Monolayer amphiphilic molecules

In a traditional concept of a Langmuir monolayer, amphiphilic molecules are spread at the air-water interface. After the evaporation of organic solvent, the amphiphilic molecules stay at the interface. When compressed at this interface, the amphiphilic molecules start to reorient themselves and eventually form a compaet monolayer with the hydrophilic moieties embedded in the water phase and the hydrophobic tails extruded into the air phase [6]. During this orientation and organization process, the amphiphilic molecules have the freedom to move around at the interface. This freedom has provided a unique opportunity for supramolecular chemists. 

Harris J and Rice S A 1988 A lattice model of a supported monolayer of amphiphile molecules—Monte Carlo simulations J. Ohem. Phys. 88 1298-306... 

A drop of a dilute solution (1%) of an amphiphile in a solvent is typically placed on tlie water surface. The solvent evaporates, leaving behind a monolayer of molecules, which can be described as a two-dimensional gas, due to tlie large separation between tlie molecules (figure C2.4.3). The movable barrier pushes tlie molecules at tlie surface closer together, while pressure and area per molecule are recorded. The pressure-area isotlienn yields infonnation about tlie stability of monolayers at tlie water surface, a possible reorientation of tlie molecules in tlie two-dimensional system, phase transitions and changes in tlie confonnation. Wliile being pushed togetlier, tlie layer at... 

The monolayer resulting when amphiphilic molecules are introduced to the water—air interface was traditionally called a two-dimensional gas owing to what were the expected large distances between the molecules. However, it has become quite clear that amphiphiles self-organize at the air—water interface even at relatively low surface pressures (7—10). For example, x-ray diffraction data from a monolayer of heneicosanoic acid spread on a 0.5-mM CaCl2 solution at zero pressure (11) showed that once the barrier starts moving and compresses the molecules, the surface pressure, 7T, increases and the area per molecule, M, decreases. The surface pressure, ie, the force per unit length of the barrier (in N/m) is the difference between CJq, the surface tension of pure water, and O, that of the water covered with a monolayer. Where the total number of molecules and the total area that the monolayer occupies is known, the area per molecules can be calculated and a 7T-M isotherm constmcted. This isotherm (Fig. 2), which describes surface pressure as a function of the area per molecule (3,4), is rich in information on stabiUty of the monolayer at the water—air interface, the reorientation of molecules in the two-dimensional system, phase transitions, and conformational transformations. 

The terminology of L-B films originates from the names of two scientists who invented the technique of film preparation, which transfers the monolayer or multilayers from the water-air interface onto a solid substrate. The key of the L-B technique is to use the amphiphih molecule insoluble in water, with one end hydrophilic and the other hydrophobic. When a drop of a dilute solution containing the amphiphilic molecules is spread on the water-air interface, the hydrophilic end of the amphiphile is preferentially immersed in the water and the hydrophobic end remains in the air. After the evaporation of solvent, the solution leaves a monolayer of amphiphilic molecules in the form of two-dimensional gas due to relatively large spacing between the molecules (see Fig. 15 (a)). At this stage, a barrier moves and compresses the molecules on the water-air interface, and as a result the intermolecular distance decreases and the surface pressure increases. As the compression from the barrier proceeds, two successive phase transitions of the monolayer can be observed. First a transition from the gas" to the liquid state. 

The most commonly used amphiphiles to build L-B hlms for tribological applications are the straight chain hydrocarbon compounds with simple functional groups such as the fatty acids, including stearic acids, arachidic acids, and behenic acids [32], but other amphiphilic molecules, e.g., 2,4-heneicosanedione and 2-docosylamina-5-nitropyridine, are also applied in some cases. There are two major systems of self-assembled monolayers, namely the alkylsilance derivatives (e.g., OTS, octadecyltrichlorosilane) on hydroxylated surfaces and the alkanethiols on metal substrates, which have been investigated extensively to examine their properties as solid lubricants and protective surface films [31 ]. 

Self-assembled monolayers of amphiphilic molecules have been deposited at surfaces since Langmuir and Blodgett developed their dip coating deposition method in 1937.4 These were briefly discussed in Chapter 10 in relation to thiol... 

It is thus seen that the II of a monolayer is the lowering of surface tension due to the presence of monomolecular film. This arises from the orientation of the amphiphile molecules at the air-water or oil-water interface, where the polar group would be oriented towards the water phase, while the nonpolar part (hydrocarbon) would be oriented away from the aqueous phase. This orientation produces a system with minimum free energy. 

The most fascinating characteristic some amphiphile molecules exhibit is that, when mixed with water, they form self-assembly structures. This was already discussed in Chapter 2 on micelle formation. Since most of the biological lipids also exhibit self-assembly structure formation, this subject has been given much attention in the literature (Birdi, 1999). Lipid monolayer studies thus provide a very useful method to obtain information about SAM formation, both concerning technical systems and cell bilayer structures. 

It is found that, even a monolayer of lipid (on water), when compressed can undergo various states. In the following text, the various states of monomolecular films will be described as measured from the surface pressure, n, versus area, A, isotherms, in the case of simple amphiphile molecules. On the other hand, the Il-A isotherms of biopolymers will be described separately since these have a different nature. 

The measurements of n versus A isotherms generally exhibit, when compressed, a sharp break in the isotherms that has been connected to the collapse of the mono-layer under given experimental conditions. The monolayer of some lipids, such as cholesterol, is found to exhibit an unusual isotherm (Figure 4.7). The magnitude of FI increases very little as compression takes place. In fact, the collapse state or point is the most useful molecular information from such studies. It has been found that this is the only method that can provide information about the structure and orientation of amphiphile molecules at the surface of water (Birdi, 1989). 

The structure and orientation of the deposited amphiphile molecules have been found to be governed by the angle of contact between the monolayer and the solid surface. The deposited monolayers, in general, have been characterized as X- Y-, and Z -type, and their molecular arrangements can be described as follows. 

Maierhofer AP, Brettreich M, Burghardt S, Vostrowsky O, Hirsch A, Langridge S, Bayer TM. Structure and electrostatic interaction properties of monolayers of amphiphilic molecules... 

Some amphiphilic molecules such as oleic acid and hexadecyl alcohol containing an alkyl chain and a polar head group form monolayers on the surface of water. The polar head groups of these molecules are attracted to and are in contact with water while their hydrocarbon tails protrude above it (Figure 15). The term monolayer implies the presence of a uniform mono-molecular film on the surface of water. Monolayer films can be classified as gaseous, liquid, or solid depending upon the degree of compression and the effective area per molecule. Clearly the liquid phase of a monolayer film and, more so, the solid represent constrained environments for individual molecules of amphiphiles. Monolayers, just like micelles, are dynamic species. 

Figure 15. (a) A schematic representation of organic amphiphilic molecules at air-water interface, (b) Schematic representation of the various deposition modes for monolayer films and the resulting L-B assemblies. (Reproduced with permission from H. Kuhn, D. Mobius, and H. Bucher, Physical Methods of Chemistry, Vol. I, Part IIIB, A. Weissberger and B. W. Rossiter, Eds., Wiley, New York, 1972, p. 577.)... 

Figure 4.1. Schematic diagram of the formation of a Langmuir-Blodgett film. Each amphiphilic molecule is represented by a circle with a tail, where the circle denotes the hydrophilic end of the molecule. The left hand diagram represents the deposition of a monolayer on a hydrophilic substrate moving upwards. The right hand diagram represents the deposition of a second layer during the downward movement of the substrate.

The adsorption of amphiphilic molecules at the surface of a liquid can be so strong that a compact monomolecular film, abbreviated as monolayer, is formed. There are amphiphiles which, practically, do not dissolve in the liquid. This leads to insoluble monolayers. In this case the surface excess T is equal to the added amount of material divided by the surface area. Examples of monolayer forming amphiphiles are fatty acids (CH3(CH2) c 2COOH) and long chain alcohols (CH3(CH2)nc iOH) (see section 12.1). 

Figure 13.2 Langmuir and PLAWM trough with a monolayer indicated by amphiphilic molecules.

The analogy between three- and two-dimensional phase diagrams can be carried much further. Monomolecular amphiphilic films show ordered phases similar to three-dimensional systems [579], The phases of an amphiphilic monolayer can be detected most conveniently in pressure-area (7r-versus-OA) isotherms. These may look different for different substances. The behavior of simple amphiphilic molecules, like long-chain alcohols, amines, or acids, was extensively investigated (reviews Refs. [580,581]). In monolayers so-called mesophases can occur. In a mesophase the tail groups are ordered over relatively large areas, while the order in the hydrophilic head groups is only over a much smaller distances. 

Amphiphilic molecules form monomolecular films on liquid surfaces. Some amphiphiles, such as phospholipids, with a large hydrophobic tail are practically insoluble in water and therefore form insoluble monolayers at the air-water interface. 

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