On the feasibility of recognition of nucleic acid sequences by metal-ion-carrying oligonucleotides

Application of a Metal‐Mediated Base Pair to the Detection of Medicinally Relevant Single Nucleotide Polymorphisms

“…Similarly, the investigation of surface‐deposited DNA films shows strongly sequence‐ and base‐pair‐dependent results, ranging from increasing to decreasing charge‐transfer resistance of the films . Another potential application of metal‐mediated base pairs has been proposed in the context of recognizing entire nucleic acid sequences . Towards this end, several artificial nucleobases have been developed for discrimination of canonical nucleobases by metal‐mediated base‐pairing .…”

1,8‐Dimercuri‐6‐Phenyl‐1H‐Carbazole as a Monofacial Dinuclear Organometallic Nucleobase

“…[1] As many double-helicalo ligonucleotides incorporating metal-mediated base pairs exhibit higher thermals tabilityt han respective duplexes comprising solely of canonical Watson-Crick base pairs, oligonucleotides functionalized with metal ions could also find use as high-affinity probesf or otherwise elusive targets, such as miRNA. [2] Covalently metallated oligonucleotides have the potential to further widen the scope to therapeutic applications. [3] The greatest duplex stabilizations have been achieved with di-or trinuclearm etal-mediated base pairs featuring two or three bridging metal ions between two specifically designed artificial nucleobases.…”

“…Oligonucleotide ON1 z was assembled on an automated DNA/RNA synthesizer using conventional phosphoramidite strategy. For the 6-phenyl-1H-carbazole C-nucleoside building block 2,t he coupling time was extended to 300 s. Dimercuration of ON1 z was carried out in aqueous solution of Hg(OAc) 2 and NaOAc at 55 8C, Scheme2). As atisfactory conversion was achieved in 16 hours, after whicht he crude product ON1 z-Hg 2 was purified by RP-HPLC.…”

Oligonucleotides Incorporating Palladacyclic Nucleobase Surrogates

“…Metal-mediated base-pairing hasa ttracted increasing attention over the past decade, mainly because of potential applications in DNA nanotechnology, [1] such as sensors for metal ions, [2] molecular wires, [3] and DNA-templated nanoparticles. [4] The superior hybridization affinityo fm etal-ion-carrying oligonucleotides [5] could also make them valuable chemotherapeutic agents, but intracellular concentrations of suitable transition metals are too low to support metal-mediated base-pairing. In other words, the bridgingmetal ion mustb es upplied with the therapeutico ligonucleotide and the oligonucleotide metal complex must resist dissociation under the metal-deficient conditions of the cell.…”