Molecular Simulations of Analyte Partitioning and Diffusion in Liquid Crystal Sensors

Chemoresponsive liquid crystal (LC) sensors are promising platforms for the detection of vapor-phase analytes. Understanding the transport of analyte molecules within LC films could guide the design of LC sensors with improved selectivity. In this work, we use molecular dynamics simulations to quantify the partitioning and diffusion of nine small-molecule analytes, including four common atmospheric pollutants, in model systems representative of LC sensors. We first parameterize all-atom models for 4-cyano-4′-pentylbiphenyl (5CB), a mesogen typically used for LC sensors, and all analytes. We validate these models by reproducing experimentally determined 5CB structural parameters, 5CB diffusivity, and analyte Henry's law constants in 5CB. Using the all-atom models, we calculate analyte solvation free energies and diffusivities in bulk 5CB. These simulation-derived quantities are then used to parameterize an analytical mass-transport model to predict sensor activation times. These results demonstrate that differences in analyte–LC interactions can translate into distinct activation times to distinguish activation by different analytes. Finally, we quantify the effect of LC composition by calculating analyte solvation free energies in TL205, a proprietary LC mixture. These calculations indicate that varying the LC composition can modulate activation times to further improve sensor selectivity. These results thus provide a computational framework for guiding LC sensor design by using molecular simulations to predict analyte transport as a function of LC composition.