[Preparation of liquid crystal-based molecularly imprinted monolith and its molecular recognition thermodynamics]

Molecularly imprinted polymers (MIPs) incorporated with liquid crystalline monomers can imprint and recognize templates at a very low level of crosslinking, thus addressing challenges associated with conventional MIPs, such as the embedding of the imprinted sites, low binding capacity, and slow mass transfer due to the high degree of crosslinking. Compared with traditional MIPs, the prepared MIPs have a greater number of easily binding sites, which can effectively overcome the embedding and low utilization of imprinting sites. Simultaneously, with a decrease in the level of chemical crosslinking, the mass transfer of template molecules can be significantly improved. However, the imprinting effect of liquid crystalline MIPs is generally weaker than that of traditional MIPs due to the low degree of crosslinking. Therefore, to obtain liquid crystalline MIPs with a good imprinting effect, a series of low-crosslinked liquid crystalline molecularly imprinted monoliths were prepared by graft polymerization and evaluated by high performance liquid chromatography (HPLC) to systematically determine the relation between the polymerization parameters and the affinity of the resulting liquid crystalline MIPs. In this experiment, trimethylolpropane trimethacrylate (TRIM) was used to synthesize a monolithic column skeleton with toluene and dodecyl alcohol as porogens. (S)-Naproxen was used as a template and liquid crystalline monomer 4-(4-cyanophenyl)-cyclohexyl ethylene (CPCE) was added for grafting to synthesize the liquid crystalline MIP monolith. The influence of the acetonitrile content and pH in the mobile phase on the chromatographic retention of the template molecule was investigated. The results showed that the main force of MIP recognizing naproxen changed from hydrogen bonding to hydrophobic interaction by the addition of the liquid crystalline monomer. Frontal analysis and adsorption isotherm fitting, including Langmuir, Freundlich, and Scatchard fitting, showed that when the crosslinking degree was 15%, the liquid crystalline MIPs exhibited the highest imprinting factor and heterogeneity, and the specific adsorption was stronger than non-specific adsorption. By analyzing the stoichiometric displacement model, the total affinity of the MIP monoliths for the template molecules (ln A) was determined to be 0.645, significantly higher than that of its analogues, indicating that the liquid crystalline imprinted monolith had a higher total affinity for the template molecule. The spatial matching degree (nβ) of the template molecule to the cavity structures of MIPs was also very high, and only inferior to that of ketoprofen. Nevertheless, the ln A value of ketoprofen was only 0.242, which indicated that the spatial effect was not the key factor in determining the recognition ability of liquid crystalline imprinting systems. An analysis of the separation thermodynamics revealed that the separation of the liquid crystalline MIPs was an entropy-controlled process, while that of conventional liquid crystalline-free MIPs was an enthalpy-controlled process. Based on the above results, the addition of a liquid crystalline monomer may alter the recognition mechanism of MIPs, and an appropriately low crosslinking degree can significantly improve the recognition performance of liquid crystalline MIPs, paving the way for a new generation of MIPs.