Maxwell displacement current allows to study structural changes of gramicidin A in monolayers at the air-water...

We applied methods of measurement Maxwell displacement current (MDC) pressure-area isotherms and dipole potential for analysis of the properties of gramicidin A (gA) and mixed gA/DMPC monolayers at an air-water interface. The MDC method allowed us to observe the kinetics of formation of secondary structure of gA in monolayers at an air-water interface. We showed, that secondary structure starts to form at rather low area per molecule at which gA monolayers are in gaseous state. Changes of the MDC during compression can be attributed to the reorientation of dipole moments in a gA double helix at area 7 nm(2)/molecule, followed by the formation of intertwined double helix of gA. The properties of gA in mixed monolayers depend on the molar fraction of gA/DMPC. At higher molar fractions of gA (around 0.5) the shape of the changes of dipole moment of mixed monolayer was similar to that for pure gA. The analysis of excess free energy in a gel (18( ) degrees C) and in a liquid-crystalline phase (28( ) degrees C) allowed us to show influence of the monolayer structural state on the interaction between gA and the phospholipids. In a gel state and at the gA/DMPC molar ratio below 0.17 the aggregates of gA were formed, while above this molar ratio gA interacts favorably with DMPC. In contrast, for DMPC in a liquid-crystalline state aggregation of gA was observed for all molar fractions studied. The effect of formation ordered structures between gA and DMPC is more pronounced at low temperatures.