期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 60, 期 19, 页码 10919-10927出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202015834
关键词
direct coordination; ligand exchange; metalloenzymes; ruthenium; transfer hydrogenation
资金
- EPSRC [EP/N509620/1, EP/R513180/1]
- Peterhouse, Cambridge
- Chemistry Department
- EPSRC [1800459] Funding Source: UKRI
The study focuses on generating artificial metalloenzymes through ligand exchange, with a fast and robust procedure developed using Ru-II(eta(6)-arene)(bipyridine) complexes. By successfully introducing metal cofactors into proteins to generate catalysts, the research demonstrates a significant increase in catalytic activity.
Many natural metalloenzymes assemble from proteins and biosynthesised complexes, generating potent catalysts by changing metal coordination. Here we adopt the same strategy to generate artificial metalloenzymes (ArMs) using ligand exchange to unmask catalytic activity. By systematically testing Ru-II(eta(6)-arene)(bipyridine) complexes designed to facilitate the displacement of functionalised bipyridines, we develop a fast and robust procedure for generating new enzymes via ligand exchange in a protein that has not evolved to bind such a complex. The resulting metal cofactors form peptidic coordination bonds but also retain a non-biological ligand. Tandem mass spectrometry and F-19 NMR spectroscopy were used to characterise the organometallic cofactors and identify the protein-derived ligands. By introduction of ruthenium cofactors into a 4-helical bundle, transfer hydrogenation catalysts were generated that displayed a 35-fold rate increase when compared to the respective small molecule reaction in solution.
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