A three-component hydrogen bonded framework.

A porous three-component hydrogen bonded framework, 1⋅biphen⋅TP, was prepared from a tetra-amidinium component (14+) and two different dianions, benzene-1,4-dicarboxylate (terephthalate, TP2-) and biphenyl-4,4'-dicarboxylate (biphen2-). Interestingly, when the framework was prepared in ethanol/water, 1⋅biphen⋅TP forms even when an excess of either dicarboxylate is present. However, when only water is used as solvent, only two-component frameworks are formed.

Hydrogen-bonded frameworks containing aliphatic 3D linkers show high-capacity water vapour sorption.

Hydrogen-bonded frameworks were prepared from a tetra-amidinium component and three-dimensional cubane and bicyclopentane dicarboxylate linkers. Despite the incorporation of aliphatic components, the frameworks demonstrate strong and reversible uptake of water vapour, with one of the frameworks showing water uptake at very low relative humidity.

Charge "mis-matched" hydrogen bonded frameworks for cation exchange and dye sorption.

Anionic hydrogen bonded frameworks were synthesised from di or tetra-amidinium hydrogen bond donor components and a charge "mis-matched" tecton possessing a 5- charge but only four hydrogen bond accepting groups. The net negative charge on the framework skeletons necessitates the presence of a cation in the framework channel. In one of the frameworks, the initially incorporated organic cation was rapidly displaced by smaller inorganic cations, or the cationic dye methylene blue. This facilitated the effective and selective removal of this dye from water.

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.

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 Kd 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.

Use of modulators and light to control crystallisation of a hydrogen bonded framework.

The effect of concentration, organic co-solvent, and salt modulators on the crystallisation of a hydrogen bonded framework was studied. The framework contains ∼1.4 nm wide channels and contains a diazobenzene based dicarboxylate anion. Light-induced cis/trans switching of this anion was also used to control crystallisation.

Molecularly Imprinted Polymeric Nanoparticles by Precipitation Polymerization and Characterization by Quantitative NMR Spectroscopy.

An optimized synthetic methodology for the preparation of highly homogeneous MIP nanoparticles by the precipitation method is presented. A quantitative 1H NMR method that was developed to estimate template incorporation, polymer composition and conversion, and binding capacities and selectivities is also described. While the experiment presented here is exemplified by an MIP formulation using (±)-propranolol as the template, methacrylic acid as the functional monomer and ethylene glycol dimethacrylate as the crosslinker, the methods and techniques are applicable to other precipitation MIP systems.