Bifacial Base-Pairing Behaviors of 5-Hydroxyuracil DNA Bases through Hydrogen Bonding and Metal Coordination.
A novel bifacial ligand-bearing nucleobase, 5-hydroxyuracil (U(OH) ), which forms both a hydrogen-bonded base pair (U(OH) -A) and a metal-mediated base pair (U(OH) -M-U(OH) ) has been developed. The U(OH) -M-U(OH) base pairs were quantitatively formed in the presence of lanthanide ions such as Gd(III) when U(OH) -U(OH) pairs were consecutively incorporated into DNA duplexes. This result established metal-assisted duplex stabilization as well as DNA-templated assembly of lanthanide ions. Notably, a duplex possessing U(OH) -A base pairs was destabilized by addition of Gd(III) ions. This observation suggests that the hybridization behaviors of the U(OH) -containing DNA strands are altered by metal complexation. Thus, the U(OH) nucleobase with a bifacial base-pairing property holds great promise as a component for metal-responsive DNA materials.
Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033 (Japan).
Yusuke
Y
Takezawa
Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033 (Japan).
Kotaro
K
Nishiyama
Institute of Advanced Energy, Graduate School of Energy Science, Kyoto University, Gokasho, Uji, Kyoto 611-0011 (Japan).
Tsukasa
T
Mashima
Institute of Advanced Energy, Graduate School of Energy Science, Kyoto University, Gokasho, Uji, Kyoto 611-0011 (Japan).
Masato
M
Katahira
Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033 (Japan). shionoya@chem.s.u-tokyo.ac.jp.
Mitsuhiko
M
Shionoya
D020029:Base Pairing; D056831:Coordination Complexes / Q000737:chemistry*; D004247:DNA / Q000737:chemistry* / Q000378:metabolism; D005682:Gadolinium / Q000737:chemistry*; D006860:Hydrogen Bonding; D007477:Ions / Q000737:chemistry*; D014498:Uracil / Q000031:analogs & derivatives* / Q000737:chemistry / Q000378:metabolism
D056831:Coordination Complexes; D007477:Ions; C045975:5-hydroxyuracil; D014498:Uracil; D004247:DNA; D005682:Gadolinium
DNA hybridization; DNA structures; bioinorganic chemistry; lanthanides; metal-mediated base pair