Stabilization and induction of oligonucleotide i-motif structure via graphene quantum dots.

DNA i-motif structures have been found in telomeric, centromeric DNA and many in the promoter region of oncogenes; thus they might be attractive targets for gene-regulation processes and anticancer therapeutics. We demonstrate in this work that i-motif structures can be stabilized by graphene quantum dots (GQDs) under acidic conditions, and more importantly GQDs can promote the formation of the i-motif structure under alkaline or physiological conditions. We illustrate that the GQDs stabilize the i-motif structure through end-stacking of the bases at its loop regions, thus reducing its solvent-accessible area. Under physiological or alkaline conditions, the end-stacking of GQDs on the unfolded structure shifts the equilibrium between the i-motif and unfolded structure toward the i-motif structure, thus promoting its formation. The possibility of fine-tuning the stability of the i-motif and inducing its formation would make GQDs useful in gene regulation and oligonucleotide-based therapeutics.