We propose a Poisson-Boltzmann electrostatic theory for DNA/cationic l
ipid complexes modeled as a stack of aligned DNA chains intercalated w
ith lipid bilayers, a structure suggested by the recent X-ray synchrot
ron studies of Radler et al. Poisson-Boltzmann theory is shown to pred
ict that the isoelectric point - where the DNA and cationic lipid char
ges are in balance - is unstable against absorption of extra DNA or li
pid material. The instability is caused by the entropy gain obtained f
ollowing the release of small ions inside the complex and is manifeste
d by singular behavior of the rod-rod spacing near the isoelectric poi
nt. We apply the theory to a discussion of the results of Radler et al
.