Headgroups phospholipid monolayers

A theoretical approach based on the electrical double layer correction has been proposed to explain the observed enhancement of the rate of ion transfer across zwitter-ionic phospholipid monolayers at ITIES [17]. If the orientation of the headgroups is such that the phosphonic group remains closer to the ITIES than the ammonium groups, the local concentration of cations is increased at the ITIES and hence the current observed due to cation transfer is larger than in the absence of phospholipids at the interface. This enhancement is evaluated from the solution of the PB equation, and calculations have been carried out for the conditions of the experiments presented in the literature. The theoretical results turn out to be in good agreement with those experimental studies, thus showing the importance of the electrostatic correction on the rate of ion transfer across an ITIES with adsorbed phospholipids. 

The phospholipid monolayers examined in this study were all saturated, symmetric, 1,2-diacyl-j -glycero-3-phosphate-based lipids. Four different lipid headgroups attached to the phosphate were examined choline, ethanolamine, glycerol and serine. Each lipid features a glycerol backbone, two saturated fatty acid chains and a phosphatidyl headgroup. 

Bayerl, T. M., Thomas, R. K., Penfold, J., Rennie, A. and Sackmann, E. (1990). Specular reflection of neutrons at phospholipid monolayers. Changes of mono-layer structure and headgroup hydration at the transition from expanded to the condensed phase. Biophys. J. 57 1095-1098. 

When a monolayer of phospholipids is adsorbed at the ITIES, there must be a modification of the electrical structure of the interface [60]. Since we aim at describing the effect of this monolayer on the rate of ion transfer in a simple way, we assume a sharp interface also in the presence of phospholipids. The hydrophobic tails are located in the organic phase (negative x region), and the hydrophilic headgroups are located in the aqueous phase (positive X region). 

The environment of a cell membrane is often modeled by a monolayer of phospholipid on the air-water interface. Our attempts to detect enantiomeric recognition in such films has largely involved dipalmitoylphosphatidyl choline (DPPC), which has a chiral headgroup situated at the junction of two 16-carbon unit chains. 

Both the N- (a-methylbenzy 1) stearamide and phospholipid systems as detailed above proved to be difficult systems with which to work. The inability of N- a-methylbenzy 1)stearamide to form stable monolayers or even to spread from the crystal on anything but very acidic subphases presents a significant technical challenge despite the presence of a chiral headgroup that is unobstructed by other molecular features. On the other hand, the phospholipid surfactants that spread to form stable films both from solution and from their bulk crystals on pure water subphases at ambient temperatures displayed no discernible enantiomeric discrimination in any film property. The chiral functionality on these biomolecules is apparently shielded from intermolecular interactions with other chiral centers to the extent... 

The phase behavior of monolayers is determined by the molecular structure of the am-phiphile and the conditions of the subphase. Phospholipids, for example, attract each other because of van der Waals interactions between the alkyl chains. The longer the alkyl chains, the more strongly the phospholipids attract each other. Thus, the LE-LC transition pressure will decrease with increasing chain length (at constant temperature). Double bonds in the alkyl chains increase this phase transition pressure. Charges and oriented dipole moments (see Chapter 6) in the headgroups, lead to a repulsion between the phopholipids and increase the pressure at which the transition occurs. Salts in the subphase, screen this repulsion and decrease the transition pressure. 

Figure 2.10 shows the methylene and methyl symmetric stretch region of the spectrum for each headgroup before (solid squares) and after (solid triangles) the exposure of the monolayer to halothane. For each spectrum shown, there is a small increase in the overall intensity when halothane is present. This increase occurs across the entire spectrum for each of the phospholipids smdied. We believe that the small change in intensity... 

---