Mesoscopic simulations of temperature-dependent anchoring and wetting behavior at aqueous–liquid crystal interfaces in the presence of a rod–coil amphiphilic monolayer

Dissipative particle dynamics simulations have been applied to study the temperature dependent anchoring and wetting behavior of thermotropic liquid crystals (LCs) in the presence of a rod–coil amphiphilic monolayer at the aqueous–LC interface. Upon cooling in the nematic phase, a thermally-induced anchoring transition from homeotropic through tilted to planar has been observed. The growth and propagation of smectic order from the interfaces to the bulk nematic LCs are demonstrated to be mainly responsible for this novel transition sequence. In particular, when a complete smectic layer in the amphiphile monolayer is induced around the bulk transition of nematic–smectic-A, the propagation of homeotropic alignment fails instantly and a unique planar anchoring configuration is formed instead. While heating towards the isotropic phase, simulation results show that the nematic–isotropic transition of confined LCs is slightly shifted to a higher temperature, and a nematic wetting layer with homeotropic alignment appears in the rod block monolayer when the bulk LCs is isotropic. Our systematic simulations throughout the whole phase regimes of LCs provide important molecular-level insight into how the coupling between the ordering of LCs and adsorbents and their temperature dependencies affect the anchoring behavior in this complex system, which should be instrumental in the rational design and application of advanced LC-based biosensors with optimal operating temperature range.