Paramagnetic Decoration of DNA origami Nanostructures by Eu3+ Coordination

The folding of DNA into arbitrary two- and three-dimensional shapes, called DNA origami, represents a powerful tool for the synthesis of functional nanostructures. Here, we present the first approach toward the paramagnetic functionalization of DNA origami nanostructures by utilizing post-assembly coordination with Eu3+ ions. In contrast to the usual formation of toroidal dsDNA condensates in the presence of trivalent cations, planar as well as rod-like DNA origami maintain their shape and monomeric state even under high loading with the trivalent lanthanide. Europium-coordination was demonstrated by the change in Eu3+ luminescence upon binding to the two DNA origami. Their natural circular dichroism in the Mg2+- and Eu3+-bound state was found to be very similar to that of genomic DNA, evidencing little influence of the DNA origami superstructure on the local chirality of the stacked base pairs. In contrast, the magnetic circular dichroism of the Mg2+-bound DNA origami deviates from that of genomic DNA. Furthermore, the lanthanide affects the magnetic properties of DNA in a superstructure-dependent fashion, indicative of the existence of superstructure-specific geometry of Eu3+ binding sites in the DNA origami that are not formed in genomic DNA. This simple approach lays the foundation for the generation of DNA origami with taylored lanthanide-specificity. Such systems do not require covalent modifications and can be used for the magnetic manipulation of DNA nanostructures or for the paramagnetic alignment of molecules in NMR spectroscopy.