Zinc substitution of cobalt in vitamin B12: zincobyric acid and zincobalamin as luminescent structural B12‐mimics
Zinc substitution of cobalt in vitamin B12: zincobyric acid and zincobalamin as luminescent structural B12‐mimics
Replacing the central cobalt ion of vitamin B12 by other metals has been a long-held aspiration within the B12-field. Herein, we describe the synthesis from hydrogenobyric acid of zincobyric acid (Znby) and zincobalamin (Znbl), the Zn-analogues of the natural cobalt-corrins cobyric acid and vitamin B12, respectively. The solution structures of Znby and Znbl were studied by NMR-spectroscopy. Single crystals of Znby were produced, providing the first X-ray crystallographic structure of a zinc corrin. The structures of Znby and of computationally generated Znbl were found to resemble the corresponding CoII-corrins, making such Zn-corrins potentially useful for investigations of B12-dependent processes. The singlet excited state of Znby had a short life-time, limited by rapid intersystem crossing to the triplet state. Znby allowed the unprecedented observation of a corrin triplet (ET=190 kJ mol−1) and was found to be an excellent photo-sensitizer for 1O2 (ΦΔ=0.70).
14568-14572
Kieninger, Christoph
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Baker, Joseph A.
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Podewitz, Maren
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Wurst, Klaus
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Jockusch, Steffen
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Lawrence, Andrew D.
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Deery, Evelyne
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Gruber, Karl
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Liedl, Klaus R.
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Warren, Martin J.
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Kräutler, Bernhard
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4 September 2019
Kieninger, Christoph
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Baker, Joseph A.
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Podewitz, Maren
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Wurst, Klaus
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Jockusch, Steffen
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Lawrence, Andrew D.
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Deery, Evelyne
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Gruber, Karl
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Liedl, Klaus R.
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Warren, Martin J.
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Kräutler, Bernhard
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Kieninger, Christoph, Baker, Joseph A., Podewitz, Maren, Wurst, Klaus, Jockusch, Steffen, Lawrence, Andrew D., Deery, Evelyne, Gruber, Karl, Liedl, Klaus R., Warren, Martin J. and Kräutler, Bernhard
(2019)
Zinc substitution of cobalt in vitamin B12: zincobyric acid and zincobalamin as luminescent structural B12‐mimics.
Angewandte Chemie International Edition, 58 (41), .
(doi:10.1002/anie.201908428).
Abstract
Replacing the central cobalt ion of vitamin B12 by other metals has been a long-held aspiration within the B12-field. Herein, we describe the synthesis from hydrogenobyric acid of zincobyric acid (Znby) and zincobalamin (Znbl), the Zn-analogues of the natural cobalt-corrins cobyric acid and vitamin B12, respectively. The solution structures of Znby and Znbl were studied by NMR-spectroscopy. Single crystals of Znby were produced, providing the first X-ray crystallographic structure of a zinc corrin. The structures of Znby and of computationally generated Znbl were found to resemble the corresponding CoII-corrins, making such Zn-corrins potentially useful for investigations of B12-dependent processes. The singlet excited state of Znby had a short life-time, limited by rapid intersystem crossing to the triplet state. Znby allowed the unprecedented observation of a corrin triplet (ET=190 kJ mol−1) and was found to be an excellent photo-sensitizer for 1O2 (ΦΔ=0.70).
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Angew Chem Int Ed - 2019 - Kieninger - Zinc Substitution of Cobalt in Vitamin B12 Zincobyric acid and Zincobalamin as
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e-pub ahead of print date: 17 August 2019
Published date: 4 September 2019
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Local EPrints ID: 488469
URI: http://eprints.soton.ac.uk/id/eprint/488469
ISSN: 1433-7851
PURE UUID: aa0368ff-101e-4848-8287-7f73a3f77533
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Date deposited: 22 Mar 2024 17:50
Last modified: 26 Mar 2024 03:05
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Author:
Christoph Kieninger
Author:
Joseph A. Baker
Author:
Maren Podewitz
Author:
Klaus Wurst
Author:
Steffen Jockusch
Author:
Andrew D. Lawrence
Author:
Evelyne Deery
Author:
Karl Gruber
Author:
Klaus R. Liedl
Author:
Martin J. Warren
Author:
Bernhard Kräutler
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