Invited Talk 21st International Conference on Biological Inorganic Chemistry 2025

Hybridized metal-organic capsules binding with enzymes for biomimetic catalysis (123531)

Chunying Duan 1 2
  1. State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing, Jiangsu, China
  2. School of Chemistry , Dalian University of Technology, Dalian, Liaoning, China

Supramolecular approaches to combining established natural enzymes with artificial catalysts have become a vital form to achieve efficient and selective catalytic conversions in a bio-orthogonal way.1 The construction of disparate abiological functional groups within the active domain of enzymes in bioinorganic hybrid systems is becoming a highly promising route toward unusual catalytic results immersed in one-pot intricate catalytic networks. As the metal-organic capsules with decorated cofactors enable the efficient proton/electron transfer between the inner and outer spaces of the microenvironment without the cofactor shuttling,2 we envisioned that a supramolecular approach that included the cofactors (i.e., NADH and FAD) and its mimics into the surface of a catalyst-functionalized assembly would be a new approach to combine multiple individual active sites into catalytic pockets of enzymes, enabling biological cascades by merging abiotic catalysis with cofactor-dependent enzymatic reactions in one working module.3 By installing both NADH and heme analogues into a flavin model contained heteroleptic metal-organic rectangle, such cytochrome P450 oxygenase analogue could efficiently catalytic oxidative cascade in tandem with dehydrogenases.4 By grafting a cage-dye-NADH clathrate clathrate with glucose dehydrogenase (GDH), a consecutive photoinduced electron-transfer approach to reform biomass into fuels and active H-source for nitroarene reduction was achieved (Figure 1). The grafting enzyme combines artificial photocatalysis and enzymatic dehydrogenation to innovate a unique paradigm for the sustainable energy scheme that combines energy of two photons in one turnover cycle.5 The host-guest approach to simultaneously introduce virous functional groups into different enzymes paves a way for the application of bio-inorganic systems in bionic catalysis.

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Figure 1. Construction of bio-inorganic systems containing metal-organic capsules binding with enzymes.

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  2. Wei, J.; Zhao, L.; Zhang, Y.; Han, G.; He, C.; Wang, C.; Duan, C. J. Am. Chem. Soc., 2023, 145, 6719-6729.
  3. Cai, J.; Zhao, L.; He, C.; Li, Y.; Duan. C. Nat. Commun., 2021, 12, 5092.
  4. Cai, J.; Zhao, L.; Li, Y.; He, C.; Wang, C.; Duan, C. JACS Au, 2022, 2, 1736-1746.
  5. Li, Z.; Cai, J.; Wang, L.; Duan, C. ACS Catal., 2024, 14, 16374-16382.