Air-water interface, monolayers

The adsorption of mixed surfactants at the air—water interface (monolayer formation) is mechanistically very similar to mixed micelle formation. The mixed monolayer is oriented so that the surfactant hydrophilic groups are adjacent to each other. The hydrophobic groups are removed from the aqueous environment and are in contact with other hydrophobic groups or air. Therefore, the forces tending to cause monolayers to form are similar to those causing micelles to form and the thermodynamics and interactions between surfactants are similar in the two aggregation processes. 

For studies involving air/water interface monolayers or Langmuir-Blodgett techniques, a submarine UME is required. Such an electrode is immersed in the solution and approached to the layer from below (110, 160). The submarine electrode consists simply of a conventional UME of the desired metal and size that is fixed to a glass J tube by Teflon tape or Epoxy (Figure 12.34). 

A number of assembly methods employ self-assembly of nanoparticles at the air-water interface. Monolayers (and subsequent multilayers) can be formed at the interface due particle interaction and transferred to a solid substrate by controlled dip-coating and vertical deposition methods similar to Langmuir-Blodgett film deposition [81-86]. Regular monolayers of polymer colloids can also be assembled via an electrohydrodynamic route, whereby electrophoretically deposited particles between two electrodes can be manipulated to cluster in the presence of an electric field. On application of an AC or DC field, contrary to electrostatic norms, the like-charged particles are observed to coalesce producing large close-packed 2D crystalline domains [87]. 

When polymerization is effected at the air-water interface, monolayer polymer films may result. Such films have attracted a great deal of attention in recent years by virtue of their similarity to biological membranes. Polymeric films do not really fall within the strict definition of liquid crystal polymers. However, the molecular arrangement of the side chains resembles that found in many liquid crystal phases, most notably the lamellar phase, and could therefore realistically be described as one half of a lamellar sheet. Bilayer films, on the other hand, may be thought of as a single lamellar layer, and therefore the comparison becomes even more appropriate. The technical applications of polymer membranes are extremely diverse and for these reasons a short section will be devoted to their history, their uses and their current status. 

The external reflection of infrared radiation can be used to characterize the thickness and orientation of adsorbates on metal surfaces. Buontempo and Rice [153-155] have recently extended this technique to molecules at dielectric surfaces, including Langmuir monolayers at the air-water interface. Analysis of the dichroic ratio, the ratio of reflectivity parallel to the plane of incidence (p-polarization) to that perpendicular to it (.r-polarization) allows evaluation of the molecular orientation in terms of a tilt angle and rotation around the backbone [153]. An example of the p-polarized reflection spectrum for stearyl alcohol is shown in Fig. IV-13. Unfortunately, quantitative analysis of the experimental measurements of the antisymmetric CH2 stretch for heneicosanol [153,155] stearly alcohol [154] and tetracosanoic [156] monolayers is made difflcult by the scatter in the IR peak heights. 

Many complex systems have been spread on liquid interfaces for a variety of reasons. We begin this chapter with a discussion of the behavior of synthetic polymers at the liquid-air interface. Most of these systems are linear macromolecules however, rigid-rod polymers and more complex structures are of interest for potential optoelectronic applications. Biological macromolecules are spread at the liquid-vapor interface to fabricate sensors and other biomedical devices. In addition, the study of proteins at the air-water interface yields important information on enzymatic recognition, and membrane protein behavior. We touch on other biological systems, namely, phospholipids and cholesterol monolayers. These systems are so widely and routinely studied these days that they were also mentioned in some detail in Chapter IV. The closely related matter of bilayers and vesicles is also briefly addressed. 

Proteins, like other macromolecules, can be made into monolayers at the air-water interface either by spreading, adsorption, or specific binding. Proteins, while complex polymers, are interesting because of their inherent surface activity and amphiphilicity. There is an increasing body of literature on proteins at liquid interfaces, and here we only briefly discuss a few highlights. 

A study by Bames and co-workers of the equilibrium spreading behavior of dimyristol phosphatidylcholine (DMPC) reconciles the differences between spreading of bulk solids and dispersions of liposomes [41]. This study shows the formation of multibilayers below the monolayer at the air-water interface. An incipient phase separation, undetectable by microscopy, in DMPC-cholesterol... 

The SHG/SFG technique is not restricted to interface spectroscopy of the delocalized electronic states of solids. It is also a powerful tool for spectroscopy of electronic transitions in molecules. Figure Bl.5.13 presents such an example for a monolayer of the R-enantiomer of the molecule 2,2 -dihydroxyl-l,l -binaphthyl, (R)-BN, at the air/water interface [ ]. The spectra reveal two-photon resonance features near wavelengths of 332 and 340 mu that are assigned to the two lowest exciton-split transitions in the naphtli-2-ol... 

Zhao X L, Ong S W and Eisenthal K B 1993 Polarization of water-molecules at a charged interface. Second harmonic studies of charged monolayers at the air/water interface Chem. Phys. Lett. 202 513-20... 

Monolayers at the Air—Water Interface. Molecules that form monolayers at the water—air interface are called amphiphiles or surfactants (qv). Such molecules are insoluble in water. One end is hydrophilic, and therefore is preferentially immersed in the water the other end is hydrophobic, and preferentially resides in the air, or in a nonpolar solvent. A classic example of an amphiphile is stearic acid, C H COOH, wherein the long hydrocarbon... 

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. 

In tbe first attempt to prepare a two-dimensional crystalline polymer (45), Co y-radiation was used to initiate polymerization in monolayers of vinyl stearate (7). Polymerization at the air—water interface was possible but gave a rigid film. The monomeric monolayer was deposited to give X-type layers that could be polymerized in situ This polymerization reaction, quenched by oxygen, proceeds via a free-radical mechanism. 

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). 

Fig.4.53. Experimental and simulated PM (polarization modulated) IRRAS spectra of single monolayers of (A) PEG and (B) K(LK)7 at the air-water interface. The surface pressure was 20 mN m [4.281],...

Another interesting class of phase transitions is that of internal transitions within amphiphilic monolayers or bilayers. In particular, monolayers of amphiphiles at the air/water interface (Langmuir monolayers) have been intensively studied in the past as experimentally fairly accessible model systems [16,17]. A schematic phase diagram for long chain fatty acids, alcohols, or lipids is shown in Fig. 4. On increasing the area per molecule, one observes two distinct coexistence regions between fluid phases a transition from a highly diluted, gas -like phase into a more condensed liquid expanded phase, and a second transition into an even denser... 

Shinkai [15] concluded that p-zert-butyl calix[n]ar-ene tetra esters form stable monolayers at the air-water interface and the metal responds, therein, quite differently from that in solution. They reported that examination of the metal template effect on the conformer distribution established that when the metal cation present in the base used serves as a template, the cone conformer results are predominant [16]. Hence, Na in... 

The process of adsorption of polyelectrolytes on solid surfaces has been intensively studied because of its importance in technology, including steric stabilization of colloid particles [3,4]. This process has attracted increasing attention because of the recently developed, sophisticated use of polyelectrolyte adsorption alternate layer-by-layer adsorption [7] and stabilization of surfactant monolayers at the air-water interface [26], Surface forces measurement has been performed to study the adsorption process of a negatively charged polymer, poly(styrene sulfonate) (PSS), on a cationic monolayer of fluorocarbon ammonium amphiphilic 1 (Fig. 7) [27],... 

Salts of fatty acids are classic objects of LB technique. Being placed at the air/water interface, these molecules arrange themselves in such a way that its hydrophilic part (COOH) penetrates water due to its electrostatic interactions with water molecnles, which can be considered electric dipoles. The hydrophobic part (aliphatic chain) orients itself to air, because it cannot penetrate water for entropy reasons. Therefore, if a few molecnles of snch type were placed at the water surface, they would form a two-dimensional system at the air/water interface. A compression isotherm of the stearic acid monolayer is presented in Figure 1. This curve shows the dependence of surface pressure upon area per molecnle, obtained at constant temperature. Usually, this dependence is called a rr-A isotherm. 

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. 

The other method of monolayer transfer from the air/water interface onto solid substrates is illustrated in Figure 2. This method is called the Langmuir-Schaefer technique, or horizontal lift. It was developed in 1938 by I. Langmuir and V. Schaefer for deposition of protein layers. Prepared substrate horizontally touches the monolayer, and the layer transfers itself onto the substrate surface. The method is often used for the deposition of rigid monolayers and for protein monolayers, hi both cases the apphcation of the Lang-muir-Blodgett method produces defective films. 

A large number of potential applications for organized protein monolayers have recently motivated considerable research activity in this field (Boussaad et al. 1998, Kiselyova et al. 1999). Construction of specific interaction-directed, self-assembled protein films has been performed at the air-water interface. The Langmuir-Blodgett (LB) technique has been extensively used to order and immobilize natural proteins on solid surfaces (Tronin et... 

FIG. 7 Brewster-angle microscopy Image of POAS monolayer at air/water interface at pH 1 and various pressures. 

The Langmuir-Blodged (LB) technique allows one to form a monolayer at the water surface and to transfer it to the surface of supports. Formation of the BR monolayer at the air/water interface, however, is not a trivial task, for it exists in the form of membrane fragments. These fragments are rather hydrophilic and can easily penetrate the subphase volume. In order to decrease the solubility, the subphase usually contains a concentrated salt solution. The efficiency of the film deposition by this approach (Sukhorukov et al. 1992) was already shown. Nevertheless, it does not allow one to orient the membrane fragments. Because the hydrophilic properties of the membrane sides are practically the same, fragments are randomly oriented in opposite ways at the air/water interface. Such a film cannot be useful for this work, because the proton pumping in the transferred film will be automatically compensated i.e., the net proton flux from one side of the film to the other side is balanced by a statistically equal flux in the opposite direction. 

FIG. 1 Schematic showing the preparation of Langmuir films of latex particles at the air-water interface (a) Spreading of the latex and formation of an expanded monolayer (b) formation of the compressed monolayer. 

For the characterization of Langmuir films, Fulda and coworkers [75-77] used anionic and cationic core-shell particles prepared by emulsifier-free emulsion polymerization. These particles have several advantages over those used in early publications First, the particles do not contain any stabihzer or emulsifier, which is eventually desorbed upon spreading and disturbs the formation of a particle monolayer at the air-water interface. Second, the preparation is a one-step process leading directly to monodisperse particles 0.2-0.5 jim in diameter. Third, the nature of the shell can be easily varied by using different hydrophilic comonomers. In Table 1, the particles and their characteristic properties are hsted. Most of the studies were carried out using anionic particles with polystyrene as core material and polyacrylic acid in the shell. 

Fulda and Tieke [77] studied the effect of a bidisperse-size distribution of latex particles on the structure of the resulting LB monolayer. For this purpose, a mixed colloidal solution of particles la and lb was spread at the air-water interface. Particles la had a diameter of 434 nm, particles lb of 214 nm. The monolayer was compressed, transferred onto a solid substrate, and viewed in a scanning electron microscope (SEM). In Figure 10, SEM pictures of LB layers obtained from various bidisperse mixtures are shown. 

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