ABSTRACT
Diacylglycerides (DAGs) constitute an important category of lipids owing to their ability to form a lipid membrane, which can be used in a wide variety of biomedical applications. DAGs often include a zwitterionic polar headgroup that can influence the properties of the lipid membrane (e.g., protein adsorption, ion binding, hydration, membrane fluidity, phase stability) and affect their applicability. To clarify the effect of the charge arrangement of zwitterionic headgroups on intermolecular interactions in the DAG bilayers, we investigated the intermolecular interaction between a naturally occurring DAG (1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC)) and synthetic DAGs (which is called "inverse charge zwitterlipids (ICZLs)") whose headgroup charges were antiparallel with respect to those of DPPC. We used 1,2-dipalmitoyl-sn-glycero-3-carboxybetaine (DPCB) and 1,2-dipalmitoyl-sn-glycero-3-sulfobetaine (DPSB) as ICZLs and compared two combinations of the lipids (DPPC-DPCB and DPPC-DPSB). We obtained surface pressure-area (π-A) isotherms to elucidate the intermolecular interaction between the lipids in the monolayer at the air/water interface. We found shrinkage of the area per molecule in both lipid combinations, indicating that mixing DPPC with ICZLs results in an attractive intermolecular force. As an overall trend, the degree of shrinkage of the mixed monolayer and the thermodynamic favorability of mixing were greater in the DPPC-DPCB combination than in the DPPC-DPSB combination. These trends were also observed in the lipid bilayers, as determined from the gel-to-liquid crystal phase transition temperature (T c) of the aqueous dispersion of the lipid vesicles. In the highly compressed lipid monolayers and vesicles (lipid bilayer), the molar fractions of ICZLs, in which the intermolecular interaction reached a maximum, were 0.6-0.8 for the DPPC-DPCB combination and 0.5 (equimolar composition) for the DPPC-DPSB combination. Therefore, in the compressed monolayers and bilayers, the mechanism of intermolecular interaction between DPPC and DPCB is different from that between DPPC and DPSB.
