Spatially Organized Functional Bioreactors in Nanoscale Mesoporous MOFs for Cascade Scavenging of Intracellular ROS

The creation of artificial microenvironments with specific functionalities to mimic multiple cascade biocatalytic processes in cells is highly desirable. Here, Zr-based large-pore mesoporous metal–organic frameworks (mesoMOFs) were successfully developed for the construction of such spatially organized cascade bioreactors. Thanks to the mediating effect of the Hofmeister ion and the flexibility of Zr-MOFs, large mesopores and functional microporous mesopore walls were integrated into a single nanoplatform, ensuring the efficient mass exchange between the interconnected pore units with different sizes. As a proof of concept, natural superoxide dismutase and catalase mimic were spatially positioned in these hierarchical mesoMOFs, which formed a cascade antioxidant defense system and presented an efficient intracellular reactive oxygen species scavenging ability. This model is expected to set a conceptual guideline for the design of compartmentalized bioreactors in nanoscale MOFs to mediate the complex intracellular catalytic networks.