Influence of effective polarization on ion and water interactions within a biomimetic nanopore

Interactions between ions and water at hydrophobic interfaces within ion channels and nanopores are suggested to play a key role in the movement of ions across biological membranes. Previous molecular dynamics (MD) simulations have shown that the affinity of polarizable anions to aqueous/hydrophobic interfaces can be markedly influenced by including polarization effects through an electronic continuum correction (ECC). Here, we designed a model biomimetic nanopore to imitate the polar pore openings and hydrophobic gating regions found in pentameric ligand-gated ion channels. MD simulations were then performed using both a non-polarizable force field and the ECC method to investigate the behavior of water, Na+ and Cl- ions confined within the hydrophobic region of the nanopore. Number density distributions revealed preferential Cl- adsorption to the hydrophobic pore walls, with this interfacial layer largely devoid of Na+. Free energy profiles for Na+ and Cl- permeating the pore also display an energy barrier reduction associated with the localization of Cl- to this hydrophobic interface, and the hydration number profiles reflect a corresponding reduction in the first hydration shell of Cl-. Crucially, these ion effects were only observed through inclusion of effective polarization which therefore suggests that polarizability may be essential for an accurate description for the behavior of ions and water within hydrophobic nanoscale pores, especially those that conduct Cl-.

SALTING-IN AND SALTING-OUT EFFECTS OF POLYPHENOLS, AROMATIC COMPOUNDS, AND AMINO ACIDS ON POLY (N-ISOPROPYLACRYLAMIDE) AND EGG WHITE AQUEOUS SOLUTIONS

Introduction. Understanding the biophysical phenomena related to the Hofmeister series or cosmotropic/chaotropic properties of ions requires experimental data on specific ion effects of large organic molecules.Problem Statement. Specific ion effects are of significant importance for biophysics and medicine. It is interesting to find out if additives with biologically relevant anions can interact with proteins and avoid aggregation.Purpose. The purpose of this research is to study the stabilizing/destabilizing effects in Poly(N-isopropylacrylamide) (PNIPAM)/water, hen egg white/water systems under influence of substances of various classes of different hydrophobia.Materials and Methods. Materials: sodium salts: salicylate, ferulate, benzoate, vanillate, cinnamate; humic acid sodium salt, hydroxy-sodium benzoate, glycine, L-alanine, sodium L-glutamate, D-(—)-quinnic acid, PNIPAM, egg white. Methods: measurement of the transition temperature (TT) of PNIPAM/water and the denaturationtemperature of the egg white / water systems.Results. Ion-specific effects have been studied with the use of models based on the research of the transition temperature (TT) evolution of binary PNIPAM / water mixtures (for heating from 0 to 35°C) and the denaturation temperature of the egg white / water (for heating from 48 to 65°C). The dependences of these temperatureson the content of substances that occur in live nature have been received at pH = 7.4.Conclusions. The results have shown the tendencies of the additive solubilizing effects on PNIPAM and egg white. The majority of substances studied has the salting-out effect on PNIPAM / water in the order NaBz ~ NaCinn < L-NaGlu ~ NaFer. For NaSal and NaHum; the salting-in effect has been established. For the egg white, all additives show the salting-in effect. In PNIPAM and egg white systems, NaBz and L-NaGlu demonstrate the opposite effects. The results have been compared with the ones for binary mixtures of water/di-propylene glycolpropyl ether (DPnP).

Specific Ion Effects on the Behavior of Mixtures of Sodium Iso-Butyl Xanthate and Sodium Diethyl Dithiophosphate during the Flotation of a Cu-Ni-PGM Ore: Effects of CaCl2 and NaCl

Inorganic electrolytes present in the process water used during froth flotation may have both beneficial and detrimental effects. These effects are said to be ion specific, as some ions may result in enhanced froth stability, increased mineral recoveries and decreased concentrate grades, while others may bring the opposite effects. Onsite process water quality variations have intensified the need to understand the relationship between inorganic electrolytes and flotation reagents on flotation performance. The use of mixtures of thiol collectors in sulfide flotation is a common practice across the globe; however, very few investigations have considered these in process waters of varying compositions. This study considers the effect of common cations, Na+ and Ca2+, in process water on the behavior of mixtures of thiol collectors. Single-salt solutions of NaCl and CaCl2 at an ionic strength of 0.0213 mol·dm−3 were used to investigate the behavior of mixtures of two thiol collectors. These were carefully selected to understand how mixtures of thiol collectors behave in the presence of a monovalent cation versus a polyvalent cation. Bench-scale froth flotation tests were conducted using a Cu-Ni-PGM ore from the Merensky Reef. The results have shown that the divalent cation, Ca2+, resulted in higher %Cu and %Ni recoveries at all collector mixtures compared to the monovalent cation, Na+. The concentrate grades were, however, slightly compromised, as slightly more gangue reported to the concentrate in the presence of Ca2+. This behavior is attributed to the effect of polyvalent cations on bubble coalescence and froth stability.