Recognition of Polymer Terminus by Metal-Organic Frameworks Enabling Chromatographic Separation of Polymers.

Unlike commonly used molecular recognition techniques, recognition of polymer structures requires an additional aspect of extremely high recognition ability, by which marginal structural differences can be identified in a large polymer chain. Herein we show that metal-organic frameworks (MOFs) can recognize polymer terminal structures, thus enabling the first reported chromatographic separation of polymers. End-functionalized polyethylene glycols (PEGs) are selectively inserted into the MOF channel, the insertion kinetics being dependent on the projection size of the PEG terminus. This size-selective insertion mechanism facilitates precise discrimination of end-functionalized PEGs using liquid chromatography (LC). An MOF-packed column thus provides an efficient and easily accessible method for the separation of such end-functionalized polymers using conventional LC systems.

Topological entrapment of macromolecules during the formation of metal-organic framework.

Here we present our preliminary results on a novel approach to encapsulate large guest molecules in nanoporous materials, metal-organic frameworks (MOFs), via a newly discovered in situ crystal formation. This method has exciting prospects not only in the design of new organic/inorganic hybrids but also in capturing and separating molecules that are significantly larger than the actual pore size of the host MOF.

Mixed Metal-Organic Framework Stationary Phases for Liquid Chromatography.

Strategic design of the stationary phase in liquid chromatography (LC) is crucial for modern separation science. Herein, a design approach using mixed metal-organic frameworks (MOFs) as tunable LC stationary phases is proposed. Three MOFs with an isostructural pillared-layer structure are employed, with pore sizes tuned by the systematic design of the constituent ligands, using 1,4-benzenedicarboxylate (bdc), 1,4-naphthalenedicarboxylate (ndc), and 9,10-anthracenedicarboxylate (adc). Packed columns filled with the MOFs and their mixed-particle/solid-solution stationary phases are prepared and examined for the retention capability of polyethylene glycol (PEG) in LC. While the MOF-packed columns filled with binary mixtures of different MOF particles provide good control of the retention with respect to the particle mixing ratio, the columns filled with mixed-linker solid-solution MOFs show a significant multicomponent effect on the retention behavior. Specifically, mixed-linker solid-solution MOFs consisting of bdc/ndc binary ligands are found to show a strong retention that surpasses even their parent MOFs, namely, pure bdc- and ndc-MOF stationary phases. The retention behavior on the MOF-packed columns is explained by the specific nanostructures of the solid-solution MOFs, which affects the balance between substrate affinity and adsorption kinetics into the MOF pores, dictating the total retention capability. The results provide an extra dimension for stationary phase design using MOFs as a promising recognition medium for LC.