Department of Chemistry, University of Sheffield, Sheffield, S3 7HF, UK.
Physical Organic Chemistry Centre, School of Chemistry, Cardiff University, Main Building Park Place, Cardiff, CF10 3AT, UK.
Chemistry. 2017 Apr 24;23(23):5467-5477. doi: 10.1002/chem.201605750. Epub 2017 Feb 20.
With the long-term aim of enhancing the binding properties of dinuclear Ru -based DNA light-switch complexes, a series of eight structurally related mono- and dinuclear systems are reported in which the linker of the bridging ligand has been modulated. These tethered systems have been designed to explore issues of steric demand at the binding site and the thermodynamic cost of entropy loss upon binding. Detailed spectroscopic and isothermal titration calorimetry (ITC) studies on the new complexes reveal that one of the linkers produces a dinuclear system that binds to duplex DNA with an affinity (K >10 m ) that is higher than its corresponding monometallic complex and is the highest affinity for a non-threading bis-intercalating metal complex. These studies confirm that the tether has a major effect on the binding properties of dinuclear complexes containing intercalating units and establishes key design rules for the construction of dinuclear complexes with enhanced DNA binding characteristics.
为了长期提高双核 Ru 基 DNA 光开关配合物的结合特性，报道了一系列 8 个结构相关的单核和双核体系，其中桥连配体的连接子得到了调制。这些连接体系旨在探索结合部位的空间需求问题以及结合时熵损失的热力学代价。对新配合物的详细光谱和等温滴定量热法 (ITC) 研究表明，其中一个连接子产生了一个双核体系，与双链 DNA 的亲和力 (K >10 m ) 高于其相应的单核配合物，是对非穿线双嵌入金属配合物的最高亲和力。这些研究证实，连接子对含有嵌入单元的双核配合物的结合特性有重大影响，并为构建具有增强 DNA 结合特性的双核配合物建立了关键的设计规则。
