Scharf Philipp, Jash Biswarup, Kuriappan Jissy A, Waller Mark P, Müller Jens
Westfälische Wilhelms-Universität Münster, Institut für Anorganische und Analytische Chemie, Corrensstrasse 28/30, 48149 Münster (Germany).
Current address: University of Iceland, Science Institute, Dunhagi 3, 107 Reykjavík (Iceland).
Chemistry. 2016 Jan 4;22(1):295-301. doi: 10.1002/chem.201503405. Epub 2015 Nov 20.
An artificial nucleoside surrogate with 1H-imidazo[4,5-f][1,10]phenanthroline (P) acting as an aglycone has been introduced into DNA oligonucleotide duplexes. This nucleoside surrogate can act as a bidentate ligand, and so is useful in the context of metal-mediated base pairs. Several duplexes involving a hetero base pair with an imidazole nucleoside have been investigated. The stability of DNA duplexes incorporating the respective Ag(I) -mediated base pairs strongly depends on the sequence context. Quantum mechanical/molecular mechanical (QM/MM) calculations have been performed in order to gain insight into the factors determining this sequence dependence. The results indicated that, in addition to the stabilizing effect that results from the formation of coordinative bonds, destabilizing effects may occur when the artificial base pair does not fit optimally into the surrounding B-DNA duplex.
一种以1H-咪唑并[4,5-f][1,10]菲咯啉（P）作为糖苷配基的人工核苷类似物已被引入DNA寡核苷酸双链体中。这种核苷类似物可作为双齿配体，因此在金属介导的碱基对方面很有用。已经研究了几种涉及含咪唑核苷的杂合碱基对的双链体。包含各自Ag(I)介导碱基对的DNA双链体的稳定性强烈依赖于序列背景。为了深入了解决定这种序列依赖性的因素，已经进行了量子力学/分子力学（QM/MM）计算。结果表明，除了形成配位键产生的稳定作用外，当人工碱基对不能最佳地适配周围的B-DNA双链体时，可能会出现去稳定作用。
