Orderly MOF-Assembled Hybrid Monolithic Stationary Phases for Nano-Flow HPLC

We report an approach that polymerizable handle-modified nanosized metal organic frameworks (MOFs) are used as independent monomers to be covalently organized by crosslinking molecules (CLMs) into an orderly MOF-assembled hybrid monolithic stationary phase, overcoming the respective problems of previously reported MOF-mixed or embedded stationary phases so far. It has a hierarchical micro-, meso-, and macropore structure throughout the monolithic matrix that is donated from MOF themselves, formed via CLM crosslinking in-between MOFs and expended by porogenic solvents, and a tunable surface chemistry derived inherently from MOFs, regulated by CLMs and initiated by the mobile phases as well. Such a pore structure and surface chemistry display multiplex interactions of sieving and electrostatic repulsion in addition to the polarity-based interactions that synergistically govern the partitioning way and degree of target molecules between the stationary and mobile phases, thus offering the ability to simultaneously separate small and large molecules during one chromatographic run on a nano-flow capillary high-performance liquid chromatography platform. A baseline mutual separation with the HETP and R_s of, for example, 9.2 μm butylbenzene and 4.56 (butylbenzene and pentylbenzene), 7.9 μm (phenylalanine) and 3.50 (tryptophan and phenylalanine), and 7.0 μm (myoglobin) and 1.91 (bovine serum albumin and myoglobin) was achieved when UiO-66/NH-methacrylate was exemplified as a model of MOFs and 1,6-hexanediol dimethacrylate and stearyl methacrylate together as CLMs. Not limited to the MOFs and CLMs demonstrated here, other available MOFs and CLMs or newly designed and synthesized ones are expected to be used for constructing one's own desired monolithic stationary phases toward her/his particular purposes.