Ions regulate the charge of dipolar membranes

Using small- and wide-angle X-ray scattering we checked the effect of ion valency and lipid tail saturation level (using fully saturated lipids, hybrid lipids - containing a saturated and an unsaturated tail - and unsaturated lipids) on the interactions between dipolar membranes. We focused on the differences between multivalent, polyvalent and monovalent ions, and on the balance between the ion-dipole interactions and the structural and entropic aspects of the membrane (Langmuir 2011a, 2011b). The combined effect of temperature and osmotic stress on the interactions between dipolar membranes was also studied (J. Phys. Chem. B 2012). We performed advanced data analysis (using our analysis program X+) and compared our findings with known theories.

Ions and dipolar lipid membranes
Multivalent ions adsorb onto saturated lipid membranes and charge the membranes. The adsorption of monovalent ions or polyvalent ions (like spermine) is much weaker.

 

Ions and unsaturated dipolar lipid membranes
The adsorption of Ions (multivalent, polyvalent or monovalent) to unsaturated dipolar lipid membranes is very weak.

 

Ion-dipolar interactions vs tail entropy
Ion-dipole interactions compete with tail entropy and area per lipid headgroup.

 

We found that when the lipid tails are saturated, multivalent ions (like calcium ions) adsorb onto the lipid bilayer but only above a critical concentration, suggesting that calcium adsorption requires an initial nucleation phase (J. Phys. Chem. A 2016).

 

Adsorption mechanism
Suggested ion adsorption mechanism. (A) Schematic top view of a lipid layer; each blue sphere represents a lipid headgroup. (B) Few ions (red spheres) adsorb onto the bilayer, causing a local deformation, associated with line tension (pink lines). Counterions are shown as green spheres. (C) Ion-adsorbed lipid nucleus has formed, in which the energy gain from adsorption of another ion is greater than the energy associated with the elongation of the line tension (pink line). (D) Fully ion-adsorbed layer. (E) Side view of the dipolar lipids in the nonadsorbed state. (F.) Side view of the adsorbed state.

We have also shown that calcium ions, which initially adsorbed onto lipid membranes, were removed by increasing osmotic stress (Langmuir 2017).

osmotic stress with Ca
Osmotic-stress induces desorption of dipolar membrane bound calcium ions.

This work provides a broad and deep understanding of ion - dipolar membranal structures under a consistent framework. It models biologically relevant interactions between cell membranes and various ions and the manner in which lipid structure controls those interactions. The ability to monitor these interactions creates a tool for probing more complex membranes and assemblies and forms the basis for controlling the interactions between dipolar membranes and charged proteins or biopolymers for encapsulation and delivery applications.