Metal–nucleic acid cages

Abstract

Metal-nucleic acid cages are a promising new class of materials. Like metallo-supramolecular cages, these systems can use their metals for redox, photochemical, magnetic and catalytic control over encapsulated cargo. However, using DNA provides the potential to program pore size, geometry, chemistry and addressability, and the ability to symmetrically and asymmetrically position transition metals within the three-dimensional framework. Here we report the quantitative construction of metal-DNA cages, with the site-specific incorporation of a range of metals within a three-dimensional DNA architecture. Oligonucleotide strands containing specific environments suitable for transition-metal coordination were first organized into two DNA triangles. These triangles were then assembled into a DNA prism with linking strands. Metal centres were subsequently incorporated into the prisms at the pre-programmed locations. This unprecedented ability to position transition metals within a three-dimensional framework could lead to metal-DNA hosts with applications for the encapsulation, sensing, modification and release of biomolecules and nanomaterials.

Reprogramming the assembly of unmodified DNA with a small molecule

“…Second, selective incorporation of new properties relevant to the use of nucleic acids in materials science, synthetic biology, biotechnology and medicine can be achieved by using unnatural DNA analogs 7--11 . Finally, compared to the standard A--T/G--C duplex code, an expanded DNA alphabet grants access to increasingly complex DNA nanostructures, with potentially reduced defects 12,13 .…”

Bioinspired Self‐Assembly I: Self‐Assembled Structures

“…An example of self-assembly through a union of metallosupramolecular chemistry and DNA nanotechnology is the production of a metal-DNA cage with the impressive internal dimensions, estimated through modeling, to be 25-30 nm 3 . 91 The inspiration to create such structures clearly comes from the structure and function of metalloenzymes, where, as discussed earlier, the metal is held in a defined position within the active site.…”

Macroscopic Self‐Assembly Based on Complementary Interactions between Nucleobase Pairs

“…[2][3][4][5][6] This is an attractive recognition motif that has been used to construct highly intelligent materials. Many researchers in chemistry and materials science have developed intelligent self-assembly systems on a molecular scale, for example, DNA origami, [7][8][9] 3D nanostructures, [10][11][12] metal arrays, [13][14][15] and stimuli-responsive DNA. [16] However, how to construct well-defined self-assemblies on the macroscopic scale is still a big issue for scientists.…”