The molecular organization of a cationic matrix (DOMA) as influenced by the presence of an anionic watersoluble porphyrin (TSPP), in the mixed monolayer, molar ratio TSPP/DOMA) 1:4, has been studied by π-A isotherms, the reflection spectra, BAM images, and imaging ellipsometry at the air-water interface. A reversible collapse of the mixed film at high surface pressures is observed. The formation of an aggregate of the porphyrin molecules under compression is inferred from the reflection spectra. BAM images show the spontaneous formation of domains at 35 mN/m that become bigger during the spontaneous dense process at constant surface pressure. The reversible character of that process was also observed by BAM. The evaluation of the reflection spectra as well as the area fraction of the domains and the surrounding dark regions have led us to consider a trilayer structure for the TSPP/DOMA domains emerging during the collapse process. By using imaging ellipsometry on selected regions of interest (few microns), the thicknesses of domains (d dom) 5.045 nm) and surrounding areas (d dark) 1.764 nm) were estimated. These thickness values are in good agreement with the trilayer architecture where the DOMA molecules have retained the TSPP molecules by electrostatic interactions.

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This paper shows that it is possible to construct well-defined 2D structures at the air-water interface in which the lateral organization is controlled by means of the preparation of mixed films, and selecting the components so that there are attractive interactions between them. The goal here is to establish the lateral connection between components through self-aggregation of the dye. This can be achieved by selecting a suitable balance between the sizes of the hydrophobic and polar groups. In such a way, the domain structure depends on the ability of the tilt dye to fill the available area. Thus, the molecular organization and the domain morphology of mixed films containing dimyristoyl-phosphatidic acid (DMPA) and the hemicyanine dye, 4-[4-(dimethylamino)styryl]-1-docosylpyridinium bromide (SP), have been studied by using Grazing Incidence X-ray Diffraction (GIXD), Brewster angle microscopy (BAM), and reflection spectroscopy at the air-water interface. For this mixed system, the formation of circular domains with bright horizontal regions and dark vertical regions was observed. Furthermore, depending on the temperature, it is observed as branches grow from circular domains, whose brightness depends on the growth direction. Thus, BAM images allow us to observe some branches that, as their growth direction changes, their brightness also changes simultaneously. The GIXD experiment permits us to relate the circular domains with an orthorhombic phase and the branches grown from the circles with an Overbeck phase. In both cases, the formed structures are induced by the hemicyanine aggregation. Circular BAM domain textures have been simulated by using the Fresnel equations for biaxial anisotropic materials.

The molecular organization and the domain morphology of an anionic matrix dimyristoyl−phosphatidic acid (DMPA) as influenced by the presence of a cationic water-soluble methylene blue (MB) have been studied by using Brewster angle microscopy and reflection spectroscopy at the air−water interface. Mixed monolayers of DMPA:MB, molar ratios 5:1 and 1:1, were formed by the cospreading method. BAM images show particular domain morphologies as a function of the MB density in the mixed film: circular domains for DMPA:MB = 5:1, and domains with hexagonal shape for DMPA:MB = 1:1. The reflection measurements during the compression process of the mixed films reveal a blue shift of the visible band with respect to that of the MB monomer. This blue shift is larger for the DMPA:MB = 5:1 in comparison with that for the 1:1 monolayer, despite lower MB density. By using the extended dipole model, we demonstrate that such blue shift is due to the formation of a 2D hexagonal network of MB molecules underneath the DMPA monolayer in the mixed 1:1 film, while it is due to infinite linear aggregates in the 5:1 monolayer. BAM domain textures have been simulated by using the Fresnel equations for biaxial anisotropic materials. The results fit correctly the predictions of the extended dipole model.