Rigid films of an anionic porphyrin and a dialkyl chain surfactant

The 2D complex formed at the air-water interface between the dialkyl chain cationic surfactant, dihexadecyldimethylammonium bromide, and the anionic porphyrin, tetrakis-(4-sulfonatophenyl) porphine, was studied using surface pressure-area isotherms as well as X-ray and neutron reflection measurements. The surface structure of these films was determined by the use of simultaneously constrained analysis of the neutron and X-ray reflectometry data and BAM images. Isotopic contrast variation methods were employed to enhance the information content of the neutron reflection data. The rigid complex forms at the interface due to the electrostatic interaction between the cationic headgroups of the surfactant and the anionic functional groups at the meso position of the porphyrin. The surface pressure-area isotherms show three distinct regions on compression: an initial condensed phase that ends with a pressure peak at 36 mN m-1, a second plateau region of high compressibility, and a final condensed phase. BAM images show that at the beginning of the plateau region in the isotherm there is complete surface coverage by a monolayer. The constrained simultaneous fitting of neutron and X-ray data measured just prior to and after the pressure peak shows a structurally similar 2D complex at the interface. Modeling of X-ray reflectometry data also reveals that in the final high-pressure phase the film has folded to form a trilayer. The conclusion is that the plateau region of the isotherm is due to the formation of trilayer surface coverage through localized buckling or folding, and that after this is complete there is some condensation before final film collapse.