A novel porous polyoxometalate (POM)-based composite (Co4PW–PDDVAC) was prepared via the solidification of water-soluble polytungstate (Co4PW) on the polymeric ionic liquid dimethyldodecyl-4-polyethylene benzyl ammonium chloride (PDDVAC) via a cation-exchange reaction. The solidification was confirmed by EDS, SEM, FT-IR, TGA, and so on. The strong covalent coordination and hydrogen-bonding interaction between the highly active Co2+ of the Co4PW and the aspartic acid residues of proteinase K endowed the obtained Co4PW–PDDVAC composite with excellent proteinase K adsorption properties. Thermodynamic investigations indicate that the adsorption behavior of proteinase K was consistent with the linear Langmuir isothermal model, giving an adsorption capacity as high as 1428 mg g−1. The Co4PW–PDDVAC composite was applied in the selective isolation of highly active proteinase K from Tritirachium album Limber crude enzyme fluid.
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