Effects of Alkali Cations and Halide Anions on the
Self-Assembly of Phosphatidylcholine in Oils
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Abstract
The
interactions between ions and phospholipids are closely associated
with the structures and functions of cell membrane. Instead of conventional
aqueous systems, we systematically investigated the effects of inorganic
ions on the self-assembly of lecithin, a zwitterionic phosphatidylcholine,
in cyclohexane. Previous studies have shown that addition of inorganic
salts with specific divalent and trivalent cations can transform lecithin
organosols into organogels. In this study, we focused on the effect
of monovalent alkali halides. Fourier transform infrared spectroscopy
was used to demonstrate that the binding strength of the alkali cations
with the phosphate of lecithin is in the order Li<sup>+</sup> >
Na<sup>+</sup> > K<sup>+</sup>. More importantly, the cation–phosphate
interaction is affected by the paired halide anions, and the effect
follows the series I<sup>–</sup> > Br<sup>–</sup> > Cl<sup>–</sup>. The salts of stronger interactions with
lecithin, including LiCl, LiBr, LiI, and NaI, were found to induce
cylindrical micelles sufficiently long to form organogels, while others
remain organosols. A mechanism based on the charge density of ions
and the enthalpy change of the ion exchange between alkali halides
and lecithin headgroup is provided to explain the contrasting interactions
and the effectiveness of the salts to induce organogelation