Molecular Imprinting Using a Functional Chain Transfer Agent

This study demonstrates the feasibility of molecular imprinting using a functional chain transfer agent sans a functional monomer. Ethylene glycol dimethacrylate (EGDMA)-based MIPs were synthesised in the presence of thioglycolic acid (TGA) possessing a carboxylic acid group, capable of interacting with the chosen test template R,S-(±)-propranolol (PNL) and a labile S-H bond to facilitate an efficient chain transfer reaction. Quantitative ¹H NMR measurements showed high PNL and TGA incorporation within the MIP, indicating an efficient chain transfer process and a favourable interaction between PNL and TGA. TGA-50, with the lowest amount of CTA, showed the largest imprinting effect and an imprinting factor (IF) of 2.1. The addition of MAA to the formulation improved the binding capacity of PNL to the MIP but also increased NIP binding, resulting in a slightly decreased IF of 1.5. The K_d for the high-affinity sites of the TGA/MAA MIP were found to be two times lower (10 ± 1 μM) than that for the high-affinity sites of the TGA-only MIPs, suggesting that the incorporation of the functional monomer MAA increases the affinity towards the PNL template. Selectivity studies, cross-reactivity as well as binary competitive and displacement assays showed the TGA-based MIPs to be highly selective towards PNL against pindolol and slightly competitive against atenolol. The morphologies of the polymers were shown to be affected by the concentration of the TGA, transforming into discrete macrospheres (from small aggregates) at a higher TGA concentration.     

Correspondence on “Crystalline Porous Organic Salt for Ultrarapid Adsorption/Desorption-Based Atmospheric Water Harvesting by Dual Hydrogen Bond System”

In a recent Research Article, Ben and co-workers reported a hydrogen-bonded framework prepared from a 4⁺ tetra-amidinium component and a 4⁻ tetra-sulfonate component, termed CPOS-6. They showed that CPOS-6 could reversibly adsorb and desorb water over a narrow humidity window, and that this material offered potential for applications in atmospheric water harvesting. This conclusion was supported by experiments that showed the material was stable over 50 adsorption/desorption cycles and that the kinetics of these cycles were very rapid. In this Correspondence we present additional structural data regarding this framework in both its hydrated and dehydrated states and thus discern the mechanism of water binding. These data do not disagree with Ben and co-workers’ findings: rather they emphasise how remarkable the cyclability and rapid kinetics of adsorption/desorption are, as these processes involve a complete crystal-to-crystal rearrangement of the framework.