Cu^II-mediated stabilisation of DNA duplexes bearing consecutive ethenoadenine lesions and its application to a metal-responsive DNAzyme

Abstract

Metal-mediated nucleobase pairing can play a central role in the expression of metal-responsive DNA functions. We report the CuII-mediated stabilisation of DNA duplexes bearing damaged nucleobases, 1,N6-ethenoadenine (εA), as metal-binding...

CuII-mediated DNA base pairing of a triazole-4-carboxylate nucleoside prepared by click chemistry

“…[9][10][11][12][13][14] A variety of ligand-type synthetic nucleosides have been reported to form metalmediated base pairs in the presence of certain metal ions such as Ag I , Hg II , Cu II , and Ni II . Metal-mediated base pairing usually leads to the thermal stabilization of DNA duplexes, which has recently been applied to metal-dependent allosteric regulation of DNAzymes (catalytic DNAs) [15][16][17][18][19] and DNA aptamers. 20,21 In particular, Cu II -mediated artificial base pairing has contributed significantly to imparting DNAs with attractive properties such as magnetism, 22,23 catalytic activity, 24 and redox responsiveness.…”

Metal-dependent base pairing of bifacial iminodiacetic acid-modified uracil bases for switching DNA hybridization partner

“…The metal-mediated base pairing has been applied not only to the construction of metallo-DNA hybrid structures, [22][23][24][25][26][27] but also to the development of metal-responsive DNA molecular machines 28,29 and catalytically active DNAs (DNAzymes). [30][31][32][33][34] Aiming for efficient switching of DNA structures in response to metal ions, we focused on noncanonical 5-modified uracil (U X ) nucleobases with a metal-binding functional group (X) at the 5-position. The U X bases are expected to exhibit a "bifacial" base-paring behavior, forming hydrogen-bonded U X -A base pairs and metal-mediated U X -M-U X base pairs (M = metal ion) in the absence and presence of certain metal ions, respectively.…”

“…The metal-mediated base pairing has been applied not only to the construction of metallo-DNA hybrid structures, 22–27 but also to the development of metal-responsive DNA molecular machines 28,29 and catalytically active DNAs (DNAzymes). 30–34…”

Metal-dependent activity control of a compact-sized 8–17 DNAzyme based on metal-mediated unnatural base pairing

“…1). [12][13][14][15][16][17] Although many metal-dependent DNAzymes have been identified by in vitro selection processes, chemical modification of existing DNAzymes is expected to be a more powerful method to confer metal-responsiveness on DNAzymes at will. To this end, unnatural metal-mediated base pairs, [18][19][20][21][22][23] formed by metal complexation between two ligand-bearing nucleotides and a bridging metal ion, have been exploited as metal-responsive units in DNA.…”