Monolayer liquid-condensed

The three general states of monolayers are illustrated in the pressure-area isotherm in Fig. IV-16. A low-pressure gas phase, G, condenses to a liquid phase termed the /i uid-expanded (LE or L ) phase by Adam [183] and Harkins [9]. One or more of several more dense, liquid-condensed phase (LC) exist at higher pressures and lower temperatures. A solid phase (S) exists at high pressures and densities. We briefly describe these phases and their characteristic features and transitions several useful articles provide a more detailed description [184-187]. 

The most common two-dimensional phases in monolayers are the gaseous, liquid-expanded, liquid-condensed, and solid phases. A schematic II-A isotherm is shown in Figure 3 for a fatty acid for the phase sequence gas (G) — G -l- liquid-expanded (LE) — LE — ... 

Initially, the compression does not result in surface pressure variations. Molecnles at the air/water interface are rather far from each other and do not interact. This state is referred to as a two-dimensional gas. Farther compression results in an increase in snrface pressure. Molecules begin to interact. This state of the monolayer is referred as two-dimensional liquid. For some compounds it is also possible to distingnish liqnid-expanded and liquid-condensed phases. Continnation of the compression resnlts in the appearance of a two-dimensional solid-state phase, characterized by a sharp increase in snrface pressure, even with small decreases in area per molecule. Dense packing of molecnles in the mono-layer is reached. Further compression results in the collapse of the monolayer. Two-dimensional structure does not exist anymore, and the mnltilayers form themselves in a non-con trollable way. 

FIG. 16 Fomation of a Langmuir lipid monolayer at the air/subphase interface and the subsequent crystallization of S-layer protein, (a) Amphiphilic lipid molecules are placed on the air/subphase interface between two barriers. Upon compression between the barriers, increase in surface pressure can be determined by a Wilhelmy plate system, (b) Depending on the final area, a liquid-expanded or liquid-condensed lipid monolayer is formed, (c) S-layer subunits injected in the subphase crystallized into a coherent S-layer lattice beneath the spread lipid monolayer and the adjacent air/subphase interface. 

It has been shown by FM that the phase state of the lipid exerted a marked influence on S-layer protein crystallization [138]. When the l,2-dimyristoyl-OT-glycero-3-phospho-ethanolamine (DMPE) surface monolayer was in the phase-separated state between hquid-expanded and ordered, liquid-condensed phase, the S-layer protein of B. coagulans E38/vl was preferentially adsorbed at the boundary line between the two coexisting phases. The adsorption was dominated by hydrophobic and van der Waals interactions. The two-dimensional crystallization proceeded predominately underneath the liquid-condensed phase. Crystal growth was much slower under the liquid-expanded monolayer, and the entire interface was overgrown only after prolonged protein incubation. 

Denicourt, N., Tancrede, P., Brullemans, M. and Teissie, J. (1989) The liquid condensed difiusional transition of dipalmitoylphosphoglycerocholine in monolayers. Biophys. Chem., 33, 63-70. 

The effect of phospholipid monolayers on the rate of charge transfer has been the subject of several experimental studies, but still there is a need for additional experimental evidence. For large molecular areas, the effect on the rate of ion transfer seems to be negligible [5]. An increasing surface concentration of lipids leads to liquid expanded states where the electrostatic effects are noticeable. An enhanced rate of ion transfer across monolayers of pure phospholipids has then been observed both for the cases of tracer [11,12] and supporting electrolyte ion transfer [13,17]. Finally, the blocking effect is dominant in liquid condensed monolayers [15]. 

From these descriptions, it is seen that the films may, under given experimental conditions, show three first-order transition states, such as (i) transition from the gaseous film to the liquid-expanded (Lex), (ii) transition from the liquid-expanded (Lex) to the liquid-condensed (Lco), and (iii) from Lex or Lco to the solid state if the temperature is below the transition temperature. The temperature above which no expanded state is observed has been found to be related to the melting point of the lipid monolayer. 

In Figure 2 the ir-A and AV-A plots for SODS on O.OIM NaCl sub-solutions having different pH values are shown. In all cases, phase transitions from liquid-expanded to liquid-condensed state are evident ( ). Acidification of the subsolution Increases the transition pressure but the transition is less pronounced at the lowest pH studied. This is also accompanied by an expansion of the condensed part of the curve. Small negative surface potentials are observed over most areas. The highest potential is obtained for film spread on the pH 2.2 subsolution. For small areas, the surface potential attains a positive value. This may be related to reorientation of the dipole moments of the molecules which occur once a threshold surface concentration is exceeded (O. Mlnglns and Pethlca (7) studied the monolayer properties of SODS on various sodium chloride solutions (0.1, 0.01 and O.OOIM) at 9.5 C, and they showed that the monolayer is only stable on the more concentrated salt solutions (0.1 and O.OIM). In this work, no noticeable... 

It was established in 1945 that monolayers of saturated fatty acids have quite complicated phase diagrams (13). However, the observation of the different phases has become possible only much more recendy owing to improvements in experimental optical techniques such as fluorescence, polarized fluorescence, and Brewster angle microscopies, and x-ray methods using synchrotron radiation, etc. Thus, it has become well accepted that lipid monolayer structures are not merely solid, liquid expanded, liquid condensed, etc, but that a faidy large number of phases and mesophases exist, as a variety of phase transitions between them (14,15). 

If the area of an insoluble monolayer is isothermally reduced still further, the compressibility eventually becomes very low. Because of the low compressibility, the states observed at these low values of a are called condensed states. In general, the isotherm is essentially linear, although it may display a well-defined change in slope as tt is increased, as shown in Figure 7.6. As menlioned above, the (relatively) more expanded of these two linear portions is the liquid-condensed state LC, and the less expanded is the solid state S. It is clear from the low compressibility of these states that both the LC and S states are held together by strong intermolecular forces so as to be relatively independent of the film pressure. 

The reaction between insoluble protein monolayer and injected soluble surface-active agent was time-dependent. Injection of SDS under an unbuffered (ca. pH 6.0) liquid condensed BSA monolayer increased... 

Contaminations are also responsible for the second difference between real and ideal isotherms. At 7rc the isotherm is not perfectly horizontal but slightly tilted, in particular at elevated temperatures. Contaminations are expelled from the liquid condensed phase. Thus, when more and more of the monolayer goes into the liquid condensed phase, contaminations are enriched in the remaining liquid expanded phase. This reduces the two-dimensional... 

A general thermodynamic theory and a statistical thermodynamic approach are presented, which describe the phase transitions in insoluble monolayers, particularly the inclined transition from a liquid-expanded to a liquid-condensed phase. 

Pallas. N.R. Pethica, B.A. Liquid-expanded to liquid-condensed transition in lipid monolayers at the air/ water interface. Langmuir 1985, 1, 509. 

The pressure/area isotherm for a cholesterol monolayer is of a very noncompressible liquid condensed type (Ries, 1976). The compressibility of a cholesterol monolayer is increased only slightly on the introduction of low concentrations of Azone (X = 0.2) but if the mole fraction of Azone in the film is increased to 0.4 and above, the compressibility increases dramatically and the film can be classed as liquid expanded. Another feature of these higher Azone concentrations is a small kink in the isotherm at approximately 32 mN m. This pressure is equal to the collapse pressure of a pure Azone monolayer found by these workers, and the kink in the Azone/cholesterol isotherm may be due to squeeze-out of Azone (Schuckler and Lee, 1991). 

A mixed monolayer consisting of stearic acid (9.9%), palmitic acid (36.8%), myristic acid (3.8%), oleic acid (33.1%), linoleic acid (12.5%), and palmitoleic acid (3.6%) produces an expanded area/pressure isotherm on which Azone has no apparent effect in terms of either expansion or compressibility (Schuckler and Lee, 1991). Squeeze-out of Azone from such films was not reported, but the surface pressures measured were not high enough for this to occur. The addition of cholesterol (to produce a 50 50 mixture) to this type of fatty acid monolayer results in a reduction of compressibility. However, the addition of ceramide has a much smaller condensing effect on the combined fatty acids (ratio 55 45), and the combination of all three components (free fatty acids/cholesterol/ceramide, 31 31 38) produces a liquid condensed film of moderate compressibility. The condensed nature of this film therefore results primarily from the presence of the membrane-stiffening cholesterol. In the presence of only small quantities of Azone (X = 0.025), the mixed film becomes liquid expanded in nature, and there is also evidence of Azone squeeze-out at approximately 32 mN m. ... 

In general, these mixed monolayers seem to be destabilized by the presence of Azone, which causes a concentration-dependent transition from solid or liquid condensed behavior to a liquid expanded type of film. There is also substantial evidence that squeeze-out of Azone occurs in all cases and at similar pressures. It is therefore possible that Azone can exist as a separate phase in stratum comeum lipids at a lower pressure than in monolayers of DPPC. In either case it seems likely that Azone may well exist in pools in the stratum comeum. 

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