Depart. of Chemistry and Chemical Biology, TU Dortmund University, Otto-Hahn-Straße 6, Dortmund, 44227, Germany.
Institute for Physical and Theoretical Chemistry, Wegelerstr. 12, Rheinische Friedrich-Wilhelms-Universität Bonn, Bonn, 53115, Germany.
Chem Commun (Camb). 2018 Jul 11;54(54):7455-7458. doi: 10.1039/c8cc04053b. Epub 2018 Jun 18.
Artificial metal-base tetrads composed of square-planar Cu(pyridine) complexes were covalently attached to both the 3' and 5' ends of tetramolecular DNA G-quadruplexes [Ld(G)LdT] (L = pyridine ligand) of different lengths. Owing to the planar four-point attachment of the metal complexes, the magnetic orbitals (d) of the d-configured Cu cations are placed in a coplanar fashion, separated by the stacked guanine tetrads. Pulsed EPR-derived Cu-Cu distances and angles were found to be in agreement with those obtained from molecular dynamics simulations. DNA-confined transition metal spin labels open new ways to study oligonucleotide structure and DNA-protein complexes.
由四面体形 Cu(pyridine)配合物组成的人工金属基四联体通过共价键连接到不同长度的四分子 DNA G-四链体 [Ld(G)LdT]（L = 吡啶配体）的 3' 和 5' 末端。由于金属配合物的平面四点连接，d 构型 Cu 阳离子的磁轨道（d）以共面的方式排列，由堆叠的鸟嘌呤四联体隔开。通过脉冲 EPR 衍生的 Cu-Cu 距离和角度与分子动力学模拟得到的结果一致。DNA 限制的过渡金属自旋标记为研究寡核苷酸结构和 DNA-蛋白质复合物开辟了新途径。
