Silver(I)-mediated Hoogsteen-type base pairs
Silver(I)-mediated Hoogsteen-type base pairs
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DOI：
10.1016/j.jinorgbio.2011.07.005
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发表时间：
2011-11-01
影响因子：
3.9
通讯作者：
Mueller, Jens
中科院分区：
文献类型：
--
作者：
Megger, Dominik A.;Guerra, Celia Fonseca;Mueller, Jens
金属介导的Hoogsteen型碱基对可用于构建DNA双链体，所述DNA双链体含有沿螺旋轴沿着的金属离子的连续延伸。为了微调这种碱基对的稳定性和对不同金属离子的选择性，高度期望选择人工核碱基的可用性。在这项研究中，我们遵循的理论方法，利用色散校正的密度泛函方法来评估各种人工核碱基作为候选人的金属介导的Hoogsteen型碱基对。我们专注于银（I）介导的Hoogsteen和反向Hoogsteen型碱基对之间形成的1-脱氮和1，3-二脱氮嘌呤衍生的核碱基，分别和胞嘧啶。除了两个配位键外，这些碱基对通过氢键稳定。我们阐明了C6位置的不同取代基以及内环N3氮原子的存在或不存在对碱基对整体稳定性以及随之而来的氢键和配位键强度的影响。本研究中研究的所有人工碱基对都不如实验建立的基准碱基对C-Ag+-G稳定。由1，3-二脱氮-6-甲氧基嘌呤形成的碱基对与实验观察到的C-Ag+-C碱基对能量相等。这使得1，3-二脱氮-6-甲氧基嘌呤成为DNA中人工核碱基的一个有希望的候选者。(C)2011 Elsevier Inc. All rights reserved.
Metal-mediated Hoogsteen-type base pairs are useful for the construction of DNA duplexes containing contiguous stretches of metal ions along the helical axis. To fine-tune the stability of such base pairs and the selectivity toward different metal ions, the availability of a selection of artificial nucleobases is highly desirable. In this study, we follow a theoretical approach utilizing dispersion-corrected density functional methods to evaluate a variety of artificial nucleobases as candidates for metal-mediated Hoogsteen-type base pairs. We focus on silver(I)-mediated Hoogsteen- and reverse Hoogsteen-type base pairs formed between 1-deaza- and 1,3-dideazapurine-derived nucleobases, respectively, and cytosine. Apart from two coordinative bonds, these base pairs are stabilized by a hydrogen bond. We elucidate the impact of different substituents at the C6 position and the presence or absence of an endocyclic N3 nitrogen atom on the overall stability of a base pair and concomitantly on the strength of the hydrogen and coordinative bonds. All artificial base pairs investigated in this study are less stable than the experimentally established benchmark base pair C-Ag+-G. The base pair formed from 1,3-dideaza-6-methoxypurine is isoenergetic to the experimentally observed C-Ag+-C base pair. This makes 1,3-dideaza-6-methoxypurine a promising candidate for the use as an artificial nucleobase in DNA. (C) 2011 Elsevier Inc. All rights reserved.