Solution, Crystal and in Silico Structures of the Organometallic Vitamin B 12 -Derivative Acetylcobalamin and of its Novel Rhodium-Analogue Acetylrhodibalamin
Solution, Crystal and in Silico Structures of the Organometallic Vitamin B 12 -Derivative Acetylcobalamin and of its Novel Rhodium-Analogue Acetylrhodibalamin
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有机金属维生素 B 12 衍生物乙酰钴胺及其新型铑类似物乙酰罗二巴明的溶液、晶体和计算机结构
DOI：
10.1002/hlca.202200158
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发表时间：
2023
影响因子：
1.8
通讯作者：
Wiedemair M
中科院分区：
文献类型：
--
作者：
Wiedemair M
天然维生素B12衍生物是钴的有趣配合物，它将金属困在明显倾斜和环状收缩的corrin配体中。在这里，我们描述了用生物技术生产的无金属氢酸合成Rh(III) - corrin乙酰钴胺素（AcRhbl），并分析了有机金属维生素B12 -衍生物乙酰钴胺素（AcCbl）的钴中心被其IX族同源物铑取代的效果，从而得到AcRhbl。为了获得对两种同源金属的结构适应的详细见解，我们在水溶液、晶体和硅方法中对facchblandacrhbl2的结构进行了彻底的分析。事实上，这两种金属环中常见的核苷酸附加的环配体具有广泛的结构相似性。因此，rhodium - corrinacrhbls加入了被归类为“抗维生素B12”的B12 -模拟物的小群体，天然钴- corrinacrhbls的等结构金属类似物在生物和生物医学应用中作为关键细胞过程的选择性抑制剂具有重大潜力。
The natural vitamin B12‐derivatives are intriguing complexes of cobalt that entrap the metal within the strikingly skewed and ring‐contracted corrin ligand. Here, we describe the synthesis of the Rh(III)‐corrin acetylrhodibalamin (AcRhbl) from biotechnologically produced metal‐free hydrogenobyric acid and analyze the effect of the replacement of the cobalt‐center of the organometallic vitamin B12‐derivative acetylcobalamin (AcCbl) with its group‐IX homologue rhodium, to giveAcRhbl. The structures ofAcCblandAcRhblwere thoroughly analyzed in aqueous solution, in crystals and byin silicomethods, in order to gain detailed insights into the structural adaptations to the two homologous metals. Indeed, the common, nucleotide‐appended corrin‐ligand in these two metal corrins features extensive structural similarity. Thus, the rhodium‐corrinAcRhbljoins the small group of B12‐mimics classified as ‘antivitamins B12’, isostructural metal analogues of the natural cobalt‐corrins that hold significant potential in biological and biomedical applications as selective inhibitors of key cellular processes.