Surface pressure surfactants

Patterns of ordered molecular islands surrounded by disordered molecules are common in Langmuir layers, where even in zero surface pressure molecules self-organize at the air—water interface. The difference between the two systems is that in SAMs of trichlorosilanes the island is comprised of polymerized surfactants, and therefore the mobihty of individual molecules is restricted. This lack of mobihty is probably the principal reason why SAMs of alkyltrichlorosilanes are less ordered than, for example, fatty acids on AgO, or thiols on gold. The coupling of polymerization and surface anchoring is a primary source of the reproducibihty problems. Small differences in water content and in surface Si—OH group concentration may result in a significant difference in monolayer quahty. Alkyl silanes remain, however, ideal materials for surface modification and functionalization apphcations, eg, as adhesion promoters (166—168) and boundary lubricants (169—171). 

Ruckenstein and Li proposed a relatively simple surface pressure-area equation of state for phospholipid monolayers at a water-oil interface [39]. The equation accounted for the clustering of the surfactant molecules, and led to second-order phase transitions. The monolayer was described as a 2D regular solution with three components singly dispersed phospholipid molecules, clusters of these molecules, and sites occupied by water and oil molecules. The effect of clusterng on the theoretical surface pressure-area isotherm was found to be crucial for the prediction of phase transitions. The model calculations fitted surprisingly well to the data of Taylor et al. [19] in the whole range of surface areas and the temperatures (Fig. 3). The number of molecules in a cluster was taken to be 150 due to an excellent agreement with an isotherm of DSPC when this... 

According to Eyring (Moore and Eyring, 1938) and Joly (1956), Newtonian flow in a monolayer is the result of a cohesive attraction between surfactant molecules. For every molecule that flows from higher to lower surface pressure in a motion parallel to the canal walls, there is another molecule ready to fill the hole vacated by the first. The mechanism for this cohesive flow is presumably attractive van der Waals interactions between hydrocarbon chains. This model assumes that the average intermolecular separation in a surface-continuous monolayer does not exceed the cross-sectional area of the molecule as defined by the average molecular area A of the film at the surface pressure n in the pressurized compartment of the viscometer. 

Figure 17 shows the 11/A isotherms of racemic and enantiomeric films of the methyl esters of 7V-stearoyl-serine, -alanine, -tryptophan, and -tyrosine on clean water at 25°C. Although there appears to be little difference between the racemic and enantiomeric forms of the alanine surfactants, the N-stearoyl-tyrosine, -serine, and -tryptophan surfactants show clear enantiomeric discrimination in their WjA curves. This chiral molecular recognition is first evidenced in the lift-off areas of the curves for the racemic versus enantiomeric forms of the films (Table 2). As discussed previously, the lift-off area is the average molecular area at which a surface pressure above 0.1 dyn cm -1 is first registered. The packing order differences in these films, and hence their stereochemical differentiation, are apparently maintained throughout the compression/expansion cycles. 

The instability of these chiral monolayers may be a reflection of the relative stabilities of their bulk crystalline forms. When deposited on a clean water surface at 25°C, neither the racemic nor enantiomeric crystals of the tryptophan, tyrosine, or alanine methyl ester surfactants generate a detectable surface pressure, indicating that the most energetically favorable situation for the interfacial/crystal system is one in which the internal energy of the bulk crystal is lower than that of the film at the air-water interface. Only the racemic form of JV-stearoylserine methyl ester has a detectable equilibrium spreading pressure (2.6 0.3dyncm 1). Conversely, neither of its enantiomeric forms will spread spontaneously from the crystal at this temperature. 

Taken together, the equilibrium spreading pressures of films spread from the bulk surfactant, the dynamic properties of the films spread from solution, the shape of the Ylj A isotherms, the monolayer stability limits, and the dependence of all these properties on temperature indicate that the primary mechanism for enantiomeric discrimination in monolayers of SSME is the onset of a highly condensed phase during compression of the films. This condensed phase transition occurs at lower surface pressures for the R( —)- or S( + )-films than for their racemic mixture. 

The classic studies of Saunders( 17) demonstrated that in the presence of excess surfactant methyl cellulose (MC) would desorb from monodispersed polystyrene latices. MC is one of the most surface active water-soluble polymers (W-SPs) and it will readily dominate the surface pressure 7T (7T = cre - cr t where cr is the surface tension of water and is the surface tension of the aqueous polymer solution) of the aqueous solution. For example, hydroxyethyl cellulose (HEC) lowers the surface tension of water much less than MC or HPMC, and when the combination of HEC and MC or HPMC in water is studied, there is no notable influence of HEC on the surface pressure (Figure 2). 

The differences in time-dependent adsorption behavior between 99% PVAC at 25° and 50°C demonstrate the influence of intra- and intermolecular hydrogen bonding in the adsorption process. The limiting surface pressure of the hydrophobic water-soluble polymer appears to be 33 mN/m, approximately 7 mN/m below that of commonly used surfactants. The rate of attainment of equilibrium surface pressure values is faster if there is uniformity of the hydrophobic segments among the repeating units of the macromolecule. 

Fig. 4.6 Correlation of relative dynamic surface pressures with foam kinetics data dh/dt as a function of the type of surfactant, alkyl chain length and salt concentration [47],...

Figure 8. (A) Schematic representation of the shape of the function f(rt). The arrows represent the first order like phase transition effect. The two straight lines are f(tt) = 17.5tt + 20.0 and f(n) = O.Olrc, respectively. (B) Schematic representation of the relationship between the surface pressure (ji) and the effective concentration of surfactant at the air/water interface (T f). The solid and dashed lines represent the expected and ideal relationships, respectively.

Now we consider the relationship between the effective concentration(reff) and the surface pressure(tt) at the air/water interface. Ideally, the surface pressure is directly proportional to the concentration of surfactants. However, as the actual it-A isotherms show several specific effects, such as limiting area and points of inflexion, we shall assume the following relationships ... 

Lundquist and the Stenhagens concentrated their efforts on the physical aspects of monolayer chemistry and did not elaborate then-work much in the direction of structural variation of the surfactant molecules. Their results show clearly, however, that the response of chiral monolayers to changes in surface pressure and temperature is sharply dependent on both the molecular structure of the surfactant and the optical purity of the sample. The Stenhagens were keenly aware of the possible application of the monolayer technique to stereochemical and other structural problems (72) however, they failed to exploit the full potential suggested by their initial results and, instead, pursued the field of mass spectrometry, to which they made substantial contributions. 

The spread mixed lipid monolayer studies provide information about the packing and orientation of such molecules at the water interface. These interfacial characteristics affect many other systems. For instance, mixed surfactants are used in froth flotation. The monolayer surface pressure of a pure surfactant is measured after the injection of the second surfactant. From the change in n, the interaction mechanism can be measured. The monolayer method has also been used as a model biological membrane system. In the latter BLM, lipids are found to be mixed with other lipidlike molecules (such as cholesterol). Hence, mixed monolayers of lipids + cholesterol have been found to provide much useful information on BLM. The most important BLM and temperature melting phenomena is the human body temperature regulation. Normal body temperature is 37°C (98°F), at which all BLM function efficiently. 

A generalized nonideal mixed monolayer model based on the pseudo-phase separation approach is presented. This extends the model developed earlier for mixed micelles (J. Phys. Chem. 1983 87, 1984) to the treatment of nonideal surfactant mixtures at interfaces. The approach explicity takes surface pressures and molecular areas into account and results in a nonideal analog of Butler s equation applicable to micellar solutions. Measured values of the surface tension of nonideal mixed micellar solutions are also reported and compared with those predicted by the model. 

---