Tailored Transition‐Metal Coordination Environments in Imidazole‐Modified DNA G‐Quadruplexes
作者:Philip M. Punt、Guido H. Clever
DOI:10.1002/chem.201903445
日期:2019.11.4
ligands were introduced both at the end of tetramolecular and into the loop region of unimolecular DNA G-quadruplexes. The modified oligonucleotides were shown to complex a range of different transition-metal cations including NiII , CuII , ZnII and CoII , as indicated by UV/Vis absorption spectroscopy and ion mobility mass spectrometry. Molecular dynamics simulations were performed to obtain structural
在四分子末端和单分子DNA G-四链体的环区域都引入了两种类型的咪唑配体。如UV / Vis吸收光谱法和离子迁移质谱法所示,修饰的寡核苷酸显示出与多种不同的过渡金属阳离子络合,包括NiII,CuII,ZnII和CoII。进行分子动力学模拟以获得对所研究系统的结构见解。源自人类端粒区域(htel)的单分子序列的环区域中配体数量和位置的变化,可以实现具有精细调整的金属亲和力的独特配位环境的受控设计。结果表明,通常呈正方形平面配位的CuII对提供四个配体的系统具有更高的亲和力,NiII更喜欢带有六个配体的G-四链体。同样,配体以四面体和四面体的方式定位分别影响CuII和ZnII阳离子的结合亲和力。获得对配体排列方式的控制将促进过渡金属修饰的DNA酶的合理发展。此外,该方法适合于在单个DNA结构内结合不同类型的配体,例如通常在金属酶中发现的那些。