A host\u2013guest semibiological photosynthesis system coupling artificial and natural enzymes for solar alcohol splitting

Junkai Cai,Yanan Li,Cheng He,Chunying Duan,Liang Zhao

doi:10.1038/s41467-021-25362-4

Junkai Cai, Yanan Li + Show 3 more

Open Access

https://doi.org/10.1038/s41467-021-25362-4

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Abstract

Development of a versatile, sustainable and efficient photosynthesis system that integrates intricate catalytic networks and energy modules at the same location is of considerable future value to energy transformation. In the present study, we develop a coenzyme-mediated supramolecular host-guest semibiological system that combines artificial and enzymatic catalysis for photocatalytic hydrogen evolution from alcohol dehydrogenation. This approach involves modification of the microenvironment of a dithiolene-embedded metal-organic cage to trap an organic dye and NADH molecule simultaneously, serving as a hydrogenase analogue to induce effective proton reduction inside the artificial host. This abiotic photocatalytic system is further embedded into the pocket of the alcohol dehydrogenase to couple enzymatic alcohol dehydrogenation. This host-guest approach allows in situ regeneration of NAD+/NADH couple to transfer protons and electrons between the two catalytic cycles, thereby paving a unique avenue for a synergic combination of abiotic and biotic synthetic sequences for photocatalytic fuel and chemical transformation.

Highlights

Development of a versatile, sustainable and efficient photosynthesis system that integrates intricate catalytic networks and energy modules at the same location is of considerable future value to energy transformation
While situated inside the alcohol dehydrogenase (ADH) catalytic pocket, the coenzyme is in direct contact with two catalytic cycles in situ, which enables it to maintain a closed loop of electrons and protons, thereby allowing the formation of a versatile redoxneutral photosynthesis system to actuate a non-photoactive natural enzyme for solar chemical conversion
CoBDT2 dramatically inhibited the production of aldehyde (Fig. 3b and Supplementary Fig. 31), which might be due to the inert binding of CoBDT2 to ADH (Supplementary Fig. 21). These results demonstrated the ability of supramolecular catalysts to synergistically catalyze with natural enzymes in an efficient and compatible way, achieving a redox-neutral catalysis different from

Summary

Introduction

Development of a versatile, sustainable and efficient photosynthesis system that integrates intricate catalytic networks and energy modules at the same location is of considerable future value to energy transformation. We develop a coenzyme-mediated supramolecular host-guest semibiological system that combines artificial and enzymatic catalysis for photocatalytic hydrogen evolution from alcohol dehydrogenation This approach involves modification of the microenvironment of a dithiolene-embedded metal-organic cage to trap an organic dye and NADH molecule simultaneously, serving as a hydrogenase analogue to induce effective proton reduction inside the artificial host. This abiotic photocatalytic system is further embedded into the pocket of the alcohol dehydrogenase to couple enzymatic alcohol dehydrogenation. While situated inside the ADH catalytic pocket, the coenzyme is in direct contact with two catalytic cycles in situ, which enables it to maintain a closed loop of electrons and protons, thereby allowing the formation of a versatile redoxneutral photosynthesis system to actuate a non-photoactive natural enzyme for solar chemical conversion

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Results

Conclusion