Head groups, charge interaction

The mechanism of transfection by cationic lipids is not known, but cationic lipids probably form stable complexes with anionic DNA molecules to facilitate entry into the cell. Physical studies of DNA/DOTAP/DOPE complexes suggest that DNA molecules are arranged in a regular pattern between layers of lipid bilayer [54]. This multilamellar arrangement permits the charged lipid-head groups to interact with the charged DNA molecules. When mixtures... 

The interest in vesicles as models for cell biomembranes has led to much work on the interactions within and between lipid layers. The primary contributions to vesicle stability and curvature include those familiar to us already, the electrostatic interactions between charged head groups (Chapter V) and the van der Waals interaction between layers (Chapter VI). An additional force due to thermal fluctuations in membranes produces a steric repulsion between membranes known as the Helfrich or undulation interaction. This force has been quantified by Sackmann and co-workers using reflection interference contrast microscopy to monitor vesicles weakly adhering to a solid substrate [78]. Membrane fluctuation forces may influence the interactions between proteins embedded in them [79]. Finally, in balance with these forces, bending elasticity helps determine shape transitions [80], interactions between inclusions [81], aggregation of membrane junctions [82], and unbinding of pinched membranes [83]. Specific interactions between membrane embedded receptors add an additional complication to biomembrane behavior. These have been stud-... 

The problems of the constancy of a and the site of reaction are closely linked. It is very convenient to assume that the charge on the micellar head groups is extensively neutralized by counterions which bind specifically to the micellar surface. In this way micellar stability is associated with a balance between hydrophobic attractions between apolar groups and coulombic repulsions of the ionic head groups which will be reduced by favorable interactions with the counterions in both the Stem and the diffuse Gouy-Chapman layers. It is the behavior of the counterions which is important in considerations of their chemical reactivity. 

We can also describe the differences between these reaction types in terms of Pearson s hard-soft description (Pearson, 1966 Pearson and Songstad, 1967). Cationic micellar head groups interact best with soft bases, e.g. relatively large anions of low charge density such as bromide or arenesulfo-nate, or anionic transition states such as those for nucleophilic aromatic substitution. They interact less readily with hard bases, e.g. high charge density anions such as OH ", or anionic transition states for deacylation. 

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