Anion-specific partitioning in two-phase finite volume systems: possible implications for mechanisms of ion pumps.

In two-phase finite volume systems of electroneutral phospholipids, the electrolyte concentration is different in the two phases. The partitioning is highly anion-specific, a phenomenon not accounted for by classical electrolyte theories. It is explained if ionic dispersion forces that lead to specific ion binding are taken into account. The mechanism provides a contribution to active ion pumps not previously considered.

Extended DLVO theory: electrostatic and non-electrostatic forces in oxide suspensions.

According to classical DLVO theory all ions of background salt solution with the same ionic charge should result in the same effective force between colloidal particles. However, the relative effectiveness of different ions in influencing forces between ceramic oxide surfaces follows either a reversed Hofmeister sequence or a direct Hofmeister sequence depending on the type of oxide and if the pH is above or below the isoelectric point (iep). This ion specificity is inexplicable in classical double layer theory that deals only with pure electrostatic forces acting between the ions and the colloidal particles. A theoretical explanation is given here. At, and above, biological salt concentrations other, non-electrostatic (NES) ion specific forces act that are ignored in such modeling. In this overview we present the basic theory for the double layer near a single oxide surface and for the extended DLVO forces between oxide colloidal particles that accounts for these NES forces. We will demonstrate that ion specificity can be understood to a large degree once NES forces are included consistently in the non-linear theory.

Ion specific surface forces between membrane surfaces.

Entities such as ion distributions and forces between lipid membranes depend on effects due to the intervening salt solution that have not been recognized previously. These specific ion or Hofmeister effects influence membrane fusion. A typical illustrative example is this: measurements of forces between double-chained cationic bilayers adsorbed onto molecularly smooth mica surfaces across different 0.6-2 mM salt solutions have revealed a large degree of ion specificity [Pashley et al. J. Phys. Chem. 1986, 90, 1637]. This has been interpreted in terms of very specific anion "binding" to the adsorbed bilayers, as it would too for micelles and other self-assembled systems. However, we show here that inclusion of nonelectrostatic (NES) or ionic dispersion potentials acting between ions and the two surfaces explains such "ion binding". The observed Hofmeister sequence for the calculated pressure without any direct ion binding is given correctly. This demonstrates the importance of a source of ion specificity that has been ignored. It is due to ionic physisorption caused by attractive NES ionic dispersion potentials. There appear to be some far reaching consequences for interpretations of membrane intermolecular interactions in salt solutions.