Dinuclear Metal-Mediated Guanine–Uracil Base Pairs: Theoretical Studies of GUM2 2+ (M = Cu, Ag, and Au) Ions
Dinuclear Metal-Mediated Guanine–Uracil Base Pairs: Theoretical Studies of GUM2 2+ (M = Cu, Ag, and Au) Ions
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双核金属介导的鸟嘌呤-尿嘧啶碱基对：GUM2 2（M = Cu、Ag 和 Au）离子的理论研究
DOI：
10.1007/s10876-019-01503-0
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发表时间：
2019
影响因子：
2.8
通讯作者：
Hou Hai Li
中科院分区：
文献类型：
--
作者：
Cao Guo Jin;Hou Hai Li
具有d10 - d10闭壳相互作用的双核金属介导杂基对具有显著的稳定性。确定铸币金属介导的摆动碱基对是否也稳定是很有趣的。用密度泛函理论研究了GUM22+簇离子（G =鸟嘌呤，U =尿嘧啶，M = Cu， Ag和Au）最低层异构体的几何和电子结构。在这些双核金属介导的碱基对的最低层异构体中，尿嘧啶的2-氧-4-羟基反式n1h异构体是通过氢原子转移从尿嘧啶的典型互变异构体中衍生出来的。M22+阳离子作为一个完整的单元，通过两组紧密线性的N··M··O单元与G··U配体相互作用，而在这些配合物中，摆动碱基对（G - U）之间的互反氢键完全被M - N或M - O相互作用所取代。分子中的原子和EDA-NOCV计算确实揭示了GUM22+阳离子中的σ相互作用是ΔEOrb的首要项。得到的瞬时相互作用能ΔEintand金属-配体相互作用的键解离能给出了键强度为Cu > Au > Ag的趋势。
Dinuclear metal-mediated hetero base pairs with the d10–d10closed-shell interactions have significant stability. It is interesting to identify whether coinage metal-mediated Wobble base pairs are also stable. Geometric and electronic structures of the lowest-lying isomers of GUM22+(G = guanine, U = uracil, M = Cu, Ag, and Au) cluster ions were investigated with density functional theory. In the lowest-lying isomers of these dinuclear metal-mediated base pairs, the 2-oxo-4-hydroxy-trans-N1H isomer of uracil is derived from the canonical tautomer of uracil by the hydrogen atom transfer. M22+cations remain as an unbroken unit and interact with the G···U ligand through two sets of closely linear N···M···O units, while the reciprocal hydrogen bonds between the Wobble base pair (G–U) are entirely substituted by the M–N or M–O interactions in these complexes. The atoms in molecules and EDA–NOCV calculations really reveal that the σ interactions in GUM22+cations are the paramount term of ΔEOrb. The obtained instantaneous interaction energies ΔEintand bond dissociation energies of the metal–ligand interactions give the trend of the bond strength as Cu > Au > Ag.