Sensitive Detection of Biomolecular Adsorption by a Low-Density Surfactant Layer Using Sum-Frequency Vibrational Spectroscopy

Small molecules or proteins interact with a biomembrane in various ways for molecular recognition, structure stabilization, and transmembrane signaling. In this study, 1,2-dipalmitoyl-3-trimethylammonium-propane (DPTAP), having a choline group, was used to investigate this interaction by using sum-frequency vibrational spectroscopy. The sum-frequency spectrum characteristic of a neat monolayer changed to that of a bare air/water interface at a larger molecular area of the DPTAP molecules due to local laser heating. Upon introduction of the aromatic molecules in the subphase at around 120 angstrom(2) per molecule, the sum-frequency signal suddenly reappeared due to molecular adhesion, and this was utilized to probe the adsorption of the aromatic ring molecules in the water subphase to the choline headgroup of the DPTAP by cation-pi interaction. The onset concentrations of this sum-frequency signal change allowed a comparison of the relative interaction strengths between different aromatic molecules. A zwitterionic surfactant molecule (DPPC) was found to interact weakly compared to the cationic DPTAP molecule.