Monolayer collapsed state

Other interesting Langmuir monolayer systems include spread thermotropic liquid crystals where a foam structure forms on expansion from a collapsed state [23]. Spread monolayers of clay dispersions form a layer of overlapping clay platelets that can be subsequently deposited onto solid substrates [24]. 

The monolayer stability limit is defined as the maximum pressure attainable in a film spread from solution before the monolayer collapses (Gaines, 1966). This limit may in some cases correspond directly to the ESP, suggesting that the mechanism of film collapse is a return to the bulk crystalline state, or may be at surface pressures higher than the ESP if the film is metastable with respect to the bulk phase. In either case, the monolayer stability limit must be known before such properties as work of compression, isothermal compressibility, or monolayer viscosity can be determined. 

The dynamic surface tension of a monolayer may be defined as the response of a film in an initial state of static quasi-equilibrium to a sudden change in surface area. If the area of the film-covered interface is altered at a rapid rate, the monolayer may not readjust to its original conformation quickly enough to maintain the quasi-equilibrium surface pressure. It is for this reason that properly reported II/A isotherms for most monolayers are repeated at several compression/expansion rates. The reasons for this lag in equilibration time are complex combinations of shear and dilational viscosities, elasticity, and isothermal compressibility (Manheimer and Schechter, 1970 Margoni, 1871 Lucassen-Reynders et al., 1974). Furthermore, consideration of dynamic surface tension in insoluble monolayers assumes that the monolayer is indeed insoluble and stable throughout the perturbation if not, a myriad of contributions from monolayer collapse to monomer dissolution may complicate the situation further. Although theoretical models of dynamic surface tension effects have been presented, there have been very few attempts at experimental investigation of these time-dependent phenomena in spread monolayer films. 

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). 

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. 

For both high and low molecular weights, there is a temperature dependence. It is also clear from these Figures that the critical surface pressure values (ttc) depend markedly on temperature. The collapse state is characterized by the collapse pressure or critical surface pressure (ire)- This surface pressure can be defined as the maximum pressure value that the monolayer can reach without expulsion or rejection of the material in order to form a new tridimensional phase. 

For reasons of fouling or deactivation, it may be desirable to be able to replace immobilized enzymes in time, and for this a programmable way of adsorption and release of enzymes would be very welcome. An example of this is the use of a 4nm thin polymer film that can be thermally switched between a hydrophilic (swollen) state at 20 °C and a more hydrophobic protein-adsorbing (collapsed) state at 48 °C, integrated into a micro hotplate with fast heating options so that a protein monolayer can be adsorbed and released within 1 s (Huber et al., 2003). 

It should be pointed out at this juncture that strict thermodynamics treatment of the film-covered surfaces is not possible [18]. The reason is difficulty in delineation of the system. The interface, typically of the order of a 1 -2 nm thick monolayer, contains a certain amount of bound water, which is in dynamic equilibrium with the bulk water in the subphase. In a strict thermodynamic treatment, such an interface must be accounted as an open system in equilibrium with the subphase components, principally water. On the other hand, a useful conceptual framework is to regard the interface as a 2-dimensional (2D) object such as a 2D gas or 2D solution [ 19,20]. Thus, the surface pressure 77 is treated as either a 2D gas pressure or a 2D osmotic pressure. With such a perspective, an analog of either p- V isotherm of a gas or the osmotic pressure-concentration isotherm, 77-c, of a solution is adopted. It is commonly referred to as the surface pressure-area isotherm, 77-A, where A is defined as an average area per molecule on the interface, under the provision that all molecules reside in the interface without desorption into the subphase or vaporization into the air. A more direct analog of 77- c of a bulk solution is 77 - r where r is the mass per unit area, hence is the reciprocal of A, the area per unit mass. The nature of the collapsed state depends on the solubility of the surfactant. For truly insoluble films, the film collapses by forming multilayers in the upper phase. A broad illustrative sketch of a 77-r plot is given in Fig. 1. 

AFM was used to investigate whether a series of related molecules could be analyzed when present as SAM. The system chosen was the cholesterol molecule. The molecule cholesterol is a very important biological lipid. A cholesterol molecule with one hydroxyl group is known to oxidize into a variety of structures. These oxidized cholesterol products play an important role in many biological diseases, such as blood clots. The AFM data of the collapsed film of cholesterol (when spread on the surface of water) shows that two-dimensional crystallization takes place with very characteristic butterfly shapes. This shows, for the first time in the literature, that not all lipid monolayers collapse to give a transition from monolayer to trilayer. This shows that the collapsed state may be a two-dimensional crystal phase. 

Cholestane (as formed after oxidation of cholesterol molecule) collapsed films ° show two step heights. These steps correspond to trilayers (length of cholestane x 3 = 50 A) and six layers (100 A). This indicates that in the collapsed state the trilayer is able to form higher order two-dimensional crystals, i.e., six layers. These analyses show that in the collapsed monolayers of different lipids the following phase equilibria (with equilibrium constant, K) exist ... 

This lack of solvent-induced monolayer disorder was also observed by Pemberton and coworkers (7). Pemberton and coworkers used Raman spectroscopy to examine Cis alkylsiloxane monolayers on a SiQ/Ag substrate and found little disruption of the alkyl chains in contact with acetonitrile, as well as water. The results of Carr and Harris (19), however, showed that a Cis chromatographic stationary phase assumes a collapsed structure in water. The stationary phase can evolve from this collapsed state with the addition of an organic modifier, such as acetonitrile, to the aqueous solvent. The modifier intercalates into the monolayer, causing an increase in volume, polarity, and alkyl chain order. 

Fig. 3 Langmuir film balance schematic, a - monolayer of lipid in a quasi gas state, b -state of maximal compaction indicative of molecular area, c - monolayer collapse point reflecting monolayer rigidity. Tested monolayer was palmitic acid over H2O to produce a typical surface pressure/molecular area isotherm.

The last phase transition is to the soHd state, where molecules have both positional and orientational order. If further pressure is appHed on the monolayer, it collapses, owiag to mechanical iastabiHty and a sharp decrease ia the pressure is observed. This coUapse-pressure depends on the temperature, the pH of the subphase, and the speed with which the barrier is moved. 

Nanoparticles of the semicondnctor titanium dioxide have also been spread as mono-layers [164]. Nanoparticles of TiOi were formed by the arrested hydrolysis of titanium iso-propoxide. A very small amount of water was mixed with a chloroform/isopropanol solution of titanium isopropoxide with the surfactant hexadecyltrimethylammonium bromide (CTAB) and a catalyst. The particles produced were 1.8-2.2 nm in diameter. The stabilized particles were spread as monolayers. Successive cycles of II-A isotherms exhibited smaller areas for the initial pressnre rise, attributed to dissolution of excess surfactant into the subphase. And BAM observation showed the solid state of the films at 50 mN m was featureless and bright collapse then appeared as a series of stripes across the image. The area per particle determined from the isotherms decreased when sols were subjected to a heat treatment prior to spreading. This effect was believed to arise from a modification to the particle surface that made surfactant adsorption less favorable. 

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. 

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