Solvent-Assisted Self-Assembly of a Metal–Organic Framework Based Biocatalyst for Cascade Reaction Driven Photodynamic Therapy

Abstract

Biocatalytic reactions in living cells involve complex transformations in the spatially confined microenvironments. Inspired by biological transformation processes, we demonstrate effective biocatalytic cascade driven photodynamic therapy in tumor-bearing mice by the integration of an artificial enzyme (ultrasmall Au nanoparticles) with upconversion nanoparticles (NaYF 4 @NaYb 0.92 F 4 :Er 0.08 @NaYF 4 )zirconium/iron porphyrin metal−organic framework core−shell nanoparticles (UMOF NPs) which act as biocatalysts and nanoreactors. The construction of core−shell UMOF NPs are realized by using a unique "solventassisted self-assembly" method. The integration of ultrasmall AuNPs on the UMOFs matrix leads to glucose depletion, providing Au-mediated cancer therapy via glucose oxidase like catalytic activity. Meanwhile, the UMOF matrix acts as a nearinfrared (NIR) light photon-activated singlet oxygen generator through a continuous supply of oxygen via hydrogen peroxide decomposition upon irradiation. Such kinds of biocatalysts offer exciting opportunities for biomedical, catalytical ,and energy applications.

Tunable Polymeric Scaffolds for Enzyme Immobilization

“…Protein-NCP hybrids have been applied to a wide range of applications, such as sensing ( Wang et al, 2016 ; Gao et al, 2017 ; Vinita et al, 2018 ; Wu et al, 2019 ; Xiong et al, 2020 ), microfluidic systems ( Hu et al, 2020 ), removal of pollutants ( Shen et al, 2019 ), photodynamic therapies ( Cheng et al, 2016 ; Li et al, 2017 ; You et al, 2019 ; He et al, 2020 ), protein delivery ( Chen et al, 2018 ; Yang et al, 2019 ; Zhang et al, 2019a ; Alyami et al, 2020 ) or even for the optimization of the polymerase chain reaction (PCR) ( Sun et al, 2020 ). Undoubtedly, the nature of the ligands and metals used for the synthesis of the MOFs has a direct impact on the final structure of the hybrid and eventually on the activity of the enzyme.…”

Gold‐Nanoparticle‐Decorated Metal‐Organic Frameworks for Anticancer Therapy

“…The activity of this solid was examined in the biocatalytic cascade-driven PDT in a mice bearing tumor. [87] UMOFs matrix has provided many anchoring sites for the stabilization of Au NPs and are homogeneously dispersed with the mean diameter of 2 nm ( Figure 6) as shown by TEM. In this hybrid catalyst, Fe-porphyrin MOFs (UMOFs) NPs served as biomimetic solids to effect the transformation of H 2 O 2 into O 2 by the MOFs shell.…”

“…UMOFs: Upconversion MOFs. Reproduced with permission from ref [87]. Copyright 2020 American Chemical Society.…”

“…a) Synthesis of core-shell-shell UCNPs; b) synthesis of core-shell UMOFs@Au NPs and c) synergistic cascade reactions for cancer therapy-mediated PDT by core-shell UMOFs@Au NPs. Reproduced with permission from ref [87]. Copyright 2020 American Chemical Society.…”

The prototypes of nanozyme-based nanorobots

“…In this scheme, decorated with Au nanozymes, the newly synthesized MOF nanozyme possessed GOx-like and catalase-like activities. With the capability of converting NIR light to generate 1 O 2 , the MOF nanozyme further killed the cancer cells (He et al 2020). Glucoses were depleted by MOF nanozymes in tumor cells, leading to the loss of nutrition in these cancer cells.…”