Reversed Cation Selectivity of G8 -Octamer and G16 -Hexadecamer towards Monovalent and Divalent Cations

Chem Asian J. 2020 Apr 1;15(7):1030-1034. doi: 10.1002/asia.202000016. Epub 2020 Mar 6.

Abstract

A reverse-binding-selectivity between monovalent and divalent cations was observed for two different self-assembly G16 -hexadecamer and G8 -octamer systems. The dissociation constant between G4 -quadruplex and monomer was calculated via VT-1 H NMR experiments. Quantitative energy profiles revealed entropy as the key factor for the weaker binding toward Ba2+ compared with K+ in the G8 -octamer system despite stronger ion-dipole interactions. This study is the first direct comparison of the G4 -quartet binding affinity between mono and divalent cations and will benefit future applications of G-quadruplex-related research. Further competition experiments between the G8 -octamer and 18-crown-6 with K+ demonstrated the potential of this G8 system as a new potassium receptor.

Keywords: G-quadruplex; G-quadruplex dissociation; cation selectivity; entropy; guanosine self-assembly; potassium receptor.