The Structure of Linkers Affects the DNA Binding Properties of Tethered Dinuclear Ruthenium(II) Metallo‐Intercalators

With the long‐term aim of enhancing the binding properties of dinuclear RuII‐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 e...

Full description

Saved in:
Bibliographic Details
Published in:Chemistry : a European journal 2017-04, Vol.23 (23), p.5467-5477
Main Authors: Saeed, Hiwa K., Saeed, Ibrahim Q., Buurma, Niklaas J., Thomas, Jim A.
Format: Article
Language:English
Subjects:
Affinity
Binding
Binding Sites
Chemistry
Coordination Complexes - chemistry
Deoxyribonucleic acid
Design engineering
DNA
DNA - chemistry
Entropy
Intercalating Agents - chemistry
intercalation
isothermal titration calorimetry (ITC)
Ligands
luminescence
Magnetic Resonance Spectroscopy
ruthenium
Ruthenium - chemistry
Tethers
Titration calorimetry
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:With the long‐term aim of enhancing the binding properties of dinuclear RuII‐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 (Kb >107 m−1) 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. Strengthening links: The DNA binding properties of non‐threading dinuclear RuII(dppz) bis‐intercalators are highly dependent on the nature of their linker ligand. Judicious selection of the connectivity and structure of the tether enhances binding by two orders of magnitude compared to previously reported systems.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201605750