Hierarchically encapsulating enzymes with multi-shelled metal-organic frameworks for tandem biocatalytic reactions

Abstract

Biocatalytic transformations in living organisms, such as multi-enzyme catalytic cascades, proceed in different cellular membrane-compartmentalized organelles with high efficiency. Nevertheless, it remains challenging to mimicking biocatalytic cascade processes in natural systems. Herein, we demonstrate that multi-shelled metal-organic frameworks (MOFs) can be used as a hierarchical scaffold to spatially organize enzymes on nanoscale to enhance cascade catalytic efficiency. Encapsulating multi-enzymes with multi-shelled MOFs by epitaxial shell-by-shell overgrowth leads to 5.8~13.5-fold enhancements in catalytic efficiencies compared with free enzymes in solution. Importantly, multi-shelled MOFs can act as a multi-spatial-compartmental nanoreactor that allows physically compartmentalize multiple enzymes in a single MOF nanoparticle for operating incompatible tandem biocatalytic reaction in one pot. Additionally, we use nanoscale Fourier transform infrared (nano-FTIR) spectroscopy to resolve nanoscale heterogeneity of vibrational activity associated to enzymes encapsulated in multi-shelled MOFs. Furthermore, multi-shelled MOFs enable facile control of multi-enzyme positions according to specific tandem reaction routes, in which close positioning of enzyme-1-loaded and enzyme-2-loaded shells along the inner-to-outer shells could effectively facilitate mass transportation to promote efficient tandem biocatalytic reaction. This work is anticipated to shed new light on designing efficient multi-enzyme catalytic cascades to encourage applications in many chemical and pharmaceutical industrial processes.

Antibacterial Vancomycin@ZIF-8 Loaded PVA Nanofiber Membrane for Infected Bone Repair

“…The particle composition and drug encapsulation were further characterized by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). The XRD patterns in Figure S1a confirm the characteristic peaks (7.3°, 10.4°, 12.8°, 14.8°, 16.5°, 18.1°, 22.2°, 24.6°, 26.7°, 29.8°) of ZIF-8 and V@Z [ 23 , 24 ], suggesting that the addition of Van did not affect the composition of ZIF-8. Figure S1b shows the characteristic diffraction peaks of ZIF-8 at 3135, 2925, 1584 cm − 1 , corresponding to the aromatic and aliphatic C-H groups and the stretching vibrations of C=N in imidazole, respectively.…”

Confining enzymes in porous organic frameworks: from synthetic strategy and characterization to healthcare applications

“…In addition, the inter-enzyme distance could be adjusted by tuning the epitaxial growth cycles of ZIF-8, and the results suggested the close positioning of the enzyme-1-loaded and enzyme-2-loaded shells along the inner-to-outer shells, favoring the biocascade reactions by shortening the transportation path between the spatially confined enzymes. 90 This method shows ability to mimic biological systems, in which the spatial The cavity structure of MOFs can be controlled and filled independently. Thus, considering this, designing hierarchical MOFs containing various types of cages with different dimensions is another efficient method to precisely control the distribution of each enzyme in a single MOF.…”

“…7a). 90 In the first step, enzyme-1 was embedded in ZIF-8 via a de novo approach. The resulting ZIF-8 biocomposite was used as the core to seed the overgrowth of the ZIF-8 shell in the second step and enzyme-2 was encapsulated during this epitaxial overgrowth.…”

A triphenylamine-based Pt(ii) metallacage via coordination-driven self-assembly for nonlinear optical power limiting

“…Coordination-chemistry-driven self-assembly has emerged in the last decade as a straightforward synthetic approach and has provided increasingly intricate and functional supramolecular coordination complexes (SCCs), [1][2][3][4] including both metalorganic frameworks (MOFs) [5][6][7] and metal-organic polyhedra (MOPs). 8,9 The chemical and structural diversity, tunability, flexibility, and permanent porosity of these materials make them valuable for a wide range of applications in guest encapsulation, [10][11][12] catalysis, 13,14 sensors, [15][16][17] bioimaging agents, 18,19 and so on. Another advantage unique to SCCs is the availability of sufficient pore space to accommodate functional groups on the building blocks without interfering with their linkage or alignment.…”