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To be dinuclear or not: Z-DNA induction by nickel complexes

机译:是否为双核:镍配合物诱导Z-DNA

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The left-handed Z-DNA has been identified as a gene regulating element. Therefore the generation of Z-DNA through metal complexes might be an innovative way for the regulation of gene expression. Use of the new dinuclear complex N,N,N',N'-tetrakis-[2(3,5-dimethylpyrazol-1-yl)ethyl]-1,3- propylenediamine-bis(nickel(II) dinitrate) (2) reversibly induced Z-DNA formation. However, when a 1:1 ratio of metal/dinucleating ligand was used as a control, the midpoint of the B- to Z-DNA transition was at the same nickel concentration as in case of the dinuclear complex. The novel mononuclear analogue, N-methyl-N,N-bis-[2(3,5-dimethylpyrazol-1-yl)ethyl]amine- nickel (II)-dinitrate (3) was inducing the Z-DNA at a similar ratio versus nucleotides as free nickel(II) itself. For the first time, proton and nickel binding constants for the bis-[2-(pyrazol-1-yl)ethyl]amine ligand system are reported and discussed. Both nickel complexes 2 and 3 were structurally characterized by single crystal analysis. Furthermore, the synthesis of the two new ligands, N,N,N',N'-tetrakis-[2-(3,5-dimethylpyrazol -1-yl)ethyl]-1,2-propylenediamine (4) and N-methyl-N,N-bis-[2(3,5-dimethylpyrazol-1-yl)ethyl]amine (5) is described. The two major synthetic pathways leading to polypyrazoyl amines in general are critically discussed with respect to yield, reproducibility and handling of the intermediates.
机译:左手Z-DNA已被鉴定为基因调节元件。因此,通过金属络合物生成Z-DNA可能是调节基因表达的创新方法。使用新的双核络合物N,N,N',N'-四-[2(3,5-二甲基吡唑-1-基)乙基] -1,3-丙二胺-双(镍(二)镍)(2 )可逆地诱导Z-DNA的形成。但是,当使用金属/异核配体的1:1比例作为对照时,B-Z-DNA过渡的中点与双核络合物的镍浓度相同。新型单核类似物N-甲基-N,N-双-[2(3,5-二甲基吡唑-1-基)乙基]胺-镍(II)-精制物(3)在相似的条件下诱导Z-DNA游离镍(II)本身与核苷酸的比率。首次报道和讨论了双-[2-(吡唑-1-基)乙基]胺配体系统的质子和镍结合常数。镍配合物2和3均通过单晶分析进行结构表征。此外,还合成了两个新的配体N,N,N',N'-四-[2-(3,5-二甲基吡唑-1-基)乙基] -1,2-丙二胺(4)和N-描述了甲基-N,N-双-[2(3,5-二甲基吡唑-1-基)乙基]胺(5)。通常就中间体的产率,可再现性和操作性,对导致聚吡唑酰基胺的两个主要合成途径进行了严格的讨论。

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