The potential of mean force (PMF) acting between two simple ions surrounded by SPC/E water have been determined by molecular dynamics (MD) simulations using a spherical cavity approach. Such effective ion-ion potentials were obtained for Me-Me, Me-Cl-, and Cl(-)-Cl- pairs, where Me is a Li+, Na+, K+, Mg2+, Ca2+, Sr2+, and Ba2+ cation. The ionic sizes estimated from the effective potentials are not pairwise additive, a feature in the frequently used primitive model for electrolytes. The effective potentials were used in Monte Carlo (MC) simulations with implicit water to calculate mean ion activity coefficients of LiCl, NaCl, KCl, MgCl2, CaCl2, SrCl2, and BaCl2. Predicted activities were compared with experimental ones in the electrolyte concentration range 0.1-1 M. A qualitative agreement for LiCl and a satisfactory agreement for NaCl were found, whereas the predictions for KCl by two K+ models were less coherent. In the case of alkaline earth metal ions, all experimental activities were successfully reproduced at c = 0.1 M. However, at higher concentrations, similar deviations occurred for all divalent cations, suggesting that the dependence of the permittivity on the salt concentration and the polarization deficiency arising from the ordering of water molecules in the ion hydration shells are important in such systems.

Polarization deficiency and excess ion hydration free energy at an electric field E (ion hydration free energy at the field E subtracted by the ion hydration free energy at zero field) of hydrated calcium, sodium, and chloride ions have been determined by Monte Carlo simulations. A spherical cell containing either one ion and molecular water or only molecular water subjected to an external electrical field was used. The permittivity of pure water decreases as E is increased, in quantitative agreement with previous simulation studies and the Booth theory. The excess ion hydration free energy depends quadratically on E up to ca. 2.5·108 V/m, whereas it becomes linear in E at higher field due to dielectric saturation. The values of the excess ion hydration free energies are in quantitative agreement with measured dependencies of the relative permittivity of electrolyte solution upon the ion concentration. A primitive polarization model of electrolyte solution near charged interfaces is proposed. The use of this model leads to an additional effective repulsive force acting on hydrated ions near charged surfaces and significantly affects the distribution of calcium ions near such surfaces.

Modified Poisson-Boltzmann (MPB) equations have been numerically solved to study ionic distributions and mean electrostatic potentials around a macromolecule of arbitrarily complex shape and charge distribution. Results for DNA are compared with those obtained by classical Poisson-Boltzmann (PB) calculations. The comparisons were made for 1:1 and 2:1 electrolytes at ionic strengths up to 1 M. It is found that ion-image charge interactions and interionic correlations, which are neglected by the PB equation, have relatively weak effects on the electrostatic potential at charged groups of the DNA. The PB equation predicts errors in the long-range electrostatic part of the free energy that are only approximately 1.5 kJ/mol per nucleotide even in the case of an asymmetrical electrolyte. In contrast, the spatial correlations between ions drastically affect the electrostatic potential at significant separations from the macromolecule leading to a clearly predicted effect of charge overneutralization.

Hydration of films of pig gastric mucin was studied using a quartz crystal microbalance with dissipation monitoring (QCM-D) equipped with a humidity module. As a prerequisite, the water adsorption isotherm of a clean silica surface was determined. Atomic force microscopy was used to characterize the changes occurring on the silica surface after repeated sorption/desorption and cleaning cycles. The water sorption isotherms of several hundreds of nanometers thick mucin films were obtained in QCM-D experiments using analysis of overtone behavior. The results show that the sorption isotherms are not dependent on the film thicknesses and are in good agreement with sorption calorimetric data on mucin in the bulk phase. Moreover, hydration-induced changes of rheological properties of mucin films were investigated using a model-free approach. The ratio of G'/G″ was evaluated as a function of relative humidity. The transition from solidlike behavior to liquidlike behavior was observed in the same humidity range as in sorption calorimetric experiments. Thus, ability of QCM-D to monitor glass transition in biopolymers was demonstrated.