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金属促进的 2,6-二乙酰基吡啶双(2-氨基苯甲酰腙)镧系元素配合物的合成、表征、晶体结构和 RNA 切割能力。

Metal-promoted synthesis, characterization, crystal structure and RNA cleavage ability of 2,6-diacetylpyridine bis(2-aminobenzoylhydrazone) lanthanide complexes.

机构信息

Faculty of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60-780 Poznań, Poland.

出版信息

J Inorg Biochem. 2013 Sep;126:38-45. doi: 10.1016/j.jinorgbio.2013.05.005. Epub 2013 May 24.

DOI:10.1016/j.jinorgbio.2013.05.005
PMID:23770667
Abstract

New 2,6-diacetylpyridine bis(2-aminobenzoylhydrazone) lanthanide complexes were formed in the metal-induced one-step [1+2] condensation reaction between 2,6-diacetylpyridine and 2-aminobenzoylhydrazide in the presence of lanthanide (La(3+), Pr(3+), Nd(3+), Sm(3+), Eu(3+), Gd(3+), Tb(3+), Dy(3+), Ho(3+), Er(3+), Tm(3+) or Yb(3+)) nitrates as template agents. The analytical and spectral characterizations of all the compounds were correlated with the single crystal X-ray structural determination of Eu(3+), Gd(3+), Tb(3+), Dy(3+) and Er(3+) nitrate complexes. The Eu(3+), Gd(3+), Tb(3+)and Dy(3+) complexes of pentadentate 2,6-diacetylpyridine bis(2-aminobenzoylhydrazone) with the N3O2 set of donor atoms display a high and relatively rare coordination number of 11, whereas the Er(3+) ion complex is 9-coordinated, which is consistent with the lanthanide contraction phenomenon. The scission of 21-mer RNA was assessed for Eu(3+), Gd(3+) and Tb(3+) nitrate complexes. Lanthanide complexes not covalently attached to the oligonucleotide are able to cleave RNA at the target site in a sequence-selective or non-selective manner depending on the presence of protecting 12-mer 2'OMe RNA.

摘要

新型 2,6-二乙酰基吡啶双(2-氨基苯甲酰腙)镧系元素配合物是通过在镧系元素(La(3+)、Pr(3+)、Nd(3+)、Sm(3+)、Eu(3+)、Gd(3+)、Tb(3+)、Dy(3+)、Ho(3+)、Er(3+)、Tm(3+)或Yb(3+))硝酸盐作为模板剂存在的情况下,2,6-二乙酰基吡啶与 2-氨基苯甲酰腙之间的金属诱导一步[1+2]缩合反应形成的。所有化合物的分析和光谱特性都与 Eu(3+)、Gd(3+)、Tb(3+)、Dy(3+)和 Er(3+)硝酸盐配合物的单晶 X 射线结构测定相关联。五配位的 2,6-二乙酰基吡啶双(2-氨基苯甲酰腙)与 N3O2 供体原子组的 Eu(3+)、Gd(3+)、Tb(3+)和 Dy(3+)配合物具有高且相对罕见的 11 配位数,而 Er(3+)离子配合物则为 9 配位,这与镧系收缩现象一致。对 Eu(3+)、Gd(3+)和 Tb(3+)硝酸盐配合物进行了 21 聚核苷酸 RNA 的断裂评估。未与寡核苷酸共价连接的镧系元素配合物能够在靶位以序列选择性或非选择性方式切割 RNA,具体取决于是否存在保护的 12 聚体 2'OMe RNA。

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