Reversible Collapse of Insoluble Monolayers: New Insights on the Influence of the Anisotropic Line Tension of the Domain

• Published in: The journal of physical chemistry. B Vol. 113; no. 40; pp. 13249 - 13256
• Main Authors: González-Delgado, Antonio M, Pérez-Morales, Marta, Giner-Casares, Juan J, Muñoz, Eulogia, Martín-Romero, María T, Camacho, Luis
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 08.10.2009
• Subjects: B: Surfactants, Membranes
• ISSN: 1520-6106; 1520-5207
• DOI: 10.1021/jp9055158

In this paper, we study the collapse of a mixed insoluble monolayer formed by a cationic matrix, dioctadecyl-dimethylammonium bromide (DOMA), and a tetra-anionic porphyrin, tetrakis(4-sulfonatophenyl)porphyrin (TSPP), in a molar ratio TSPP/DOMA = 1:4. During the collapse of this system, we visualized the formation of circular domains consisting exclusively of trilayer, although the domains coalescence was not observed. The coexistence of trilayer and monolayer at the final step of the collapse cannot be interpreted exclusively in terms of a thermodynamic phase equilibrium, intervening as an additional factor the anisotropic line tension of the domain. A high line tension implies a high resistance to the domain deformation, and the anisotropy of the line tension implies the lack of coalescence between these domains, which has been experimentally observed by Brewster angle microscopy for us. Under these circumstances, the domains of collapsed material could enclose monolayer regions where the local surface pressure drops thus stopping the collapse process. The collapse of the TSPP/DOMA system is reversible, that is, the return of the three-dimensional material to the monolayer fits into a simple kinetics according to the nucleation−growth-collision theory. As for the collapse, the reverse process is also affected by the line tension of the domains. This paper relates the high line tension and the anisotropic line tension of a given domains with the reversible nature of the collapse process.