In the FeGP cofactor of [Fe]-hydrogenase, low-spin FeII is in complex with two CO ligands and a pyridinol derivative; the latter ligates the iron with a 6-acylmethyl substituent and the pyridinol nitrogen. A guanylylpyridinol derivative, 6-carboxymethyl-3,5-dimethyl-4-guanylyl-2-pyridinol (3), is produced by the decomposition of the FeGP cofactor under irradiation with UV-A/blue light and is also postulated to be a precursor of FeGP cofactor biosynthesis. HcgC and HcgB catalyze consecutive biosynthesis steps leading to 3. Here, we report an in vitro biosynthesis assay of the FeGP cofactor using the cell extract of the ΔhcgBΔhcgC strain of Methanococcus maripaludis, which does not biosynthesize 3. We chemically synthesized pyridinol precursors 1 and 2, and detected the production of the FeGP cofactor from 1, 2 and 3. These results indicated that 1, 2 and 3 are the precursors of the FeGP cofactor, and the carboxy group of 3 is converted to the acyl ligand.
|Original language||English (US)|
|Journal||Angewandte Chemie - International Edition|
|State||Published - May 23 2022|
Bibliographical noteFunding Information:
We thank Thomas Lie and John A. Leigh for providing us with the mutated strains. We thank Johann Heider and Rudolf K. Thauer for helpful discussion. This work was supported by Deutsche Forschungsgemeinschaft, Priority Program, Iron‐Sulfur for Life (SPP1927, SH87/1‐1 and SH87/1‐2) and by the Max Planck Society to S.Sh. and by the Swiss National Science Foundation (200021_181977) to X.H. Open Access funding enabled and organized by Projekt DEAL. M. maripaludis
© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.
- Acyl Ligands
- FeGP Cofactor
- Iron-Sulfur Proteins/chemistry
PubMed: MeSH publication types
- Research Support, Non-U.S. Gov't
- Journal Article