Structural and Dynamical Studies of a Lipid-Nanoclay Composite Layer at the Air-Water Interface.

We modulate the adsorption affinities of nanoclay particles for the air-water interface by changing the cationic surface charge composition of the lipid monolayer and thereby tune the attractive electrostatic interaction between the positively charged lipid layer and the zwitterionic nanoclay particles in the water subphase. Our findings emphasize the significance of electrostatic interaction between lipids and the nanoclay, as well as its impact on the structural and viscoelastic features of the composite layer. We use surface pressure (Π)-mean molecular area () isotherms, atomic force microscope (AFM), Brewster angle microscopy (BAM), and energy dispersive X-ray spectrsocopy (EDXS) measurements to analyze the structure phases of lipid and lipid-nanoclay composite interfacial layer. The Π- isotherm curve shows that the lipid-nanoclay composite layer has a larger lift-off area than the neat lipid layer, indicating that nanoparticles adsorb at the lipid layer via electrostatic interaction between lipid and nanoclay molecules. The surface density of the adsorbed nanoclay particles increases with an increase in the composition of the cationic lipid molecules. The stress relaxation response of the composite layer, measured using step compression measurements, exhibits exponential decay and ubiquitous dependence on the cationic dimyristoy-trimethylammonium propane (DMTAP) composition in the lipid layer with crossover to faster relaxation dynamics at DMTAP > 0.75. The power-law study of the frequency-dependent dynamic viscoelastic responses of the interfacial layer, measured using the barrier oscillation method, reveals a transition from glass-like response from neat lipid layer to gel-like dynamic response for the lipid-nanoclay composite layer. A solid-like behavior is evident for all the interface layers with dilation elastic modulus (') > dilational viscous modulus (″); however, the dynamic response of the neat layer is largely frequency-independent, whereas lipid-nanoclay composite layers with DMTAP > 0.75 reveal a frequency-dependent dynamic responses. The frequency-dependent power-law exponent of ', ″ increases on increasing the fractional composition of cationic DMTAP from 0.1 to 1.0, which forms a saturated interface of laponite particles and behaves as a viscoelastic gel in 2D.