Monovalent Counterions Research Articles

Reentrant Variation of Single-Chain Elasticity of Polyelectrolyte Induced by Monovalent Salt.

The interactions between monovalent counterions and polyelectrolyte are important in chemical and biological systems. The condensation and screening effect of counterions complicate the polyelectrolyte solutions. By means of single-molecule AFM, the single-chain mechanics of a strong polyelectrolyte, poly(sodium styrenesulfonate) (PSSNa), in KCl aqueous solutions over almost whole concentration range have been studied. The M-FJC model has been used to describe the single-chain elasticity of PSSNa in KCl solutions with a parameter of single-chain modulus (K0). Along with the increase of the concentration of KCl from zero to almost the saturation concentration, a reentrant variation of K0 of single PSSNa chain can be observed. When [K+] is between 0.01 to 3 M, the charges on the PSSNa backbone are almost completely screened, i.e., the PSSNa chain is virtually neutral in this case. Because K0 has a positive correlation with the net charge of the polymer chain, the increased K0 at very high KCl concentrations (≥3.5 M) indicates that the chain is charged again. Due to the negative charges on the backbone of PSSNa, only the positively charged counterions (K+) can be adsorbed on the chain. Thus, the PSSNa chain should be positively charged when KCl concentrations ≥3.5 M. That is, the charge inversion occurs in this case, which is induced by a monovalent salt. This finding may lay the foundation for the future applications of drug delivery and gene therapy.

Temperature Response of Charged Colloidal Particles by Mixing Counterions Utilizing Ca2+/Na+ Montmorillonite as Model System

The osmotic pressure and the aggregation of charged colloids as a function of temperature have been investigated using Monte Carlo and molecular dynamics simulations for different ratios of monovalent and divalent counterions. In the simulations the water is treated as a temperature-dependent dielectric continuum, and only the electrostatic interactions are considered. It was found that the temperature response can be controlled, i.e., the osmotic pressure can increase, decrease, or be kept constant, as a function of temperature depending on the monovalent/divalent counterion ratio. The increase in osmotic pressure with temperature, which occurs at low enough surface charge density and/or low fraction of divalent ions, can be understood from the DLVO theory. The origin of the opposite behavior can be explained by the enhanced attractive electrostatic ion–ion correlation interactions with temperature. The constraint is that the absolute value of the surface charge density of the colloids must be above a certain threshold, i.e., high enough such that the attractive ion–ion correlations can dominate the interaction regarding the divalent ions. The current conclusions are supported by the microstructural characterization of Ca2+/Na+-montmorillonite clay using small-angle X-ray scattering. A qualitative agreement is observed between the simulations and the experimental data.

Ionic tethering contributes to the conformational stability and function of complement C3b.

C3b, the central component of the alternative pathway (AP) of the complement system, coexists as a mixture of conformations in solution. These conformational changes can affect interactions with other proteins and complement regulators. Here we combine a computational model for electrostatic interactions within C3b with molecular imaging to study the conformation of C3b. The computational analysis shows that the TED domain in C3b is tethered ionically to the macroglobulin (MG) ring. Monovalent counterion concentration affects the magnitude of electrostatic forces anchoring the TED domain to the rest of the C3b molecule in a thermodynamic model. This is confirmed by observing NaCl concentration dependent conformational changes using single molecule electron microscopy (EM). We show that the displacement of the TED domain is compatible with C3b binding to Factor B (FB), suggesting that the regulation of the C3bBb convertase could be affected by conditions that promote movement in the TED domain. Our molecular model also predicts mutations that could alter the positioning of the TED domain, including the common R102G polymorphism, a risk variant for developing age-related macular degeneration. The common C3b isoform, C3bS, and the risk isoform, C3bF, show distinct energetic barriers to displacement in the TED that are related to a network of electrostatic interactions at the interface of the TED and MG-ring domains of C3b. These computational predictions agree with experimental evidence that shows differences in conformation observed in C3b isoforms purified from homozygous donors. Altogether, we reveal an ionic, reversible attachment of the TED domain to the MG ring that may influence complement regulation in some mutations and polymorphisms of C3b.

Morphologies of spherical polyampholyte brushes: Effects of counterion valence and charged monomer sequence

We study the conformational behavior of spherical brushes composed of polyampholyte chains end-grafted onto spherical particles in the presence of monovalent and tetravalent counterions using molecular dynamics simulations. The overall net charge for each chain consisting of both positively and negatively charged segments is zero. The dependences of the structural properties of the brushes on the chain stiffness, grafting density and charge sequence along the chains are examined systemically. For the diblock brushes, our results indicate that increasing the chain rigidity leads to a significant effect of counterion valence and a reduced collapsing degree of the brushes. At high chain stiffness, the number of high-valent counterions trapped in the brushes is diminished compared to the cases with monovalent counterions, corresponding to lower osmotic pressure. For the flexible brushes, the short-range and electrostatic interactions depending on the charge sequence, determine the conformational transition of the brushes, whereas the effect of counterion valence becomes weaker. In the presence of high-valent counterions, the brushes which consist of polyampholyte chains with blocks of medium length, adopt a slightly stretched conformation owing to relatively strong electrostatic correlation between high-valent counterions and oppositely charged monomers.

Competition between excluded-volume and electrostatic interactions for nanogel swelling: effects of the counterion valence and nanogel charge.

In this work the equilibrium distribution of ions around a thermo-responsive charged nanogel particle in an electrolyte aqueous suspension is explored using coarse-grained Monte Carlo computer simulations and the Ornstein-Zernike integral equation theory. We explicitly consider the ionic size in both methods and study the interplay between electrostatic and excluded-volume effects for swollen and shrunken nanogels, monovalent and trivalent counterions, and for two different nanogel charges. We find good quantitative agreement between the ionic density profiles obtained using both methods when the excluded repulsive force exerted by the cross-linked polymer network is taken into account. For the shrunken conformation, the electrostatic repulsion between the charged groups provokes a heterogeneous polymer density profile, leading to a nanogel structure with an internal low density hole surrounded by a dense corona. The results show that the excluded-volume repulsion strongly hinders the ion permeation for shrunken nanogels, where volume exclusion is able to significantly reduce the concentration of counterions in the more dense regions of the nanogel. In general, we demonstrate that the thermosensitive behaviour of nanogels, as well as their internal structure, is strongly influenced by the valence of the counterions and also by the charge of the particles. On the one hand, an increase of the counterion valence moves the swelling transition to lower temperatures, and induces a major structuring of the charged monomers into internal and external layers around the crown for shrunken nanogels. On the other hand, increasing the particle charge shifts the swelling curve to larger values of the effective radius of the nanogel.

Interactions between silica particles in the presence of multivalent coions.

Forces between charged silica particles in solutions of multivalent coions are measured with colloidal probe technique based on atomic force microscopy. The concentration of 1 : z electrolytes is systematically varied to understand the behavior of electrostatic interactions and double-layer properties in these systems. Although the coions are multivalent the Derjaguin, Landau, Verwey, and Overbeek (DLVO) theory perfectly describes the measured force profiles. The diffuse-layer potentials and regulation properties are extracted from the forces profiles by using the DLVO theory. The dependencies of the diffuse-layer potential and regulation parameter shift to lower concentration with increasing coion valence when plotted as a function of concentration of 1 : z salt. Interestingly, these profiles collapse to a master curve if plotted as a function of monovalent counterion concentration.

Base sequence specificity of counterion binding to DNA: what can MD simulations tell us?

Nucleic acids are highly charged biopolymers whose secondary structure is strongly dependent on electrostatic interactions. Solvent molecules and ions are also believed to play an important role in mediating and directing both sequence recognition and interactions with other molecules, such as proteins and a variety of ligands. Therefore, to fully understand the biological functions of DNA, it is necessary to understand the interactions with the surrounding counterions. It is well known that monovalent counterions can bind to the minor groove of DNA with consecutive sequences of four, or more, adenine and thymine (A-tracts) with relatively long residence times. However, much less is known about their binding to the backbone and to the major groove. In this work, we used molecular dynamics simulations to both investigate the interactions between the backbone and major groove of DNA and one of its physiological counterions (Na+) and evaluate the relationship between these interactions and the nucleotide sequence. Three dodecamers, namely CGAAAATTTTCG, CGCTCTAGAGCG, and CGCGAATTCGCG, were simulated using the Toukan–Rahman flexible SPC water model and Smith and Dang parameters for Na+, revealing a significant sequence dependence on the ion binding to both backbone and major groove. In the absence of experimental data on the atomistic details of the studied interactions, the reliability of the results was evaluated performing the simulations with additional sets of potential parameters for ions and solvent, namely the Ȧqvist or the Joung and Cheatham ion parameters and the TIP3P water model. This allowed us to evaluate the results by verifying which features are preserved independently from the parameters adopted.

Effect of nanomaterial and media physicochemical properties on Ag NM aggregation kinetics

Nanomaterial (NM) aggregation is a key process determining their environmental, fate behavior and effects. Nanomaterials are typically engineered to remain kinetically stable; however, in environmental and toxicological media, NMs are prone to aggregation. The aggregation kinetics of NM is typically quantified by measuring their attachment efficiency (α) and critical coagulation concentration (CCC). Several studies measured α and CCC for Ag NMs with a major focus on investigating the effects of ionic strength, ion valency and natural organic matter, with few studies investigating other environmental factors such as light and dissolved oxygen and none investigating the effect of particle size, buffer type and concentration, or surface coverage by capping agent. A survey of recent research articles reporting CCC values for Ag NMs reveals substantial variation in experimental conditions and particle stability with CCC values of monovalent and divalent counterions covering a wide range (ca. 25 to infinity for monovalent counterions and 1.6 to infinity for divalent counterions).Here, we rationalize the differences in the CCC values for Ag NMs based on the variability in the experimental conditions, which includes NM and medium physicochemical properties. Capping agents determines NM stability mechanism with citrate, sodium dodecyl sulfate (SDS), and alginate stabilizing NM by electrostatic mechanism; whereas polyvinylpyrrolidone (PVP), casein, dextrin, tween, branched polyethyleneimine (BPEI), and Gum Arabic stabilizing NMs by steric mechanisms. The CCC values for Ag NMs with different capping agents follow the order citrate∼alginate∼SDS<casein<dextrin<PVP<tween<branched polyethyleneimine (BPEI)∼gum Arabic. For charge stabilized Ag NMs, the CCC increases with the decrease in NM size and buffer concentration and decreases with light irradiation. For sterically stabilized PVP-Ag NMs, the CCC increases with the coating concentration/surface coverage and completely coated Ag NMs do not undergo aggregation even at high salt concentrations.

On describing the equilibria in mixed solutions of polyelectrolytes and simple salts using the law of mass action

Abstract The validity of the law of mass action in its simplest form (using only the molar concentration) was examined for the case of the binding of counterions to polyions in mixed solutions of a polyelectrolyte and a simple + 1:− 1 salt at 25 °C. The study was made for a polyelectrolyte with a linear charge density ξ = 1.8 and monovalent counterions; both the counterions from the original polyelectrolyte as well as those from the added simple salt interact with the polyion only via Coulombic interactions (specific interactions are absent). For the given system, the apparent equilibrium constant for the binding of the counterions to the polyion was evaluated from the fraction of free counterions. The latter was calculated from the cell model of cylindrical symmetry for the studied polyelectrolyte in a salt-free solution and was confirmed experimentally. With the use of this apparent equilibrium constant, K s-LMA , the fraction of free counterions f as well as the degree of charge neutralization of the polyion, θ, derived from f were evaluated in the concentration range of the polyelectrolyte's repeating units, c p , from 1·10 − 7 to 1 monomol/dm 3 . These calculations were made for three different ratios of the concentration of the added simple salt, c s , and c p ( c s / c p = 0, 1, and 4). Additionally, from the simple law of mass action the calculated values for f were also verified for the case of the titration of the linear polyelectrolyte ( c p = 0.02 monomol/dm 3 ) with the + 1:− 1 salt. In this latter case the results obtained from the simple law of mass action were compared with both the prediction of the cell model and the available experimental results. In all the studied cases the application of the simple law of mass action generally provided poor results; however, a significant improvement was obtained by including the term exp(− ϕ) in the equilibrium constant, ϕ being the dimensionless electrostatic potential at the surface of the polyion.

Simulations of Polyelectrolyte Adsorption to a Dielectric Like-Charged Surface.

We explore, using the recently developed efficient Monte Carlo simulation method, the interaction of an anionic polyelectrolyte solution with a like-charged dielectric surface. In addition to polyions, the solution also contains salt with either monovalent, divalent, or trivalent counterions. In agreement with recent experimental observations, we find that multivalent counterions can lead to strong adsorption of polyions onto the surface. On the other hand, addition of a 1:1 electrolyte diminishes the adsorption induced by the multivalent counterions. Dielectric discontinuity at the interface is found to play only a marginal role in polyion adsorption.

Unexpected Like-Charge Self-Assembly of a Biguanide-Based Antimicrobial Polyelectrolyte.

Polyelectrolyte chains dissolved in good solvent are expected to collapse in compact configurations in the presence of multivalent ions. Here, we show that a weakly charged, hydrophilic polyelectrolyte containing biguanide groups self-assembles in water also in the presence of monovalent counterions, even at low salt concentrations. The polymer assembles in a compact, ordered, hairpin-like shape that, with increasing the ionic strength of the solution, can collapse further in three- or five-folded structures. Neither water nor ions mediate the self-assembly which, instead, is driven by the like-charge pairing of the biguanide units. The thermodynamics of the self-assembly show that the self-association is enthalpically driven, is isodesmic (at least at low aggregation number), and is favored by increasing salt concentration. This unique self-assembly behavior may be linked to the well-known polymer's antimicrobial properties and could help in rationalizing its biological activity.

Charge reversal of sulfate latex induced by hydrophobic counterion: effects of surface charge density

We studied experimentally and theoretically the charge reversal of sulfate latex colloid in the presence of monovalent hydrophobic counterion TPP+ (tetraphenylphosphonium). The intrinsic or chemical energy of adsorption of TPP+ on the latex was evaluated from the concentration at charge reversal. The isoelectric point (IEP) increases with increasing the surface or electrokinetic charge density of sulfate latex spheres. That is, at low surface or electrokinetic charge density, the charge inversion concentration is low, and IEP shifts to higher values with the increase of surface or electrokinetic charge density. The intrinsic energy of adsorption decreases with increasing the surface or electrokinetic charge density. Finally, our experimental and theoretical results suggest that the hydrophobicity is a determining factor for the charge inversion of hydrophobic colloids, and the intrinsic energy of adsorption also varies with the variations of surface or electrokinetic charge density.

Synthesis of oxocarbon-encapsulated gold nanoparticles with blue-shifted localized surface plasmon resonance by pulsed laser ablation in water with CO2 absorbers

Colloidal suspensions of oxocarbon-encapsulated gold nanoparticles have been synthesized in a one-step procedure by pulsed-laser ablation (PLA) at 532 nm of a solid gold target placed in aqueous solution containing CO2 absorbers, but without any stabilizing agent. Multi-wavelength surface enhanced Raman spectroscopy allows the identification of adsorbed amorphous carbon and graphite, Au-carbonyl, Au coordinated CO2-derived bicarbonates/carbonates and hydroxyl groups around the AuNPs core. Scanning electron microscopy, energy dispersive x-ray analysis and high resolution transmission electron microscopy highlight the organic shell structure around the crystalline metal core. The stability of the colloidal solution of nanocomposites (NCs) seems to be driven by solvation forces and is achieved only in neutral or basic pH using monovalent hydroxide counter-ions (NaOH, KOH). The NCs are characterized by a blue shift of the localized surface plasmon resonance (LSPR) band typical of metal-ligand stabilization by terminal π-back bonding, attributed to a core charging effect caused by Au-carbonyls. Total organic carbon measurements detect the final content of organic carbon in the colloidal solution of NCs that is about six times higher than the value of the water solution used to perform PLA. The colloidal dispersions of NCs are stable for months and are applied as analytical probes in amino glycoside antibiotic LSPR based sensing.

Anomalous temperature behavior in clay swelling due to ion-ion correlations

We show, experimentally and theoretically, that swelling of both natural and refined clays has an anomalous temperature behavior depending on counterion valency. In an aqueous clay dispersion dominated by monovalent counterions the swelling pressure increases with temperature as expected from entropic arguments. In a clay with predominantly divalent counterions, the opposite behavior is found. The explanation is due to the fact that ion-ion correlations increase with temperature. Ion-ion correlations are important at strong electrostatic coupling and in an aqueous solution the dielectric permittivity, , drops with increased temperature, T, in such a way that the product also decreases. Thus, the net effect is an increased coupling.

Influence of higher valent ions on flexible polyelectrolyte stiffness and counter-ion distribution.

We investigate the influence of counter-ion valency on the flexibility of highly charged flexible polymer chains using molecular dynamics simulations that include both salt and an explicit solvent. As observed experimentally, we find that divalent counter-ions greatly reduce the chain persistence length, lp, in comparison with monovalent counter-ions. On the other hand, polyelectrolyte chains having trivalent counter-ions adopt a much more compact conformation than polyelectrolytes having monovalent and divalent counter-ions. We demonstrate that the tendency of polyelectrolyte chains to become deformed by proximal high valence counter-ions is due to chain "coiling" around the counter-ions. In particular, we find that the number of contacts that the proximal counter-ions have with the polyelectrolyte dictates the extent of chain coiling. This ion-binding induced coiling mechanism influences not only the conformational properties of the polyelectrolyte, but also the counter-ion distribution around the chain. Specifically, we find that higher valent counter-ions lead both to a counter-ion enrichment in close proximity to the polyelectrolyte and to a significant reduction in the spatial extent of the diffuse counter-ion cloud around the polyelectrolyte.

Complex formation between polyelectrolytes and oppositely charged oligoelectrolytes.

We study the complex formation between one long polyanion chain and many short oligocation chains by computer simulations. We employ a coarse-grained bead-spring model for the polyelectrolyte chains and model explicitly the small salt ions. We systematically vary the concentration and the length of the oligocation and examine how the oligocations affects the chain conformation, the static structure factor, the radial and axial distribution of various charged species, and the number of bound ions in the complex. At low oligocation concentration, the polyanion has an extended structure. Upon increasing the oligocation concentration, the polyanion chain collapses and forms a compact globule, but the complex still carries a net negative charge. Once the total charge of the oligocations is equal to that of the polyanion, the collapse stops and is replaced by a slow expansion. In this regime, the net charge on the complexes is positive or neutral, depending on the microion concentration in solution. The expansion can be explained by the reduction of the oligocation bridging. We find that the behavior and the structure of the complex are largely independent of the length of oligocations, and very similar to that observed when replacing the oligocations by multivalent salt cations, and conclude that the main driving force keeping the complex together is the release of monovalent counterions and coions. We speculate on the implications of this finding for the problem of controlled oligolyte release and oligolyte substitution.

Structure and dynamics of water and lipid molecules in charged anionic DMPG lipid bilayer membranes.

Molecular dynamics simulations have been used to investigate the influence of the valency of counter-ions on the structure of freestanding bilayer membranes of the anionic 1,2-dimyristoyl-sn-glycero-3-phosphoglycerol (DMPG) lipid at 310 K and 1 atm. At this temperature, the membrane is in the fluid phase with a monovalent counter-ion and in the gel phase with a divalent counter-ion. The diffusion constant of water as a function of its depth in the membrane has been determined from mean-square-displacement calculations. Also, calculated incoherent quasielastic neutron scattering functions have been compared to experimental results and used to determine an average diffusion constant for all water molecules in the system. On extrapolating the diffusion constants inferred experimentally to a temperature of 310 K, reasonable agreement with the simulations is obtained. However, the experiments do not have the sensitivity to confirm the diffusion of a small component of water bound to the lipids as found in the simulations. In addition, the orientation of the dipole moment of the water molecules has been determined as a function of their depth in the membrane. Previous indirect estimates of the electrostatic potential within phospholipid membranes imply an enormous electric field of 10(8)-10(9) V m(-1), which is likely to have great significance in controlling the conformation of translocating membrane proteins and in the transfer of ions and molecules across the membrane. We have calculated the membrane potential for DMPG bilayers and found ∼1 V (∼2 ⋅ 10(8) V m(-1)) when in the fluid phase with a monovalent counter-ion and ∼1.4 V (∼2.8 ⋅ 10(8) V m(-1)) when in the gel phase with a divalent counter-ion. The number of water molecules for a fully hydrated DMPG membrane has been estimated to be 9.7 molecules per lipid in the gel phase and 17.5 molecules in the fluid phase, considerably smaller than inferred experimentally for 1,2-dimyristoyl-sn-glycero-3-phosphorylcholine (DMPC) membranes but comparable to the number inferred for 1,2-dilauroyl-sn-glycero-3-phosphoethanolamine (DLPE) membranes. Some of the properties of the DMPG membrane are compared with those of the neutral zwitterionic DMPC bilayer membrane at 303 K and 1 atm, which is the same reduced temperature with respect to the gel-to-fluid transition temperature as 310 K is for the DMPG bilayer membrane.

Charged Nanoparticle Attraction in Multivalent Salt Solution: A Classical-Fluids Density Functional Theory and Molecular Dynamics Study.

Negatively charged nanoparticles (NPs) in 1:1, 1:2, and 1:3 electrolyte solutions are studied in a primitive ion model using molecular dynamics (MD) simulations and classical density functional theory (DFT). We determine the conditions for attractive interactions between the like-charged NPs. Ion density profiles and NP-NP interaction free energies are compared between the two methods and are found to be in qualitative agreement. The NP interaction free energy is purely repulsive for monovalent counterions, but can be attractive for divalent and trivalent counterions. Using DFT, the NP interaction free energy for different NP diameters and charges is calculated. The depth and location of the minimum in the interaction depend strongly on the NPs' charge. For certain parameters, the depth of the attractive well can reach 8-10 kBT, indicating that kinetic arrest and aggregation of the NPs due to electrostatic interactions is possible. Rich behavior arises from the geometric constraints of counterion packing at the NP surface. Layering of counterions around the NPs is observed and, as secondary counterion layers form the minimum of the NP-NP interaction free energy shifts to larger separation, and the depth of the free energy minimum varies dramatically. We find that attractive interactions occur with and without NP overcharging.

Forces between silica particles in the presence of multivalent cations

Forces between negatively charged silica particles in aqueous electrolyte solutions were measured with the colloidal probe technique based on the atomic force microscope (AFM). The present study focuses on the comparison of monovalent and multivalent counterions, namely K+, Mg2+, and La3+. The force profiles can be well described with the theory of Derjaguin, Landau, Verwey, and Overbeek (DLVO) down to distances of about 4nm. At smaller distances, the forces become strongly repulsive due to additional non-DLVO repulsion. In the presence of La3+, one observes an additional attractive force with a range of about 1nm at intermediate salt concentrations. This force is probably related to ion-ion correlations, but could also be influenced by surface charge heterogeneities or charge fluctuation forces.

Impact of Monovalent Counter-ions on the Conformation of Flexible Polyelectrolytes Having Different Molecular Architectures

ABSTRACTWe explore the impact of monovalent counter-ions on the molecular conformation of highly charged flexible polyelectrolytes for a range of molecular topologies (linear chains, stars, and unknotted and trefoil rings) by molecular dynamics simulations that include an explicit solvent having short range interaction with the polyelectrolyte. In particular, we investigate how the counter-ions near the polyelectrolytes with variable mass influence the average molecular shape. We also characterize the interfacially “bound” counter-ions by calculating the time-averaged number of interfacial counter-ions, as well as the degree to which the polyelectrolytes wrap around the counter-ions by calculating the number of contacts between the counter-ions and the polyelectrolyte.