Hierarchically Engineered Mesoporous Metal-Organic Frameworks toward Cell-free Immobilized Enzyme Systems

Peng Li, Qishui Chen, Timothy C. Wang, Nicolaas A. Vermeulen, B. Layla Mehdi, Alice Dohnalkova, Nigel D. Browning, Dengke Shen, Ryther Anderson, Diego A. Gómez-Gualdrón, Furkan M. Cetin, Jacek Jagiello, Abdullah M. Asiri, J. Fraser Stoddart, Omar K. Farha

Index: 10.1016/j.chempr.2018.03.001

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Abstract

Highly efficient cell-free enzymatic systems are typically difficult to achieve in traditional immobilized enzyme systems because of the lack of optimal spatial control of enzyme localization, substrate and product diffusion, and enzyme and coenzyme accessibility. Here, we report a strategy for expanding the pore apertures (from 3.3 to 6.7 nm) of a series of Zr-based metallic-organic frameworks (MOFs) (termedNU-100x,x= 3, 4, 5, 6, 7) with interconnected hierarchical pores by maintaining precise control of torsional angles associated with the linkers. As a proof of concept, we use the expandedNU-100xMOF structures to encapsulate lactate dehydrogenase (LDH) and demonstrate the use of the captured protein in a cell-free biosynthetic catalytic system. Remarkably, LDH immobilized in the large pores of the MOF is accessible to nicotinamide adenine dinucleotide coenzymes (NAD and NADH), allowing forin situcoenzyme regeneration leading to higher activity than that of the free enzyme.