The interaction of DNA with vesicles of cationic lipids mixed with varying
amounts of a zwitterionic lipid in dilute solutions was studied by isotherm
al titration microcalorimetry, differential scanning calorimetry (DSC), and
turbidity measurements. Extruded pure dimethyldioctadecylammonium bromide
(DODAB) and chloride (DODAC) vesicles and mixed vesicles with various amoun
ts of dioleoylphosphatidylethanolamine (DOPE) were investigated at 25 degre
es C. The interaction of DNA with cationic vesicles is fast and endothermic
. The enthalpy of reaction per mole of lipid added is constant with varying
charge ratio between cationic lipid and DNA but decreases with increasing
amounts of the zwitterionic lipid in the vesicle. The enthalpy change is co
nstant up to a critical charge ratio rho+/- of about 0.8 for the addition o
f lipid vesicles to DNA and 1.2 for the addition of DNA to lipid vesicles.
The enthalpy of reaction decreases with the replacement of Br- by Cl- ion a
nd is independent of cationic vesicle size in the range 50-200 nm. The effe
ct of DOPE on the thermotropic behavior of DODAB in aqueous dispersions wit
h and without DNA was investigated using DSC. Inclusion of DOPE in the DODA
B cationic vesicle increases the bilayer fluidity, e.g., decreases the melt
ing temperature, T-m. The status of the hydrocarbon chains, solid-like or f
luid, has a pronounced effect on the measured enthalpy changes and most str
ongly for the formation of positively charged, lipid-enriched aggregates.