Metal‐Mediated Base Pairs: From Characterization to Application

Abstract

The investigation of metal-mediated base pairs and the development of their applications represent a prominent area of research at the border of bioinorganic chemistry and supramolecular coordination chemistry. In metal-mediated base pairs, the complementary nucleobases in a nucleic acid duplex are connected by coordinate bonds to an embedded metal ion rather than by hydrogen bonds. Because metal-mediated base pairs facilitate a site-specific introduction of metal-based functionality into nucleic acids, they are ideally suited for use in DNA nanotechnology. This minireview gives an overview of the general requirements that need to be considered when devising a new metal-mediated base pair, both from a conceptual and from an experimental point of view. In addition, it presents selected recent applications of metal-modified nucleic acids to indicate the scope of metal-mediated base pairing.

The Structural Basis for Processing of Unnatural Base Pairs by DNA Polymerases

“…Additionally, metal‐mediated base pairs that consist of two ligand‐type nucleobases connected through a central metal ion have been developed . Through its coordination, the metal ion stably crosslinks two strands and therefore these pairs are interesting in DNA nanotechnology . Furthermore, DNA containing such pairs function as metal ion sensors and are, for example, used for the detection of Hg 2+ in specimens …”

“…[48] Through its coordination, the metal ion stably crosslinks two strands and therefore these pairs are interesting in DNA nanotechnology. [49,50] Furthermore, DNA containing such pairs function as metal ion sensors and are, for example, used for the detection of Hg 2 + in specimens. [48,50]…”

Fluorescent DNA‐Templated Silver Nanoclusters from Silver(I)‐Mediated Base Pairs

“…Hence, the ImÀAg I ÀC base pair was introduced into aD NA sequence often used in the context of other Ag I -mediated base pairs (duplex I). [10] Additional evidencef or the presence of an Im-Ag I -C base pair can be found in the Supporting Information (FigureS1). This finding is indicative of the formation of am etal-mediated base pair.…”

Covalently Palladated Oligonucleotides Through Oxidative Addition of Pd0

“…An increasing number of applications of metal-mediatedb ase pairing have been proposed over the past decade, including sensors form etal ions, molecular wires, DNA-templated nanoparticles and, more recently,r ecognitiono fn ucleic acid sequences. [1] To widen the scope of the latter application to biological systems, that is, to overcome the scarcity of transition metals available for metal-mediated base pairingi nt he intracellular medium, we have explored the possibility of using oligonucleotides with organometallic nucleobase surrogates. [2,3] We have successfully synthesizeds uch structures by two approaches-eitherd irect mercuration of electron-richs ites on aromatic rings [4] or ligand-directed cyclopalladation of benzylamine or phenylpyridine moieties.…”