Two-dimensional facets in Langmuir monolayers of 1-O-hexadecyl-rac-glycerol at the air–water interface

We study the surface phase behavior in Langmuir monolayers of 1-O-hexadecyl-rac-glycerol (C16G) by film balance and Brewster angle microscopy over a wide range of temperatures. A cusp point followed by a pronounced plateau region in the pressure–area (π–A) isotherm indicates a first-order phase transition between a lower density liquid expanded (LE) phase and a higher density liquid condensed (LC) phase at the air–water interface. A wide variety of condensed domains are found to form just after the appearance of the cusp point. The observed surface morphology was compared with that of ethylene glycol mono-n  -hexadecyl ether (C16E1) that bears an ethylene oxide (EO) unit in the head-group. As usually observed, the domains of C16E1 are found to be circular at lower temperatures and fractal at higher temperatures. Contrary to this usual behavior, the domains of C16G are found to be strip-like structures at lower temperatures, which attain increasingly compact shape as the temperature increases and finally attain faceted structures at ⩾25°C. It is concluded that a higher degree of dehydration around the head-group region of C16G appreciably reduces the hydration-induced repulsive interactions between the head-groups and imparts to the molecules an increase in hydrophobicity, thereby a closer molecular packing. As a result, the molecules form increasingly compact domains as the temperature increases. Since the head-group of C16E1 is much smaller than that of C16G, dehydration effect cannot appreciably increase its hydrophobic character. Rather, increases in subphase temperature result in a decrease in the line tension of the interface giving fractal structures at higher temperatures. In addition, the changes in enthalpy (ΔH)(ΔH) and entropy (ΔS)(ΔS) values were also calculated to understand the thermodynamic nature of condensation of the molecules in the LE–LC transition region.

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