The conformation of the alkyl chain in
α-dodecyl-ω-hydroxytris(oxyethylene)
(C12E3) in water has been studied
by C−D stretching infrared spectroscopy. This conformational
analysis is based on the fact that the
wavenumbers of the isolated C−D stretching vibrations are sensitive
to the conformation in the vicinity of
the C−D bond. Infrared spectra were measured for five
selectively monodeuterated species of C12E3,
namely
CH3(CH2)11-k
CHD(CH2)
k
-1(OCH2CH2)3OH,
where k = 1, 2, 4, 6, and 8, in the lamellar
(Lα) and isotropic
solution (L2) phases. The C−D stretching bands for
each of the monodeuterated species were assigned to
particular conformations of the specifically deuterated part of the
chain. From the observed intensities of the
C−D stretching bands, the fractions of the trans conformation around
the dodecyl C−C bonds and the
oxyethylene-adjoining O−C bond and the fractions of the consecutive
trans conformations around the two
adjoining bonds were evaluated. The conformational change at the
phase transition from L2 to Lα is
not
significant and only a small increase in the trans fraction is observed
for the C−C bonds close to the alkyl/oxyethylene interface. This implies that the conformational states
in the L2 and Lα phases in the vicinity
of
their boundary are substantially not different. In the
Lα phase, when the composition or the
temperature
approaches the region of the phase separation or transition, the trans
fractions for the C−C bonds closer to
the alkyl/oxyethylene interface and those closer to the chain terminal
decrease significantly. These observations
indicate that the conformational transformation from trans to gauche at
these chain positions makes the lamellar
structure less stable and leads eventually to the structural
destruction. The fraction of the consecutive trans
conformations may be used as a measure of the conformational order at
particular positions of the chain.
The present results show that the ordering is the highest in the
middle of the chain in the Lα and L2
phases.
This vibrational spectroscopic observation, together with the
previous NMR observations, indicates that the
alkyl/oxyethylene interface is flexible with respect to the
conformation and the orientation of the chain.