A polymer deposition-mediated surface-charge reformation strategy: reversing the MOF biomineralization behavior

Biomineralization of a porous metal-organic framework (MOF) shell onto biomacromolecule templates is a burgeoning strategy to construct robust biocatalysts. However, it strongly relies on the interfacial interaction between MOF precursors and enzyme surface, significantly limiting the generalization of this nanotechnology. Herein, we identify polymers that are well-suited for deposition onto target biomacromolecules via supramolecular interactions and introduce a polymer deposition-mediated surface-charge reformation strategy to facilitate the biomineralization of porous MOFs, including ZIF-8, ZIF-90, and ZIF-zni onto enzymes. We investigate nine commercially available polymers to find that those with dense -SO₃H and -COOH groups effectively regulate the surface-charge properties of the enzymes that are unfavorable for biomineralization. The polymer-enzyme complex thus formed retains its original bioactivity and offers significantly elevated sites to accumulate metal precursors, triggering the in-place MOF biomineralization. We demonstrate that this approach allows access to diverse MOF biocatalysts independent of the enzyme surface chemistry, which are difficult to be synthesized by previous biomineralization methods. Given the highly specific bioactivity and structural stability of the MOF biocatalysts, a chemiluminiscence sensor platform is developed for the sensitive detection of hydrogen sulfide (H₂S) biomarkers, with a low limit of detection of 0.09 nM that is superior to most of the reported methods. This study provides an effective and universal strategy for MOF biomineralization using fragile enzymes as biotemplates and offers new insights into accessing multifunctional MOF hybrid biocatalysts.