Carbon Nanoparticle-Induced Changes to Lipid Monolayer Structure at Water–Air Interfaces

Surface specific vibrational spectroscopy experiments together with surface tension measurements and spectroscopic ellipsometry data were used to characterize the effects of soluble carbon particulates on compressed and partially compressed lipid monolayers adsorbed to the water–air interface. The lipid monolayers consisted of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DPPC), and measurements were made for both tightly packed monolayers (40 Ų/molecule) and monolayers in their liquid condensed state (55 Ų/molecule). Langmuir trough data show that very small amounts of PHF (0.0075 mg/mL or 6.4 × 10^–6 M) decrease lipid film compressibility. This finding supports a cooperative adsorption mechanism whereby the soluble PHFs are drawn to the surface and associate with the insoluble DPPC monolayer. Excess free energies (ΔG_mix^E) were positive, consistent with the cooperative adsorption mechanism, and although the excess free energies are small (≤1 kJ/mol), adsorbed PHF has measurable effects on monolayer structure. Further support for the cooperative adsorption mechanism at the water–air interface comes from vibrational sum frequency generation (VSFG) experiments. Low PHF concentrations (≤0.06 mg/mL) increase DPPC acyl chain ordering in liquid condensed lipid films and decrease DPPC acyl chain ordering and film thickness in tightly packed lipid films.