Activities per year
Abstract
Artificial metalloenzymes that contain protein-anchored synthetic catalysts are attracting increasing interest. An exciting, but still unrealized advantage of non-covalent anchoring is its potential for reversibility and thus component recycling. Here we present a siderophore–protein combination that enables strong but redox-reversible catalyst anchoring, as exemplified by an artificial transfer hydrogenase (ATHase). By linking the iron(iii)-binding siderophore azotochelin to an iridium-containing imine-reduction catalyst that produces racemic product in the absence of the protein CeuE, but a reproducible enantiomeric excess if protein bound, the assembly and reductively triggered disassembly of the ATHase was achieved. The crystal structure of the ATHase identified the residues involved in high-affinity binding and enantioselectivity. While in the presence of iron(iii), the azotochelin-based anchor binds CeuE with high affinity, and the reduction of the coordinated iron(iii) to iron(ii) triggers its dissociation from the protein. Thus, the assembly of the artificial enzyme can be controlled via the iron oxidation state.
Original language | English |
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Pages (from-to) | 680-688 |
Number of pages | 9 |
Journal | Nature Catalysis |
Volume | 1 |
Issue number | 9 |
Early online date | 20 Aug 2018 |
DOIs | |
Publication status | Published - 1 Sept 2018 |
Bibliographical note
© 2018, Springer Nature. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for detailsProfiles
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Faraday Discussion Meeting Harnessing Non Covalent Interactions
Anne-Kathrin Duhme-Klair (Committee member)
12 Apr 2023 → 14 Apr 2023Activity: Participating in or organising an event › Conference
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Iron on the move: using siderophores to deliver catalysts and antimicrobials (Osaka University, Japan)
Anne-Kathrin Duhme-Klair (Invited speaker)
5 Dec 2022Activity: Talk or presentation › Invited talk
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Asian Biological Inorganic Chemistry Conference (AsBIC)
Anne-Kathrin Duhme-Klair (Keynote/plenary speaker)
28 Nov 2022 → 3 Dec 2022Activity: Participating in or organising an event › Conference
Projects
- 1 Finished
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Siderophores as anchors in artificial metalloenzymes
Duhme-Klair, A. & Wilson, K. S.
31/12/14 → 30/12/17
Project: Research project (funded) › Research
Datasets
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Redox-switchable siderophore anchor enables reversible artificial metalloenzyme assembly
Raines, D. J. (Creator), Clarke, J. E. (Contributor), Blagova, L. (Contributor), Dodson, E. J. (Contributor), Wilson, K. S. (Contributor) & Duhme-Klair, A. (Creator), University of York, 2017
DOI: 10.15124/233cf8cc-d25a-4793-b667-7557836774c1
Dataset
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Dataset associated with publication: Kinetic and structural analysis of redox-reversible artificial imine reductases
Miller, A. H. (Data Collector), Martins, I. (Contributor) & Duhme-Klair, A. (Creator), University of York, 29 Jul 2024
DOI: 10.15124/65fe7181-d559-4573-a062-40e064929706
Dataset