Structure, Dynamics, and Adsorption of Charged Guest within the Nanocavity of Polymer-Functionalized Neutral Macrocyclic Host

Host–guest encapsulation has been widely applied for purification and seizing of the metal ions. Macrocyclic crown ethers are one of the most popular hosts in the field of host–guest chemistry, which on functionalization with polymers are employed as an effective adsorbent. In spite of their vast applications, the microscopic information about their sensing mechanism toward cations/molecules is very scarce. Therefore, the present study is focused on the molecular insights of ion-exchange mechanism within the cavity of crown ether-functionalized polymers using molecular dynamics (MD) simulations. This present study investigates the molecular-level events of chloromethylated polystyrene (CMPS) bearing dibenzo-18-crown-6 (DB18C6) in the aqueous and acidic environment, which has been found to be particularly successful in sensing of various alkali and alkali earth metal ions. A strategy has been envisaged to design a crown ether-based functionalized polymeric resin, which exhibits good match of properties with the in-house-synthesized resin. The MD studies well capture the experimentally observed Langmuir-type adsorption isotherms of Li⁺ ions on crown ether-grafted polymer resins. The presence of acid reduces the adsorption of Li⁺ ions due to the competition with H₃O⁺ ions. In addition, the results revealed that the “adsorption in crown cavity” follows a dual residence time function. To the best of our knowledge, this is the first report on the adsorption isotherm of functionalized crown ether using MD simulations. The structure and dynamics of binding sites were explored using radial distribution functions and diffusion coefficients. All of these effects have been studied for different Li⁺-ion concentrations, acid concentrations, and counterions as well as different lengths of polymer chains and degrees of polymerization. Overall, the present study provides insights into and quantitative information about adsorption on the CMPS-DB18C6 resin, which might be useful in myriads of host–guest-based adsorption experiments.