Zinc substitution of cobalt in vitamin B12: Zincobyric acid and zincobalamin as luminescent structural B12‐mimics

Christoph Kieninger; Joseph A. Baker; Maren Podewitz; Klaus Wurst; Steffen Jockusch; Andrew D. Lawrence; Evelyne Deery; Karl Gruber; Klaus R. Liedl; Martin J. Warren; Bernhard Kräutler

doi:10.1002/anie.201908428

Zinc substitution of cobalt in vitamin B12: Zincobyric acid and zincobalamin as luminescent structural B12‐mimics

Christoph Kieninger, Joseph A. Baker, Maren Podewitz, Klaus Wurst, Steffen Jockusch, Andrew D. Lawrence, Evelyne Deery, Karl Gruber, Klaus R. Liedl, Martin J. Warren, Bernhard Kräutler

Research output: Contribution to journal › Article › peer-review

23 Citations (Scopus)

15 Downloads (Pure)

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).

Original language	English
Pages (from-to)	14568-14572
Number of pages	5
Journal	Angewandte Chemie-International Edition
Volume	58
Issue number	41
Early online date	17 Aug 2019
DOIs	https://doi.org/10.1002/anie.201908428
Publication status	Published - 7 Oct 2019

Access to Document

10.1002/anie.201908428Licence: CC BY

Published_VersionFinal published version, 2.21 MBLicence: CC BY

Martin Warren
- Martin.Warrenuea.acuk
- Faculty of Science - Group Leader
- Norwich Institute for Healthy Aging - Member
Person: Research Centre Member, Academic, Teaching & Research

Cite this

Kieninger, C., Baker, J. A., Podewitz, M., Wurst, K., Jockusch, S., Lawrence, A. D., Deery, E., Gruber, K., Liedl, K. R., Warren, M. J., & Kräutler, B. (2019). Zinc substitution of cobalt in vitamin B12: Zincobyric acid and zincobalamin as luminescent structural B12‐mimics. Angewandte Chemie-International Edition, 58(41), 14568-14572. https://doi.org/10.1002/anie.201908428

@article{1a64fb0572674f118f2048fca987e02b,

title = "Zinc substitution of cobalt in vitamin B12: Zincobyric acid and zincobalamin as luminescent structural B12‐mimics",

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).",

author = "Christoph Kieninger and Baker, {Joseph A.} and Maren Podewitz and Klaus Wurst and Steffen Jockusch and Lawrence, {Andrew D.} and Evelyne Deery and Karl Gruber and Liedl, {Klaus R.} and Warren, {Martin J.} and Bernhard Kr{\"a}utler",

year = "2019",

month = oct,

day = "7",

doi = "10.1002/anie.201908428",

language = "English",

volume = "58",

pages = "14568--14572",

journal = "Angewandte Chemie-International Edition",

issn = "1433-7851",

publisher = "Wiley",

number = "41",

}

Kieninger, C, Baker, JA, Podewitz, M, Wurst, K, Jockusch, S, Lawrence, AD, Deery, E, Gruber, K, Liedl, KR, Warren, MJ & Kräutler, B 2019, 'Zinc substitution of cobalt in vitamin B12: Zincobyric acid and zincobalamin as luminescent structural B12‐mimics', Angewandte Chemie-International Edition, vol. 58, no. 41, pp. 14568-14572. https://doi.org/10.1002/anie.201908428

TY - JOUR

T1 - Zinc substitution of cobalt in vitamin B12: Zincobyric acid and zincobalamin as luminescent structural B12‐mimics

AU - Kieninger, Christoph

AU - Baker, Joseph A.

AU - Podewitz, Maren

AU - Wurst, Klaus

AU - Jockusch, Steffen

AU - Lawrence, Andrew D.

AU - Deery, Evelyne

AU - Gruber, Karl

AU - Liedl, Klaus R.

AU - Warren, Martin J.

AU - Kräutler, Bernhard

PY - 2019/10/7

Y1 - 2019/10/7

N2 - 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).

AB - 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).

U2 - 10.1002/anie.201908428

DO - 10.1002/anie.201908428

M3 - Article

VL - 58

SP - 14568

EP - 14572

JO - Angewandte Chemie-International Edition

JF - Angewandte Chemie-International Edition

SN - 1433-7851

IS - 41

ER -

Zinc substitution of cobalt in vitamin B12: Zincobyric acid and zincobalamin as luminescent structural B12‐mimics

Abstract

Access to Document

Profiles

Martin Warren

Cite this