Structure and Lateral Interaction in Mixed Monolayers of Dioctadecyldimethylammonium Chloride (DOAC) and Stearyl Alcohol

π–<i>A</i> isotherms, atomic force microscopy (AFM), and sum frequency generation (SFG) vibrational spectroscopy are employed to investigate the molecular structure and lateral interactions in mixed monolayers of dioctadecyldimethylammonium chloride (DOAC) and stearyl alcohol (SA) at air/water and air/solid interfaces. To avoid possible interference between the two molecules in the SFG spectroscopic measurements, perprotonated DOAC and perdeuterated SA (dSA) were used. The thermodynamic analyses for the π–<i>A</i> isotherms show that DOAC is miscible with dSA. SFG observations reveal that DOAC molecules become conformationally ordered as dSA molecules are introduced into the monolayer. AFM observations demonstrate coexistence of DOAC-rich and dSA-rich domains in the mixed monolayer with ratios different from their initial composition in the subphase. The present study suggests that DOAC molecules in the mixed monolayer are condensed by mixing with dSA in which the repulsive interactions between positively charged head groups of the DOAC molecules are largely reduced along with an increase of van der Waals interactions with dSA

Effect of Functional Group on the Monolayer Structures of Biodegradable Quaternary Ammonium Surfactants

The monolayer structures and conformational ordering of cationic surfactants including the biodegradable quaternary ammonium molecules have been systematically characterized by π–<i>A</i> isotherm, surface potential, atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and sum frequency generation (SFG) vibrational spectroscopy. It was found that the monolayer of the typical dialkyl dimethylammonium on the water surface was less densely packed along with many conformational <i>gauche</i> defects. The packing density and ordering of these monolayers were improved as halide ions were added to the subphase. A similar condensation effect was also observed when amide or ester groups are present in the alkyl tails of the surfactant. These results are discussed on the basis of the repulsive electrostatic interactions between the terminal ammonium moieties, the hydrogen bonding between the functional groups in the alkyl chains, as well as the flexibility of the alkyl chains in these surfactants. The present study is crucial to understanding the relationship between the interfacial structures and the functionalities of the biodegradable quaternary ammonium surfactants