Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo nám. 2, 16610 Praha 6, Czech Republic.
Phys Chem Chem Phys. 2011 Jan 7;13(1):100-3. doi: 10.1039/c0cp01534b. Epub 2010 Nov 3.
Metal atoms with a closed-shell electronic structure and positive charge as for example the Au(I), Pt(II), Ag(I), Tl(I) or Hg(II) atoms do not in some compounds repel each other due to the so-called metallophilic attraction (P. Pyykkö, Chem. Rev., 1997, 97, 597-636). Here we highlight the role of the Hg(II)Hg(II) metallophilic attraction between the consecutive metal-mediated mismatched base pairs of nucleic acids. Usually, the base stacking dominates the non-covalent interactions between steps of native nucleic acids. In the presence of metal-mediated base pairs these non-covalent interactions are enriched by the metal-base interactions and the metallophilic attraction. The two interactions arising due to the metal linkage of the mismatches were found in this study to have a stabilizing effect on nucleic acid structure. The calculated data are consistent with recent experimental observations. The stabilization due to the metallophilic attraction seems to be a generally important concept for the nucleic acids containing heavy metals with short contacts.
具有满壳电子结构和正电荷的金属原子，例如 Au(I)、Pt(II)、Ag(I)、Tl(I) 或 Hg(II) 原子，在某些化合物中不会因所谓的金属亲合性而相互排斥 (P. Pyykkö, Chem. Rev., 1997, 97, 597-636)。在这里，我们强调了 Hg(II)Hg(II) 金属亲合性在连续的金属介导的碱基对错配的核酸之间的作用。通常，碱基堆积主导着天然核酸中梯级之间的非共价相互作用。在金属介导的碱基对存在的情况下，这些非共价相互作用通过金属-碱基相互作用和金属亲合性得到丰富。由于碱基错配的金属键合而产生的两种相互作用在本研究中被发现对核酸结构具有稳定作用。计算数据与最近的实验观察结果一致。由于金属亲合性引起的稳定作用似乎是含有重金属的核酸的一个普遍重要的概念，这些核酸具有短接触。
