Imidazolium-based ionic liquids binding to DNA: Mechanical effects and thermodynamics of the interactions.

We performed a robust characterization of the molecular interactions between the DNA molecule and two imidazolium-based ionic liquids (ILs): 1-Butyl-3-methylimidazolium chloride ([bmim]Cl) and 1-Octyl-3-methylimidazolium chloride ([omim]Cl), using single molecule approaches (optical and magnetic tweezers) and bulk techniques (isothermal titration calorimetry and conductivity measurements). Optical and magnetic tweezers allowed us to obtain the changes on the mechanical properties of the DNA complexes formed with both ILs, as well as the relevant physicochemical (binding) parameters of the interaction. Despite the weak binding measured between DNA and the two ILs, we identify a transition on the regime of polymer elasticity of the complexes formed, which results in a relevant DNA compaction for high IL concentrations. In addition, isothermal titration calorimetry and conductivity complemented the single molecule investigation, giving a complete thermodynamic characterization of the interactions and allowing the identification of the most relevant driving forces at various different concentration ranges of the ILs. Based on the results obtained with all the employed techniques, we propose a model for the binding schemes involving DNA and both [bmim]Cl and [omim]Cl.