Incorporation and Exclusion of Long Chain Alkyl Halides in Fatty Acid Monolayers at the Air−Water Interface
journal contributionposted on 21.12.2010, 00:00 by M. Roxana Sierra-Hernández, Heather C. Allen
Mixed monolayers of deuterated palmitic acid C15D31COOH (dPA) and deuterated stearic acid C17D35COOH (dSA) with 1-bromoalkanes of different alkyl chain length (C4 to C16) at the air−water interface were investigated. Alkanes and 1-chlorohexadecane ClC16H33 (ClHex) were also studied to compare the effects of the halogen on the mixed monolayers. Surface pressure−area isotherms and Brewster angle microscopy (BAM) were used to obtain the organization and phase behavior, providing a macroscopic view of the mixed monolayers. A molecular-level understanding of the interfacial molecular organization and intermolecular interactions was obtained by using vibrational sum frequency generation (SFG) spectroscopy and infrared reflection−absorption spectroscopy (IRRAS). It was found that from the alkyl halide molecules investigated 1-bromopentadecane, BrC15H31 (BrPent), 1-bromohexadecane, BrC16H33 (BrHex), and ClHex incorporate into the fatty acid monolayers. Alkanes of 15- and 16-carbon chain length do not incorporate into the fatty acid monolayer, which suggests that the halogen is needed for incorporation. Isotherms and spectra suggest that BrHex molecules are squeezed out, or excluded, from the fatty acid monolayer as the surface pressure is increased, while BAM images confirm this. Additionally, SFG spectra reveal that the alkyl chains of both fatty acids (dPA and dSA) retain an all-trans conformation after the incorporation of alkyl halide molecules. BAM images show that at low surface pressures BrHex does not affect the two-dimensional morphology of the dPA and dSA domains and that BrHex is miscible with dPA and dSA. We also present for the first time BAM images of BrHex deposited on a water surface, which reveal the formation of aggregates while the surface pressure remains unchanged from that of neat water.