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Construction of a whole-cell biohybrid catalyst using a Cp*Rh (III)-dithiophosphate complex as a precursor of a metal cofactor
| Title: | Construction of a whole-cell biohybrid catalyst using a Cp*Rh (III)-dithiophosphate complex as a precursor of a metal cofactor |
| Authors: | Kato, Shunsuke Browse this author | | Onoda, Akira Browse this author →KAKEN DB | | Grimm, Alexander R. Browse this author | | Schwaneberg, Ulrich Browse this author | | Hayashi, Takashi Browse this author →KAKEN DB |
| Keywords: | Biohybrid catalyst | | Artificial metalloenzyme | | Whole-cell catalyst | | Rhodium | | C-H bond functionalization |
| Issue Date: | Mar-2021 |
| Publisher: | Elsevier |
| Journal Title: | Journal of Inorganic Biochemistry |
| Volume: | 216 |
| Start Page: | 111352 |
| Publisher DOI: | 10.1016/j.jinorgbio.2020.111352 |
| Abstract: | A whole-cell biohybrid catalyst where a (pentamethylcyclopentadienyl)rhodium(III) (Cp*Rh(III)) complex was covalently incorporated into the cavity of nitrobindin (NB), a beta-barrel protein, was prepared on an E. coli cell surface to produce isoquinolines via C(sp2)-H bond activation. In this whole-cell biohybrid system, the Cp*Rh (III)-dithiophosphate complex with latent catalytic activity was utilized as a precursor of the metal cofactor. Strong chelation of the dithiophosphate ligands protects the rhodium complex from being deactivated by abundant nucleophiles in cellular environments during conjugation of the cofactor with the protein scaffold. The whole-cell biohybrid catalyst was then activated upon addition of Ag+ ion to dissociate the dithiophosphate ligands and promoted cycloaddition of acetophenone oxime with diphenylacetylene. Furthermore, the activity of the Cp*Rh(III)-linked whole-cell biohybrid catalyst was enhanced 2.1-fold by introducing glutamate residues at positions adjacent to the Cp*Rh(III) cofactor. These results indicate that the use of the Cp*Rh(III)dithiophosphate complex with switchable activity from a "latent" form to an "active" form provides a new strategy for generating whole-cell biohybrid catalysts. |
| Type: | article |
| URI: | http://hdl.handle.net/2115/82313 |
| Appears in Collections: | 環境科学院・地球環境科学研究院 (Graduate School of Environmental Science / Faculty of Environmental Earth Science) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)
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