Monolayer Behavior of Pure F-DPPC and Mixed Films with DPPC Studied by Epifluorescence Microscopy and Infrared Reflection Absorption Spectroscopy.

Abstract The monolayer behavior of a DPPC derivative with a single fluorination in one of its terminal methyl groups (F-DPPC) at air-water interface was investigated by epifluorescence microscopy and infrared reflection absorption spectroscopy (IRRAS). Epifluorescence microscopy was utilized to study the shape and morphology of liquid-condensed (LC) domains observed upon compression of the film. IRRAS was employed for the determination of chain order and orientation. The shapes of LC-domains in a monolayer of F-DPPC are more dependent on the rate of compression than those of DPPC. The LC domains of F-DPPC display pronounced fractal growth patterns depending on the compression speed. The evolution of LC domain occurs under dominating electrostatic dipolar forces in F-DPPC. IRRAS measurements with the analysis of the frequency of the methylene stretching vibrations as a function of film compression show that the acyl chains in an F-DPPC monolayer in the LE-phase are more disordered than those in a DPPC film. The reason for the higher chain disorder in LE phase F-DPPC monolayers is a back folding of the fluorinated sn-2 chain terminus towards the air-water interface leading to larger molecular area requirement. Angular dependent IRRA spectra of monolayers at a surface pressures of 30 mN m-1 show that in the LC phase DPPC and F-DPPC exhibit a similar tilt of the acyl chains of ca. 28-30° relative to the surface normal. F-DPPC is ideally miscible with L-DPPC-d62 having the same chirality, as indicated by epifluorescence images and by IRRAS. However, the LC domains in an equimolar mixture of D-DPPC and F-DPPC having opposite chirality show multi-lobed complex domain patterns indicating chiral phase separation within LC domains.