Headgroup volumes of seven dioleoyl lipid species, calculated from cov
alent radii, are shown to correlate linearly (r = 0.95) with the abili
ty of those lipids to alter the midpoint temperature of the lamellar t
o inverted hexagonal phase transition (L(alpha) --> H(II)) of a 95 mol
e fraction percent phosphatidylethanolamine matrix. The results illust
rate the utility of the shape concept and basic considerations of head
group volume as a predictive tool for the determination of lipid struc
ture.