layer increases slightly upon charging the grafting surface. The molecular theory describes the structure of the polyelectrolyte layer well in all the different regimes that we have studied.     

Electrophoresis of a spherical dispersion of polyelectrolytes in a salt-free solution

The electrophoretic behavior of a spherical dispersion of polyelectrolytes of arbitrary concentration is analyzed theoretically under a salt-free condition, that is, the liquid phase contains only counterions which come from the dissociation of the functional groups of polyelectrolytes. We show that, in general, the surface potential of a polyelectrolyte increases nonlinearly with its surface charge. A linear relation exists between them, however, when the latter is sufficiently small; and the more dilute the concentration of polyelectrolytes, the broader the range in which they are linearly correlated. If the amount of surface charge is sufficiently large, counterion condensation occurs, and the rate of increase of surface potential as the amount of surface charge increases declined. Also, it leads to an inverse in the perturbed potential near the surface of a polyelectrolyte, and its mobility decreases accordingly. For a fixed amount of surface charge, the lower the concentration of polyelectrolytes and/or the lower the valence of counterions, the higher the surface potential. The qualitative behavior of the mobility of a polyelectrolyte as the amount of its surface charge varies is similar to that of its surface charge.     

Counterion condensation and release in micellar solutions

Counterion condensation and release in micellar solutions are investigated by direct measurement of counterion concentration with ion-selective electrode. Monte Carlo simulations based on the cell model are also performed to analyze the experimental results. The degree of counterion condensation is indicated by the concentration ratio of counterions in the bulk to the total ionic surfactant added, alpha< or =1. The ionic surfactant is completely dissociated below the critical micelle concentration (cmc). However, as cmc is exceeded, the free counterion ratio alpha declines with increasing the surfactant concentration and approaches an asymptotic value owing to counterion condensation to the surface of the highly charged micelles. Micelle formation leads to much stronger electrostatic attraction between the counterion and the highly charged sphere in comparison to the attraction of single surfactant ion with its counterion. A simple model is developed to obtain the true degree of ionization, which agrees with our Monte Carlo results. Upon addition of neutral polymer or monovalent salts, some of the surfactant counterions are released to the bulk. The former is due to the decrease of the intrinsic charge (smaller aggregation number) and the degree of ionization is increased. The latter is attributed to competitive counterion condensation, which follows the Hefmeister series. This consequence indicates that the specific ion effect plays an important role next to the electrostatic attraction.     

Counterion condensation in hydrosols of single-crystalline detonation nanodiamond particles obtained by air annealing of their agglomerates

The pattern of previously recorded dependences of the specific surface charge and electrophoretic mobility of monodisperse detonation nanodiamond particles on pH of aqueous KCl solutions suggests that counterions are condensed on the particle surface. Counterion condensation is considered in terms of the Levin model, and the experimental ratios between the densities of the electrokinetic and surface charges of dispersed particles, as well as the fractions of condensed counterions, are calculated as depending on pH and KCl concentration in nanodiamond hydrosols. The obtained dependences lead to the conclusion that counterion condensation on the surface of detonation nanodiamond particles does indeed take place.     

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.     

Electrophoretic evidence for a new type of counterion condensation

A systematic capillary electrophoresis study uncovered how polyelectrolyte effective charge density varies with backbone charge spacing and solvent dielectric constant. The study primarily focused on aliphatic ionenes, a special class of polyelectrolytes, which possess regularly spaced quaternary ammonium groups in the backbone. Complete ionization of functional units and good solvency in water or mixtures of water with lower dielectric constant solvents (methanol, acetonitrile) enabled continuous measurements of ionene effective charge density through the onset of counterion condensation. Ionenes with both uniform and alternating charge spacing were examined. As expected, effective charge density rose linearly with fixed charge density to a critical value, above which effective charge density remained constant. Deviating from expectation, the onset of condensation did not occur at a critical fixed charge density. Instead, condensation initiated at a constant critical Bjerrum length. The same onset condition was found for quaternized poly(vinyl pyridine)s. These experimental results suggest a new form of condensation, one driven by ion-pairing of polyelectrolyte with counterions. In support of this hypothesis, the onset of condensation appeared to correlate with counterion size. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3616–3627, 2004     

Explicit ions condensation around strongly charged polyelectrolytes and spherical macroions: the influence of salt concentration and chain linear charge density. Monte Carlo simulations

The condensation of monovalent counterions and trivalent salt particles around strong rigid and flexible polyelectrolyte chains as well as spherical macroions is investigated by Monte Carlo simulations. The results are compared with the condensation theory proposed by Manning. Considering flexible polyelectrolyte chains, the presence of trivalent salt is found to play an important role by promoting chain collapse. The attraction of counterions and salt particles near the polyelectrolyte chains is found to be strongly dependent on the chain linear charge density with a more important condensation at high values. When trivalent salt is added in a solution containing monovalent salt, the trivalent cations progressively replace the monovalent counterions. Ion condensation around flexible chains is also found to be more efficient compared with rigid rods due to monomer rearrangement around counterions and salt cations. In the case of spherical macroions, it is found that a fraction of their bare charge is neutralized by counterions and salt cations. The decrease of the Debye length, and thus the increase of salt concentration, promotes the attraction of counterions and salt particles at the macroion surface. Excluded volume effects are also found to significantly influence the condensation process, which is found to be more important by decreasing the ion size.     

Electrophoretic mobility of a liquid drop in a salt-free medium

A theory is proposed for the electrophoretic mobility mu of dilute spherical liquid drops of radius a in salt-free media containing only counterions (e.g., nonaqueous media). As in the case of the electrophoretic mobility of rigid particle in salt-free media, there is a certain critical value of the drop surface charge separating two cases, that is, the low-surface-charge case and the high-surface-charge case. For the low-surface-charge case, mu coincides with that of a drop in an electrolyte solution in the limit of very low electrolyte concentrations kappaa-->0 (Hückel's limit), where kappa is the Debye-Hückel parameter. For the high-surface-charge case, however, mu becomes constant independent of the drop surface charge, since the counterion condensation takes place near the drop surface.     

Transport properties of some cationic polysaccharides 2. Charge density effect

The charge density effect on the behavior of some cationic polysaccharides in aqueous and nonaqueous (methanol) solutions was studied by viscometric and conductometric measurements. The polyelectrolytes investigated contain quaternary ammonium salt groups, N-alkyl-N,N-dimethyl-2-hydroxypropylene ammonium chloride, attached to a dextran backbone. This new class of polyelectrolytes has various linear charge density parameters, xi, located below and above the critical threshold value of counterions condensation, xi(c)=1(xi=0.25-3.18). The viscometric data revealed that all copolymers exhibit a polyelectrolyte behavior and were plotted in the terms of Rao equation. The conductometric measurements of solutions of these copolymers were presented as a function of polymer concentration and charge density. The results were analyzed within the Manning's theory and lower experimental values of the equivalent conductivity than the theoretical ones were found. Possible reasons of this discrepancy have been discussed. The interaction parameters were evaluated and these were found to depend on both the polymer concentration and the charge density. The conductometric behavior of these cationic polysaccharides has shown that counterion condensation is not a threshold phenomenon, their association to the charged groups of the polyions taking place for xi>1 as well as xi<1.     

Overcharging of nanoparticles in electrolyte solutions

Monte Carlo simulations are performed to investigate the effects of salt concentration, valence and size of small ions, surface charge density, and Bjerrum length on the overcharging of isolated spherical nanoparticles within the framework of a primitive model. It is found that charge inversion is most probable in solutions containing multivalent counterions at high salt concentrations. The maximum strength of overcharging occurs near the nanoparticle surface where counterions and coions have identical local concentrations. The simulation results also suggest that both counterion size and electrostatic correlations play major roles for the occurrence of overcharging.     

利用荧光非辐射能量转移观察磺酸基聚电解质分子链形态

2-丙烯酰胺基-2-甲基丙磺酸(AMPS)与N,N-二甲基丙烯酰胺(DMAA)共聚合成了一系列电荷密度为5%～99%的强聚电解质,并分别用萘和芘标记.随试样电荷密度升高,用分子间非辐射能量转移(NRET)测定的聚电解质接触质量浓度ρ^*从0.55减小到0.25g/L,比激基缔合物荧光测定的ρ^*约小一个数量级.在稀溶液范畴内,随试样电荷密度增加,分子链间的NRET先减弱,至AMPS质量分数达30%后又增强.该现象可用Manning的反离子凝聚与聚电解质聚集理论予以定性说明.     

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.     

Thermodynamic characterization of rare Earth salts of strong polyacid copolymers

Stoichiometric La3+, Ce3+, and Nd3+ salts of poly[(vinyl alcohol)-co-(vinyl sulfate)] (PVAS) copolymer polyacids have been studied in aqueous solution without added salt. All LnPVAS salts were entirely water-soluble in the composition and concentration range investigated. Ratios of the vinyl sulfate and vinyl alcohol units in the copolymers were between 1:5 and 1:107, leading to structural charge densities both above and under the critical value needed for counterion condensation of trivalent counterions. Solvent activity, a1, has been measured by the gel deswelling method in the concentration range of 5 x 10(-4) to 1 x 10(-1) mol of counterion/kg of water (0.2-9 w/w% of the polyelectrolyte). Results are unusually high for polyelectrolytes (-2 x 10(-6) > ln a1 > -3 x 10(-4)), and they are comparable with values determined in solutions of uncharged polymers. Nevertheless, the different copolymers can be clearly distinguished; the water activity is lowered in the order of the vinyl sulfate content of the polyelectrolytes, except for the one above the critical charge density. No observable difference was caused in the thermodynamic properties by the different lanthanide counterions. Reduced osmotic pressure curves and Flory-Huggins pair interaction parameters have been calculated; both of them were used to estimate degrees of dissociation at zero as well as at finite concentrations. Degrees of dissociation are decreasing with increasing concentration or vinyl sulfate content of the copolymer. They take values between 8-36% at zero polymer concentration and they reach zero value simultaneously at approximately 1 x 10(-3) mol of polymer chains/kg of water. The average number of released counterions per polymer chain (DPn = 1005) approaches to a limit of about 4.4 with increasing vinyl sulfate content. This corresponds to average charge distances of b > or = 19 nm and charge density parameters of xi < or = 0.037. The latter is, however, a very low value and indicates a 1/9 contraction compared to the rod-like assumption.     

Varying the counterions at a charged interface

The influence of different counterions on the adsorption behavior of the ionic soluble surfactant dodecyl-dimethylammonium-pyridimium bromide is investigated. The addition of potassium halogenides to aqueous solutions of the surfactant modifies the surface activity of the amphiphile and has a profound influence on the surface tension isotherms. The measured critical micelle concentration follows the order of the periodic table of elements which is in strong contrast to the surface excess. The number density of the adsorbed surfactants at the cmc does not depend on the amount of counterions in the solution but on the nature of the counterion. Furthermore, evidence is provided that the surface region is depleted on fluoride ions. Surface second harmonic generation and ellipsometry have been used to gain direct structural information which complement the thermodynamic considerations. The combination of both optical techniques yields the number density of the condensed counterions within the compact layer. A strategy to retrieve selected parameters of the ion binding model of Radke et al. is presented. The analysis of the optical data reveal the existence of a phase transition towards a surface condensed state with increasing salt condensation.     

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.     

Electric polarizability of DNA in aqueous salt solution

Monte Carlo simulations are performed to determine the anisotropy of the electric polarizability of a model DNA fragment in aqueous salt solution. By taking into consideration the participation of coions in the electroneutrality condition, at every simulation step, we obtain a list of counterions constituting the net charge arranged in increasing order of their distance from the DNA and calculate the contribution to the dipole moment from the first n counterions in the list. We define a partial polarizability tensor due to these n counterions to understand the origin of the polarizability in close relation to the solution structure. The ionic distributions are described by the counterion condensation theory. Characteristic features of the electric properties of polyelectrolytes are reproduced. The anisotropy of the electric polarizability Deltaalpha of DNA decreases with the addition of salt, yielding values comparable to experiment. The effect of electrophoretic motion of the polyion is examined by estimating its upper limit.     

Electroosmotic velocity in an array of parallel soft cylinders in a salt-free medium

A theory of electroosmosis in an array of parallel soft cylinders (i.e. polyelectrolyte-coated cylinders) in a salt-free medium is presented. It is shown that there is a certain critical value of the particle charge and that if the particle charge is greater than the critical value, then the electroosmotic velocity becomes constant independent of the particle charge due to the counterion condensation effects, as in the case of other electrokinetic phenomena in salt-free media.