Aggregation in Langmuir films is usually understood as being a disorderly grouping of molecules turning into chaotic three-dimensional aggregates and is considered an unwanted phenomenon causing irreversible changes. In this work we present the studies of 11 compounds from the group of specific surfactants, known as bolaamphiphiles, that exhibit reversible aggregation and, in many cases, transition to well-defined multilayers, which can be considered as a layering transition. These bolaamphiphiles incorporate rigid π-conjugated aromatics as hydrophobic cores, glycerol-based polar groups and hydrophobic lateral chains. Molecules of different shapes (X-, T-, and anchor) were studied and compared. The key property of these compounds is the partial fluorination of the lateral chains linked to the rigid cores of the molecules. The most interesting feature of the compounds is that, depending on their shape and degree of fluorination, they are able to resist aggregation and preserve a monolayer structure up to relatively high surface pressures (T-shaped and some X-shaped molecules), or create well-defined trilayers (X- and anchor-shaped molecules). Experimental studies were performed using Langmuir balance, surface potential and X-ray reflectivity measurements.

Langmuir films of four X-shaped bolaamphiphiles were studied using surface pressure and Kelvin potential measurements, Brewster angle microscopy and X-ray reflectivity. The partially fluorinated bolaamphiphiles exhibit an unusual reversibility and reproducibility of Langmuir isotherms, and create very stable and well defined single- or triple layers which can be transferred to solid substrates.

We measure the frequency of collective molecular precession as a function of temperature in the ferroelectric liquid crystalline monolayer at the water-air interface. This movement is driven by the unidirectional flux of evaporating water molecules. The collective rotation in the monolayer with angular velocities ω ~ 1 s(-1) (at T = 312 K) to 10(-2) s(-1) (at T = 285.8 K) is 9 to 14 orders of magnitude slower than rotation of a single molecule (typically ω ~ 10(9) to 10(12) s(-1)). The angular velocity reaches 0 upon approach to the two dimensional liquid-to-solid transition in the monolayer at T = 285.8 K. We estimate the rotational viscosity, γ1, in the monolayer and the torque, Γ, driving this rotation. The torque per molecule equals Γ = 5.7 × 10(-8) pN nm at 310 K (γ1 = 0.081 Pa s, ω = 0.87 s(-1)). The energy generated during one turn of the molecule at the same temperature is W = 3.5 × 10(-28) J. Surprisingly, although this energy is 7 orders of magnitude smaller than the thermal energy, kBT (310 K) = 4.3 × 10(-21) J, the rotation is very stable. The potential of the studied effect lies in the collective motion of many (>10(12)) "nano-windmills" acting "in concerto" at the scale of millimetres. Therefore, such systems are candidates for construction of artificial molecular engines, despite the small energy density per molecular volume (5 orders of magnitude smaller than for a single ATPase).