Department of Chemistry, University of Turku, Vatselankatu 2, 20014, Turku, Finland.
Chemistry. 2020 Feb 17;26(10):2164-2168. doi: 10.1002/chem.201905434. Epub 2020 Jan 30.
A C-nucleoside with 6-phenyl-1H-carbazole as the base moiety has been synthesized and incorporated in the middle of an oligonucleotide. Mercuration of this modified residue at positions 1 and 8 gave the first example of an oligonucleotide featuring a monofacial dinuclear organometallic nucleobase. The dimercurated oligonucleotide formed stable duplexes with unmodified oligonucleotides placing either cytosine, guanine, or thymine opposite to the organometallic nucleobase. A highly stabilizing (ΔT =7.3 °C) Hg -mediated base pair was formed with thymine. According to DFT calculations performed at the PBE0DH level of theory, this base pair is most likely dinuclear, with the two Hg ions coordinated to O2 and O4 of the thymine base.
已合成了一种以 6-苯基-1H-咔唑为碱基部分的 C-核苷，并将其掺入寡核苷酸的中部。对该修饰残基在 1 位和 8 位的汞化反应得到了首例具有单齿二核有机金属碱基的寡核苷酸。二汞化的寡核苷酸与未修饰的寡核苷酸形成稳定的双链体，将胞嘧啶、鸟嘌呤或胸腺嘧啶与有机金属碱基相对放置。与胸腺嘧啶形成高度稳定的（ΔT = 7.3°C）Hg 介导的碱基对。根据在 PBE0DH 理论水平上进行的 DFT 计算，该碱基对最有可能是二核的，两个 Hg 离子与胸腺嘧啶碱基的 O2 和 O4 配位。
