In the traditional concept, a stable Langmuir monolayer can be formed from
amphiphilic molecules at the air-water interface with their hydrophobic alk
yl chains oriented toward the air and the polar moieties embedded in the wa
ter. The intermolecular interactions between the polar moieties and the wat
er subphase as well as the van der Waals interactions between the alkyl cha
ins are requisite to hold together the molecules of the ordered Langmuir mo
nolayers. Pure hydrocarbon chains without any polar moieties cannot form a
Langmuir monolayer. In contrast to this traditional concept, we now report
the discovery of an unusual Langmuir monolayer formed from a disubstituted
urea lipid molecule (PDA-UR). The unique property of this monolayer exists
in the fact that the polar moiety of the lipid molecule is actually suspend
ed in the air phase while one of the hydrophobic tails is in contact with w
ater. The existence of such a nontraditional monolayer is attributed to the
strong hydrogen bonding network formation between the urea functional grou
ps in the air phase. This unusual Langmuir monolayer model is soundly suppo
rted by various experimental investigations, which include the surface pres
sure-area isotherm and ellipsometry measurements, FT-IR and UV-vis absorpti
on spectroscopic studies, as well as Brewster angle and scanning tunneling
microscopic observations.