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Zinc Substitution of Cobalt in Vitamin B12 : Zincobyric acid and Zincobalamin as Luminescent Structural B12 -Mimics.
Kieninger, Christoph; Baker, Joseph A; Podewitz, Maren; Wurst, Klaus; Jockusch, Steffen; Lawrence, Andrew D; Deery, Evelyne; Gruber, Karl; Liedl, Klaus R; Warren, Martin J; Kräutler, Bernhard.
Afiliação
  • Kieninger C; Institute of Organic Chemistry and Center for Molecular Biosciences (CMBI), University of Innsbruck, 6020, Innsbruck, Austria.
  • Baker JA; School of Biosciences, University of Kent, Canterbury, CT2 7NJ, UK.
  • Podewitz M; Institute of General, Inorganic and Theoretical Chemistry and Center for Molecular Biosciences (CMBI), University of Innsbruck, 6020, Innsbruck, Austria.
  • Wurst K; Institute of General, Inorganic and Theoretical Chemistry and Center for Molecular Biosciences (CMBI), University of Innsbruck, 6020, Innsbruck, Austria.
  • Jockusch S; Department of Chemistry, Columbia University, New York, USA.
  • Lawrence AD; School of Biosciences, University of Kent, Canterbury, CT2 7NJ, UK.
  • Deery E; School of Biosciences, University of Kent, Canterbury, CT2 7NJ, UK.
  • Gruber K; Institute for Molecular Biosciences, University of, Graz, Austria.
  • Liedl KR; Institute of General, Inorganic and Theoretical Chemistry and Center for Molecular Biosciences (CMBI), University of Innsbruck, 6020, Innsbruck, Austria.
  • Warren MJ; School of Biosciences, University of Kent, Canterbury, CT2 7NJ, UK.
  • Kräutler B; Institute of Organic Chemistry and Center for Molecular Biosciences (CMBI), University of Innsbruck, 6020, Innsbruck, Austria.
Angew Chem Int Ed Engl ; 58(41): 14568-14572, 2019 10 07.
Article em En | MEDLINE | ID: mdl-31420932
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 1 O2 (ΦΔ =0.70).
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Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Assunto principal: Vitamina B 12 / Zinco / Cobalto Idioma: En Revista: Angew Chem Int Ed Engl Ano de publicação: 2019 Tipo de documento: Article
Texto completo
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Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Assunto principal: Vitamina B 12 / Zinco / Cobalto Idioma: En Revista: Angew Chem Int Ed Engl Ano de publicação: 2019 Tipo de documento: Article