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TitleAn interfacial-intramolecular electron highway for accelerated electrocatalytic CO reduction by an O-tolerant formate dehydrogenase.
Journal, issue, pagesNat Commun, Year 2026
Publish dateMar 3, 2026
AuthorsWeisong Liu / Peng Zhang / Xiufeng Wang / Kuncheng Zhang / Wenhua Yang / Huijuan Cui / Jun Liu / Junsong Sun / Chun You / Haiyang Cui / Zhiguang Zhu / Lingling Zhang /
PubMed AbstractBioelectrocatalytic CO reduction offers a sustainable route for CO bioconversion, yet remains limited by interfacial-intramolecular electron transfer and oxygen sensitivity. Here, we mine a formate ...Bioelectrocatalytic CO reduction offers a sustainable route for CO bioconversion, yet remains limited by interfacial-intramolecular electron transfer and oxygen sensitivity. Here, we mine a formate dehydrogenase from Shewanella oneidensis MR-1 (SoFdhAB) featuring completely oxygen tolerant and direct-electron-transfer (DET) electrocatalytic performances. Cryo-electron microscopy (Cryo-EM) analysis reveals an intramolecular electron highway comprising five [4Fe-4S] clusters, a regional face-face contact facilitating interfacial ET, and a unique oxygen resistance mechanism different from inactivation-activation. By acquiring a beneficial variant SoFdhAB-Y94S, a direct bioelectrocatalytic CO reduction system is constructed, accumulating 2.88 ± 0.03 mmol formate in 64 hours with a steady rate of 45.3 ± 0.5 μmol h cm and a Faradaic efficiency of 93.1 ± 5.2%. The merits of oxygen tolerance and efficient (electro)catalytic property endow SoFdhAB a robust enzyme adopted in potential application scenarios, and the inherent DET capability may inspire the interfacial engineering of other oxidoreductases.
External linksNat Commun / PubMed:41775696
MethodsEM (single particle)
Resolution2.75 Å
Structure data

64903

9vap

EMDB-64903, PDB-9vap:
Cryo-EM structure of formate dehydrogenase from Shewanella oneidensis MR-1 (SoFdhAB)
Method: EM (single particle) / Resolution: 2.75 Å

Chemicals

ChemComp-MGD:
2-AMINO-5,6-DIMERCAPTO-7-METHYL-3,7,8A,9-TETRAHYDRO-8-OXA-1,3,9,10-TETRAAZA-ANTHRACEN-4-ONE GUANOSINE DINUCLEOTIDE

ChemComp-SF4:
IRON/SULFUR CLUSTER

ChemComp-H2S:
HYDROSULFURIC ACID

ChemComp-W:
Unknown entry

Source
  • shewanella oneidensis mr-1 (bacteria)
KeywordsOXIDOREDUCTASE / Formate dehydrogenase / carbon dioxide reduction / tungsten (W)-dependent

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