Conductance of concentrated electrolytes: Multivalency and the Wien effect.

The electric conductivity of ionic solutions is well understood at low ionic concentrations of up to a few millimolar but becomes difficult to unravel at higher concentrations that are still common in nature and technological applications. A model for the conductivity at high concentrations was recently put forth for monovalent electrolytes at low electric fields. The model relies on applying a stochastic density-functional theory and using a modified electrostatic pair-potential that suppresses unphysical, short-range electrostatic interactions. Here, we extend the theory to multivalent ions as well as to high electric fields where a deviation from Ohm's law known as the Wien effect occurs. Our results are in good agreement with experiments and recent simulations.

Conductivity of Concentrated Electrolytes.

The conductivity of ionic solutions is arguably their most important trait, being widely used in electrochemical, biochemical, and environmental applications. The Debye-Hückel-Onsager theory successfully predicts the conductivity at very low ionic concentrations of up to a few millimolars, but there is no well-established theory applicable at higher concentrations. We study the conductivity of ionic solutions using a stochastic density functional theory, paired with a modified Coulomb interaction that accounts for the hard-core repulsion between the ions. The modified potential suppresses unphysical, short-range electrostatic interactions, which are present in the Debye-Hückel-Onsager theory. Our results for the conductivity show very good agreement with experimental data up to 3 molars, without any fit parameters. We provide a compact expression for the conductivity, accompanied by a simple analytical approximation.

Phase Separation of Polyelectrolytes: The Effect of Charge Regulation.

Complex coacervation, known as the liquid-liquid phase separation of solutions with oppositely charged polyelectrolytes, has attracted substantial interest in recent years. We study the effect of the charge regulation (CR) mechanism on the complex coacervation by including short-range interactions between the charged sites on the polymer chains as well as an association-dissociation energy parameter in the CR mechanism. We investigate the phase diagrams of two CR models: (i) the hopping CR model (HCR) and (ii) the asymmetric CR model (ACR). It is shown that during the phase separation that the polymers in the condensed phase are more charged than those in the dilute phase, in accordance with Le Chatelier's principle. In addition, secondary CR effects also influence the change in the volume fraction of the two phases. The latter can cause the charge difference between the two phases to change nonmonotonically as a function of the CR parameters.

Brownian motion of a charged colloid in restricted confinement.

We study the Brownian motion of a charged colloid, confined between two charged walls, for small separation between the colloid and the walls. The system is embedded in an ionic solution. The combined effect of electrostatic repulsion and reduced diffusion due to hydrodynamic forces results in a specific motion in the direction perpendicular to the confining walls. The apparent diffusion coefficient at short times as well as the diffusion characteristic time are shown to follow a sigmoid curve as a function of a dimensionless parameter. This parameter depends on the electrostatic properties and can be controlled by tuning the solution ionic strength. At low ionic strength, the colloid moves faster and is localized, while at high ionic strength it moves slower and explores a wider region between the walls, resulting in a larger diffusion characteristic time.

Critical behavior of charge-regulated macro-ions.

Based on a collective description of electrolytes composed of charge-regulated macro-ions and simple salt ions, we analyze their equilibrium charge state in the bulk and their behavior in the vicinity of an external electrified surface. The mean-field formulation of mobile macro-ions in an electrolyte bathing solution is extended to include interactions between association and dissociation sites. We demonstrate that above a critical concentration of salt, similar to the critical micelle concentration, a non-trivial distribution of charge states sets in. Such a charge state can eventually lead to a liquid-liquid phase separation based on charge regulation.

Charge oscillations in ionic liquids: A microscopic cluster model.

In spite of their enormous applications as alternative energy storage devices and lubricants, room-temperature ionic liquids (ILs) still pose many challenges from a pure scientific viewpoint. We develop an IL microscopic theory in terms of ionic clusters, which describes the IL behavior close to charged interfaces. The full structure factor of finite-size clusters is considered and allows us to retain fine and essential details of the system as a whole. Beside the reduction in the screening, it is shown that ionic clusters cause the charge density to oscillate near charged boundaries, with alternating ion-size thick layers, in agreement with experiments. We distinguish between short-range oscillations that persist for a few ionic layers close to the boundary, as opposed to long-range damped oscillations that hold throughout the bulk. The former can be captured by finite-size ion pairs, while the latter is associated with larger clusters with a pronounced quadrupole (or higher) moment. The long-wavelength limit of our theory recovers the well-known Bazant-Storey-Kornyshev (BSK) equation in the linear regime, and elucidates the microscopic origin of the BSK phenomenological parameters.

Charge regulating macro-ions in salt solutions: screening properties and electrostatic interactions.

We revisit the charge-regulation mechanism of macro-ions and apply it to mobile macro-ions in a bathing salt solution. In particular, we examine the effects of correlation between various adsorption/desorption sites and analyze the collective behavior in terms of the solution effective screening properties. We show that such a behavior can be quantified in terms of the charge asymmetry of the macro-ions, defined by their preference for a non-zero effective charge, and their donor/acceptor propensity for exchanging salt ions with the bathing solution. Asymmetric macro-ions tend to increase the screening, while symmetric macro-ions can in some cases decrease it. Macro-ions that are classified as donors display a rather regular behavior, while those that behave as acceptors exhibit an anomalous non-monotonic Debye length. The screening properties, in their turn, engender important modifications to the disjoining pressure between two charged surfaces. Our findings are in particular relevant for solutions of proteins, whose exposed amino acids can undergo charge dissociation/association processes to/from the bathing solution, and can be considered as a solution of charged regulated macro-ions, as analyzed here.

Homocysteine blood level in long-term care residents with oropharyngeal dysphagia: comparison of hand-oral and tube-enteral-fed patients.

BACKGROUND: Levels of homocysteine, methylmalonic acid, and relevant vitamins were measured and evaluated in patients with oral dysphagia (OD) receiving long-term care (LTC). METHODS: Group A was composed of 26 orally fed patients, and group B was composed of 25 patients who were fed by nasogastric tube. All patients were hospitalized in the LTC departments of the Geriatric Medical Center, Shmuel Harofe. General and nutritional status were assessed, and levels of vitamins including B12, folate, and B6 were measured along with serum homocysteine and urine methylmalonic acid levels. RESULTS: Homocysteine levels were significantly higher in the orally fed patients (p < .001); 92% had higher-than-normal homocysteine levels. The levels of vitamins B12, folate, and B6 were significantly lower in the orally fed patients (p < .001), although in most patients levels were in the normal range. Notably, the levels of homocysteine were significantly correlated with the levels of all vitamins but not with the albumin or hemoglobin values. Levels of methylmalonic acid were also higher in the orally fed patients, but the difference was not statistically significant, and there was no correlation between vitamin level and methylmalonic acid level. CONCLUSIONS: Orally fed patients with OD have substantially higher homocysteine levels and appreciably lower levels of the relevant vitamins than patients with OD who receive tube feeding. Therefore, homocysteine measurement may be the preferred indicator of vitamin intake in orally fed patients with OD.