Abstract
The hydrogen-bonding network formed between a triaminotriazine amphiphile (2C18TAZ, 1) and complementary barbituric acid (BA, 2) at the air−water interface is investigated by polarization-modulated infrared reflection absorption spectroscopy (PM-IRRAS). The molecular structure and orientation of the 1:1 hydrogen-bonding network at the air−water interface is revealed in this study. Without the addition of BA to the subphase, the NH2 scissoring of 2C18TAZ appeared in the spectrum as a broad negative absorption band between 1660 and 1605 cm-1, indicating its perpendicular orientation to the air−water interface. When BA was added to the subphase, the NH2 scissoring absorption band from the triaminotriazine moiety disappeared due to the complementary hydrogen bonding of BA to the 2C18TAZ monolayer. The formation of the rigid 1:1 hydrogen-bonding network also resulted in the disappearance of one of the ring quadrant stretch absorption bands of the 2C18TAZ molecule. New bands which are attributed to the vibration of BA can be clearly seen. Particularly, the CO stretch from BA shows up in the spectra as two negative absorption bands around 1700 cm-1. The negative signature of these two bands suggests that the BA molecules are oriented in the hydrogen-bonding network with the C-2 carbonyl positioned vertically toward the air, and the C-4 and C-6 carbonyls directed into the water subphase. This is consistent with formation of an assembly which optimizes the use of complementary hydrogen bonding between two components. Furthermore, the effect of competitive polar organic solvents in subphase, such as DMSO, on the hydrogen-bonding network has also been observed in this study. Compared to the previous IRRAS studies on the similar monolayers, the sensitivity of PM-IRRAS is obviously improved. PM-IRRAS will likely become a powerful analytical technique for the characterization of molecular structure and orientation of Langmuir monolayers at the air−water interface.
