Encapsulation of active biomolecules and/or nanoparticles in metal-organic frameworks (MOFs) remains ag reat challenge in biomedical applications.I nt his work, through astepwise in situ growth method, ablack phosphorus quantum dot (BQ) and catalase were precisely encapsulated into the inner and outer layers of MOFs,r espectively.T he integrated MOF system as at andem catalyst could convert H 2 O 2 into O 2 in MOF-stabilized catalase outer layer,and then O 2 was directly injected into MOF-sensitized BQ inner,leading to high quantum yield of singlet oxygen. Upon internalization, the photodynamic therapye fficiency of the MOF system was 8.7-fold greater than that without catalase,s howing an enhanced therapeutic effect against hypoxic tumor cells. Furthermore,b yc oupling with photothermal therapyo fB Qs, photodynamic-thermal synergistic therapyw as realized both in vitro and in vivo.
Functionalization of metal-organic frameworks (MOFs)with nanoparticles (NPs) or biomolecules has attracted great attention in catalysis,s eparation, and biomedical applications. [1] Fabrication of nanoparticle-functionalized MOFs (NP/MOFs) was usually divided into three different strategies:o ne-pot method to induce the NPs within the cavities of the MOF, [2] post-absorption of NPs onto the MOF surfaces [3] and in situ growth of MOF on pre-synthesized NPs. [4] TheN P/MOFs demonstrated efficient charge separation and excellent catalytic activity due to the uniform distribution of NPs and sensitization of MOFs. [5] On the other hand, the decoration of biomolecules,such as enzymes, DNA, and peptides,i nto MOFs was rare due to the lack of mild synthetic conditions. [6] Initially,e nzymes such as horseradish peroxidase were assembled on MOFs by surface attachment. [7] Later, ai nsitu encapsulated strategy was evolved to embed catalase into zeolitic imidazolate framework (ZIF) matrix via awater-based mild approach. [8] In our previous work, ap eptide-AuNP/ZIF-8 core-shell nanocomposite with high activity was established in am ild condition for imaging intracellular enzymes. [9] To date,the simultaneous distribution of nanoparticles and enzymes in aMOF structure remains ag reat challenge,w hich inspires us to generate aprogrammable platform as atandem catalyst for biomedical applications.Black phosphorus (BP) is ap romising metal-free nanomaterial in biological fields due to its instinct structure and good biocompatibility. [10] In particular,BPquantum dot (BQ) displays optical properties,s uch as both singlet oxygen ( 1 O 2 ) production and photothermal conversion efficiency for photodynamic therapy (PDT) and photothermal therapy (PTT), [11] respectively,o wing to the quantum confinement and edge effects. [12] Herein, for enhanced therapy in hypoxia, [13] aB Qa nd catalase co-encapsulated Materials of Institute Lavoisier (MIL-101)-type MOF heterostructure (BQ-MIL@cat-MIL) was constructed by the precise assembly of BQ in MIL to form the BQ-MIL inner,a nd followed by introduction of catalase into the outer layer of MIL (Scheme 1). Remarka...