Structural aspects of lyotropic solvation-induced transitions in phosphatidylcholine and phosphatidylethanolamine assemblies revealed by infrared spectroscopy
H. Binder et W. Pohle, Structural aspects of lyotropic solvation-induced transitions in phosphatidylcholine and phosphatidylethanolamine assemblies revealed by infrared spectroscopy, J PHYS CH B, 104(50), 2000, pp. 12039-12048
The hydration of two peculiar unsaturated lipids with phosphatidylethanolam
ine (PE) and phosphatidylcholine (PC) headgroups, namely dioctadecadienoyl
PC (DODPC) and dioleoyl PE (DOPE), has been studied at room temperature by
infrared (IR) spectroscopy including the linear dichroism. Oriented films o
f these lipids subjected to an atmosphere with definite values of relative
humidity were investigated. The choice of DODPC and DOPE was motivated by t
heir common property of undergoing a lyotropic phase transition, which, in
each case, nearly exclusively affects the polar part of the lipid aggregate
s and is, thus, termed "solvation-induced" transition. The temperature-RH p
hase diagrams of both lipids were determined. The headgroups of both lipids
form quasi-crystalline structures at small RH. The long axes of the PE and
PC moieties orient essentially parallel with respect to the polar interfac
e of; the lipid aggregates. Model-based analyses of IR linear-dichroism dat
a are consistent with the idea that about 8-12 DOPE molecules with disorder
ed chains assemble within one cross-section layer of a ribbonlike phase, P-
alpha. Dry DODPC forms a subgel phase (SG(1)) with all-trans acyl chains. A
t a critical water activity near 0.6, the molecular disorder in the polar r
egion of the lipid aggregates increases distinctly. This "headgroup melting
" reflects the solvation-induced transitions leading to the SG(II) and H-II
phases in DODPC and DOPE, respectively. Hydrogen-bonding specifics due to
the polar parts of both lipids were probed by means of H --> D exchange. Pa
rticularly stable H bonds are indicated to exist in dried DOPE.