Collapse, of monolayers

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. 

We studied the surface pressure area isotherms of PS II core complex at different concentrations of NaCl in the subphase (Fig. 2). Addition of NaCl solution greatly enhanced the stability of monolayer of PS II core complex particles at the air-water interface. The n-A curves at subphases of 100 mM and 200 mM NaCl clearly demonstrated that PS II core complexes can be compressed to a relatively high surface pressure (40mN/m), before the monolayer collapses under our experimental conditions. Moreover, the average particle size calculated from tt-A curves using the total amount of protein complex is about 320 nm. This observation agrees well with the particle size directly observed using atomic force microscopy [8], and indicates that nearly all the protein complexes stay at the water surface and form a well-structured monolayer. 

Europium oxide (EU2O3) nanorods have been prepared by the sonication of an aqueous solution of europium nitrate in the presence of ammonia. In this reaction, ammonium ions adsorbed on the Eu(OH)3 particles (formed due to the collapse of the bubbles) results in the formation of a monolayer which then fuse together by hydrogen bonding leading to the formation of nanorods [28]. 

The difference between the static or equilibrium and dynamic surface tension is often observed in the compression/expansion hysteresis present in most monolayer Yl/A isotherms (Fig. 8). In such cases, the compression isotherm is not coincident with the expansion one. For an insoluble monolayer, hysteresis may result from very rapid compression, collapse of the film to a surfactant bulk phase during compression, or compression of the film through a first or second order monolayer phase transition. In addition, any combination of these effects may be responsible for the observed hysteresis. Perhaps understandably, there has been no firm quantitative model for time-dependent relaxation effects in monolayers. However, if the basic monolayer properties such as ESP, stability limit, and composition are known, a qualitative description of the dynamic surface tension, or hysteresis, may be obtained. 

The question arises as to whether the racemic compound was formed during the collapse of the monolayer or at a certain mono-... 

Respiratory effects are more likely to occur after inhalation exposure to high concentrations of chloroform. It has been demonstrated that chloroform has a destructive influence on the pulmonary surfactant (Enhoming et al. 1986). This effect is probably due to the solubility of phospholipids in the surfactant monolayer and can cause collapse of the respiratory bronchiole due to the sudden increase in inhalation tension. Immediate death after chloroform inhalation may be due principally to this effect in the lungs (Fagan et al. 1977). It is unlikely that exposure levels of chloroform in the general environment or at hazardous waste sites would be high enough to cause these severe respiratory effects. 

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). 

This value of Aco corresponds to the cholesterol molecule oriented with the hydroxyl group pointing toward the water phase. Atomic force microscope (AFM) studies of cholesterol in Langmuir-Blodgett (LB) films has shown that there exist domain structures (see Chapter X). This has been found for different collapse lipid monolayers (Birdi, 2003). Different data have provided much information about the orientation of lipid on water (Table 4.1). 

Grazing incidence x-ray diffraction (GID) measurements have indicated that both precollapse and collapsed state monolayers at the air-water interface can be crystalline (Birdi, 1989). A general procedure was delineated that could provide near-atomic resolution of two-dimensional crystal structures of -triacontanoic acid (C29H59COOH). A monolayer composed of rod-like molecules would generally pack in such a way that each molecule has six nearest neighbors, that is, hexagonal cell. 

Changes in the collapse pressure of monolayers prepared from mixtures of I and 5 as a function of will, therefore, be ideal. In the presence of interactions, rrc m will deviate, of course, from ideal behavior. Expanding Eq. (1) (or Eq. 5) and neglecting the higher order terms led to... 

Often there is evidence of interaction between stoichiometric proportions of the components of a mixed monolayer. Evidence of interaction can be sought by measuring partial molecular areas or by studying the collapse of the mixed film. The partial molecular areas of the components of a mixed film are usually different from the molecular areas of the pure components when interaction occurs. A mixed monolayer may collapse in one of two ways (a) with no... 

For asymmetric monodendrons, an increase in compression resulted in collapse of the dendrimer and the formation of a bilayer structure with the macromolecules compressed laterally with respect to the surface normal, with an axial ratio of 2 1. This situation is illustrated in Fig. 4.13. These dendritic macromolecules are flexible enough to assume a prolate conformation under modest lateral compression in a Langmuir trough. Polyamidoamine (PAMAM) dendrimers [109] were also used by Tsukruk et al. [110] to fabricate self - assembled monolayers. The thickness of all the monolayers were much smaller than the diameter of dendritic macromolecules in solution. This behavior can indicate collapse of the dendritic macromolecules, which become highly compressed along the surface normal and flattened. (See Fig. 4.13b). 

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