Langmuir monolayers

In the case of Langmuir monolayers, film thickness and index of refraction have not been given much attention. While several groups have measured A versus a, [143-145], calculations by Knoll and co-workers [146] call into question the ability of ellipsometry to unambiguously determine thickness and refractive index of a Langmuir monolayer. A small error in the chosen index of refraction produces a large error in thickness. A new microscopic imaging technique described in section IV-3E uses ellipsometric contrast but does not require absolute determination of thickness and refractive index. Ellipsometry is routinely used to successfully characterize thin films on solid supports as described in Sections X-7, XI-2, and XV-7. 

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. 

The ability to image lateral heterogeneity in Langmuir monolayers dates back to Zocher and Stiebel s 1930 study with divergent light illumination [166]. More recently the focus shifted toward the use of fluorescence microscopy of mono-layers containing a small amount of fluorescent dye [167]. Even in single-corn-... 

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]. 

Deposited Langmuir-Blodgett films take on many of the same stmctures as the Langmuir monolayers discussed in Section IV-4C, and they are often compared to the self-assembling monolayers described in Section XI-IB. The area... 

For structures with a high curvature (e.g., small micelles) or situations where orientational interactions become important (e.g., the gel phase of a membrane) lattice-based models might be inappropriate. Off-lattice models for amphiphiles, which are quite similar to their counterparts in polymeric systems, have been used to study the self-assembly into micelles [ ], or to explore the phase behaviour of Langmuir monolayers [ ] and bilayers. In those systems, various phases with a nematic ordering of the hydrophobic tails occur. 

Patel H M, Didymus J M, Wong K K W, Hirsch A, Skiebe A, Lamparth I and Mann S 1996 Fullerates interaction of divalent metal ions with Langmuir monolayers and multilayers in mono-substituted Cgg-malonic acid J. Chem. Soc., Chem. Commun. 611-2... 

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... 

FIG. 4 Phase diagram of Langmuir monolayers at low and intermediate surface coverage (schematic). Not shown are the various phases on the condensed side at high surface coverage. 

Bead-spring models without explicit solvent have also been used to simulate bilayers [40,145,146] and Langmuir monolayers [148-152]. The amphi-philes are then forced into sheets by tethering the head groups to two-dimensional surfaces, either via a harmonic potential or via a rigid constraint. 

FIG. 8 Phase diagram of a Langmuir monolayer in a model of grafted stiff Lennard-Jones chains. LE denotes a disordered expanded phase, LC-U a condensed phase with untilted chains, LC-NN and LC-NNN condensed phases with collective tilt towards nearest neighbors and next-nearest neighbors, respectively, and LC-mod a phase which has a superstructure and an intermediate direction of tilt. (From Stadler and Schmid [151].)... 

I. INTRODUCTION TO LANGMUIR MONOLAYERS AND LANGMUIR-BLODGETT FILMS... 

B. Langmuir Monolayers and Langmuir-Blodgett Films of Fatty Acids... 

FIG. 3 An isotherm is depicted for a Langmuir monolayer of an amphiphUe showing the ft-A variation for the phase sequence gas (G) —> G + liquid-expanded (LE) —> LE —> LE + tilted condensed phase (L2) —> L2 —> vertical condensed phase (LS) —> S (solid). Schematic depictions of the molecular organization in the phases are shown above the isotherm. 

The primary classical method of study of Langmuir monolayers is clearly that of recording H-A isotherms. Another classical method applied to the study of Langmuir monolayers is the measurement of surface potential [8,9], which is sensitive to changes in the orientation and density of the molecular dipoles of the monolayer. In addition, surface potential fluctuations were clearly observed in the coexistence region of palmitic acid [35]. 

Generation of nanoparticles under Langmuir monolayers and within LB films arose from earlier efforts to form nanoparticles within reverse micelles, microemulsions, and vesicles [89]. Semiconductor nanoparticles formed in surfactant media have been explored as photocatalytic systems [90]. One motivation for placing nanoparticles within the organic matrix of a LB film is to construct a superlattice of nanoparticles such that the optical properties of the nanoparticles associated with quantum confinement are preserved. If mono-layers of capped nanoparticles are transferred, a nanoparticle superlattice can be con-... 

Formation of Metallic Nanoparticles Beneath Langmuir Monolayers... 

FIG. 14 Measurements on monolayers and LB films of CdSe nanoparticles of narrow size distribution (a) II-A isotherms for Langmuir monolayers of CdSe nanoparticles of diameter 2.5 run (curve a), 3.0 mn (curve b), 3.6 mn (curve c), 4.3 mn (curve d), and 5.3 mn (curve e). The area per nanoparticle was determined by dividing the trough area by the estimated number of particles deposited on the surface, (b) Absorbance and photoluminescence spectra of the nanoparticles in solution (A, B) and in monolayers on sulfonated polystyrene-coated glass sbdes (C. D). The nanoparticle diameters are 2.5 nm (curves labeled a), 3.6 nm (curves labeled b), and 5.3 nm (curves labeled c). The excitation wavelengths are (a) 430 nm, (b) 490 nm, and (c) 540 nm. (Reproduced with permission from Ref. 158. Copyright 1994 American Chemical Society.)... 

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