Mechanism of Time-Dependent Adsorption for Dilauroyl Phosphatidylcholine onto a Clean Air-Water Interface from a Dispersion of Vesicles.

This study focused on mechanisms of adsorption for dilauroyl phosphatidylcholine (DLPC) from a dispersion of large, unilamellar vesicles (LUVs) onto a clean air-water interface. The adsorption kinetics were tracked using dynamic surface tension measurements for 0.01-10 mM concentrations of DLPC, contained within monodisperse LUVs with mean diameters between 100 and 300 nm. Any lipid in excess of the solubility limit, determined to be 1.1(±0.7) × 10-5 mM (1.1 × 10-8 M), was assumed to be in vesicle form. The adsorption rate was found to increase with increasing lipid concentration and decreasing vesicle diameter, indicating a clear mechanistic role for the vesicles. An induction regime was observed, during which lipid adsorption occurred without significantly changing the surface tension. Pressure-area isotherm data suggested that the surface concentration at the end of this induction period was ∼50% of the concentration at saturation, with the latter estimated as 4.2(±0.7) × 10-6 mol/m2 . Convection was also introduced into these experiments to probe the importance of bulk transport mechanisms to the overall kinetics. Theoretical expressions for possible contributing mechanisms and pathways, via molecular and/or vesicle transport, were developed and used to predict associated transport time scales for different scenarios. These theoretical time scales were compared to experimentally measured characteristic times for a variety of DLPC concentrations, vesicle diameters, and convection rates. For DLPC concentrations ≥0.25 mM, our results were consistent with the monolayer formation arising from a molecular transport mechanism that is enhanced by vesicle-to-monomer exchange beneath the interface. At lower concentrations, experimental rates of adsorption increased with increasing convection, and a strong effect of lipid concentration was also observed. For DLPC ≤0.25 mM, transport controlled by direct interfacial vesicle adsorption reasonably captured the observed effect of lipid concentration; however, neither monomer nor vesicle pathway mechanisms captured the influence of convection. Understanding the adsorption kinetics for such nearly insoluble surfactant systems is important in several areas, including food emulsification, foam or microbubble formulation, spray drying techniques, and therapeutics.