Compartmentalization within Self‐Assembled Metal–Organic Framework Nanoparticles for Tandem Reactions

Abstract

Compartmentalization is an essential feature found in living cells to ensure multiple biological processes occur without being affected by undesired external influences. Here, compartmentalized systems are developed based on the self-assembly of metal-organic framework (MOF) nanoparticles into multifunctional MOF capsules (MOF-Cs). Such MOF-Cs have the capability of controlling molecular transportation and protecting interior microenvironment, thus making tandem reaction along trajectories to desired products. First of all, MOF-Cs present controlled molecular transportation derived from molecular sieving property of MOFs. Second, MOF-Cs can protect the encapsulated cargoes from denaturation and maintain their catalytic activity. Third, MOF-Cs can provide spatial segregation for incompatible species and facilitate communication between these compartments to perform tandem reactions. These compartmentalized structures offer new views in the transportation, microreactor, and biotechnology. selective catalysis was achieved by employing a time-consuming approach, which was the assembly of UiO-66 NPs around emulsion droplets with the further deposition of ZIF-8. [21] Therefore, developing a facile strategy to construct MOF capsules in order to simultaneously realize efficient encapsulation, controlled transport, compartmentalization effect, and communication capabilities remains a considerable challenge.Here, we develop a facile strategy to structure MOF capsules (MOF-Cs) by the self-assembly process of MOF NPs in the oilwater surface and using polymer precipitation as a support layer for enhancing stability. The obtained MOF-Cs own the MOFs layer for controlling molecular transportation, the hollow structure for supplying confined reaction space, and the ability of encapsulating diverse species for offering catalytic active sites. First and foremost, MOF-Cs exhibit controlled transport originated from size-sieving ability of MOFs. Second, MOF-Cs can keep the encapsulated cargoes from denaturation and preserve their catalytic activity. Third, MOF-Cs can provide spatial segregation for incompatible species. Furthermore, MOF-Cs separately encapsulated with incompatible species are capable of communicating with each other to perform multistep reactions.

Multi‐enzyme Cascade Reactions in Metal‐organic Frameworks

“…Reprinted with permission. [40] Copyright 2018, John Wiley and Sons. c, (i) Schematic of peptide-induced the compartmentalized bi-enzyme and three-enzyme super-assembly and dissembled by protease; (ii) Absorbance changes of ABTS caused by the bienzyme cascade reaction with or without peptide functionalization.…”

“…[56] Another interesting compartmented multi-enzyme biosystem was reported by Huo and co-workers. [40] GOx and HRP were first mixed with polymers in water. Subsequently, by selfassembly of the UiO-66-NH 2 nanoparticles in the oil-water interface and GOx-polymer or HRP-polymer deposition inside MOF-capsules, GOx@MOFÀ Cs and HRP@MOFÀ Cs could be obtained.…”

“…Consequently, MOFÀ Cs with sieving property not only controlled the molecular transportation, but also protected the interior enzymes from adverse external environment, thereby leading to the cascade reaction along trajectories to the desired products. [40] These compartmentalized multi-enzyme in MOF systems offer new insight in the biotechnology and advanced energy application.…”

“…[41,55,56] More excitingly, with the merits of compartmentalization strategy and communication capability of MOFs, some chemically incompatible enzymes (e. g. protease and glucose oxidase) can be coupled together to function cooperatively for chemical synthesis. [40] Therefore, appropriate multi-enzyme immobilization strategies need to be cautiously designed. Notably, with satisfying advantages, multi-enzyme cascade reactions in MOFs have been exploited in several field.…”

Size-selective molecular recognition based on a confined DNA molecular sieve using cavity-tunable framework nucleic acids

“…1a). Benefiting from the size-selective molecular recognition in the confined space of molecular sieves, size-selective catalysis is able to improve catalysis selectivity and efficiency, as well as protect the catalyst sites from catalyst poisoning, thus leading to the wide application of molecular sieve-based catalyst in industrial catalysis [18][19][20][21][22] .…”