Insights into hofmeister mechanisms: anion and degassing effects on the cloud point of dioctanoylphosphatidylcholine/water systems.

Water dispersions of dioctanoylphosphatidylcholine (diC8PC) exhibit upper consolute curves. How they are affected by some salts and other additives (D2O, urea) has already been explored and the phase separation has been interpreted within the framework of the Blankschtein-Thurston-Benedek (BTB) model. This deduces the chemical potential gain in micellar growth (Deltamu) and the intermicellar interaction coefficient (C) as fitting parameters from the coexistence curves. But, the specific mechanisms that drive such phenomena have remained obscure. To identify these mechanisms, we investigate the effects of a range of anions on the cloud points of diC8PC/H2O systems and extract the phenomenological parameters of the BTB model. We show how these parameters, for micellar growth, i.e., surface, intramolecular interactions, and for interaggregate interactions, i.e., bulk solute effects, are connected to anionic polarizabilities. Nonelectrostatic (NES) quantum mechanical fluctuation (Lifshitz or dispersion) forces missing from conventional theories are then shown to regulate lyotropic Hofmeister effects, both explicitly and implicitly.