DNA based multi-copper ions assembly using combined pyrazole and salen ligandosides

Abstract

The pyrazole and salen ligandosides, when combined, are able to create stable multi-copper ion complexing DNA duplex structures in a cooperative fashion.

Relative Strand Orientation in a DNA Duplex Controls the Nuclearity of a Metal‐Mediated Base Pair

“…The incorporation of ligand‐based nucleosides into an oligonucleotide thereby introduces metal‐binding sites into these biomolecules. The resulting conjugates of metal complexes and nucleic acids have found several applications, ranging from sensors specific for selected metal ions or predefined oligonucleotide sequences to metal‐responsive systems, an optimization of the charge‐transfer properties of DNA, and asymmetric catalysis . Most metal‐mediated base pairs contain one metal ion, even though more recently a number of dinuclear metal‐mediated base pairs have been developed .…”

pH-Dependence of the thermal stability of metallo-DNA duplexes containing ligand-type 5-hydroxyuracil nucleobases

“…In this context, Ono et al reported that 5-halogen-or 5-cyano-substituted uracil bases formed Ag(I)-mediated base pairs with deprotonation at the N3 positions more efficiently at neutral and higher pH [26]. Carell et al have more recently developed a synthetic pyrazole-type nucleoside (Pz), which formed a Cu(II)-mediated self-base pair only around pH 9 due to the deprotonation of the phenolic group of the ligand [27]. The development of pH-dependent metal-mediated base pair systems would contribute to construct functional DNAs which exhibit dual responsiveness to both metal ions and pH [28][29][30].…”

Artificial DNA Base Pairing Mediated by Diverse Metal Ions

“…Other [N,O]-type artificial nucleosides include a pyrazolylphenol-bearing one (Pz), which has a pyrazole and a phenol as metal coordination sites (Figure 7e). 63,78 A Cu(II)-mediated base pair, PzCu II Pz, was formed under basic conditions because the metal complexation of the Pz ligand requires the deprotonation of the phenolic groups. Incorporation of consecutive PzCu II Pz base pairs allowed discrete assembly of up to ten Cu 2+ ions inside the DNA duplexes.…”

“…Incorporation of consecutive PzCu II Pz base pairs allowed discrete assembly of up to ten Cu 2+ ions inside the DNA duplexes. 78 Catalytic ability of DNA duplexes containing PzCu II Pz pairs was investigated in anticipation of enantioselective reactions. 78 Although only moderate chirality transfer was observed for a DielsAlder reaction, the results suggest possible applications of metallo-base pairs.…”