The lyotropic phase behavior of the dienic lipid
1,2-bis(2,4-octadecadienoyl)-sn-glycero-3-phosphorylcholine
(DODPC) has been investigated by means of IR spectroscopy at 25 °C.
Gradual hydration has been realized
exposing the lipid to an atmosphere of variable relative humidity (RH).
Upon scans of decreasing RH, the
liquid crystalline lipid undergoes the chain-freezing transition to a
metastable gel state. By storage of the
sample at low RH, the gel transforms to a crystalline subgel designated
as SGI. Subsequent hydration induces
the conversion to a second subgel (SGII). The subgel
phases are characterized by the dense packing of the
acyl chains as indicated by the correlation field splitting of the
CH2 rocking and bending modes. Band
shifts
of phosphate group vibrations as well as the splitting of the carbonyl
stretching mode are correlated with the
hydration of the polar region of the bilayer given in terms of the
molar ratio of water to lipid. The
ν1,3(OH)
absorption band of water yields qualitative information about the
water−lipid interaction. The drastic
sharpening of this band in the SGI phase was attributed to
the reduction of water binding sites on the lipid,
leading to a more uniform population of water molecules adsorbed onto
the lipid headgroup. The external
conditions of phase transformation of DODPC were compared with
corresponding data of dimyristoylphosphatidylcholine (DMPC) having the same number of subsequent methylene
segments in the acyl chains.
Apparent differences can be attributed to the influence of the
diene groups representing a rigid spacer inserted
between the methylene chains and the ester groups of the lipid, i.e.,
in a position near the polar/apolar interface
of the bilayer.