Zinc Substitution of Cobalt in Vitamin B 12 : Zincobyric acid and Zincobalamin as Luminescent Structural B 12 -Mimics
Zinc Substitution of Cobalt in Vitamin B 12 : Zincobyric acid and Zincobalamin as Luminescent Structural B 12 -Mimics
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维生素 B 12 中钴的锌替代：锌钴酸和锌钴胺作为发光结构 B 12 模拟物
DOI：
10.1002/ange.201908428
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发表时间：
2019
影响因子：
--
通讯作者：
Kieninger C
中科院分区：
文献类型：
--
作者：
Kieninger C
用其他金属取代维生素B12的中心钴离子一直是B12领域的长期愿望。在此，我们描述了从氢丁酸合成锌钴酸（Znby）和锌钴胺（Znbl），分别是天然钴-可林的锌钴酸和维生素B12的锌类似物。 通过核磁共振光谱研究了Znby和Znbll的溶液结构。Znby的单晶被生产出来，提供了锌咕啉的第一个X射线晶体结构。Znby和计算生成的Znbl的结构被发现类似于相应的CoII-corrins，使得这种Zn-corrins可能用于研究B12-依赖性过程。Znby的单重激发态寿命较短，受到快速进入三重态的系统间跃迁的限制。Znby允许前所未有地观察到咕啉三重态（ET=190 kJ mol−1），并被发现是1 O2的优秀光敏剂（ΦΔ=0.70）。
Replacing the central cobalt ion of vitamin B12by 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 ofZnbyandZnblwere studied by NMR‐spectroscopy. Single crystals ofZnbywere produced, providing the first X‐ray crystallographic structure of a zinc corrin. The structures ofZnbyand of computationally generatedZnblwere found to resemble the corresponding CoII‐corrins, making such Zn‐corrins potentially useful for investigations of B12‐dependent processes. The singlet excited state ofZnbyhad a short life‐time, limited by rapid intersystem crossing to the triplet state.Znbyallowed the unprecedented observation of a corrin triplet (ET=190 kJ mol−1) and was found to be an excellent photo‐sensitizer for1O2(ΦΔ=0.70).