RESUMEN
Metal-organic frameworks (MOFs) are excellent catalytic materials for the hydrolytic degradation of nerve agents and their simulants. However, most of the MOF-based hydrolysis catalysts to date are reliant on liquid water media buffered by a volatile liquid base. To overcome this practical limitation, we developed a simple and feasible strategy to synthesize MOF composites that structurally mimic phosphotriesterase's active site as well as its ligated histidine residues. By incorporating imidazole and its derivative into the pores of MOF-808, the obtained MOF composites achieved rapid degradation of a nerve agent simulant (dimethyl-4-nitrophenyl phosphate, DMNP) in pure water as well as in a humid environment without liquid base. Remarkably, one of the composites Im@MOF-808 displayed the highest catalytic activity for DMNP hydrolysis in unbuffered aqueous solutions among all reported MOF-based catalysts. Furthermore, solid-phase catalysis showed that Im@MOF-808 can also rapidly hydrolyze DMNP under high-humidity conditions without bulk water or external bases. This work provides a viable solution toward the implementation of MOF materials into protective equipment for practical nerve agent detoxification.
RESUMEN
Metal-organic frameworks (MOFs) have emerged as promising candidates for a wide range of applications due to their high surface area and customizable structures, however, the minimal external hydrophilicity of MOFs has limited their biomedical implementations. Structuring of MOFs within polymer frameworks is an approach used to create hybrid materials that retain many of the MOF characteristics (e.g. high adsorption capacity) but expand the range of mechanical and surface properties as well as form factors accessible. Using this approach, hybridizing MOFs with hydrophilic hydrogels can give rise to materials with improved hydrophilicity and biocompatibility. Here, we describe the synthesis of the first Zr-based MOF-hydrogel hybrid material (composite 3) using a green chemistry approach, in which only water was used as the solvent and relatively low temperature (50 °C) was applied. Using methylene blue (MB) as a probe molecule, composite 3 exhibited greater adsorption capacity than the MOF or the hydrogel alone in aqueous solution at most tested pH values (all except pH 13). At an initial MB concentration of 0.0096 mg/mL (30.014uM) and neutral pH conditions, this new hybrid presented the highest loading of MB among similar materials (MB adsorbed = 4.361 ± 0.092 mg MB/g Zr, partition coefficient = 0.172 ± 0.004 mg/g/uM) and largely retained its adsorption capacity under varied conditions (pH 1-13 and 0.2-1.0M NaCl), rendering possible applications in drug delivery and the removal of tumor contrast agent/dye with minimal leakage due to its broad chemical stability.