title: Synthesis of nucleosides and dNTPs bearing oligopyridine ligands linked through an octadiyne tether, their incorporation into DNA and complexation with transition metal cations.
abstract: Modified nucleosides (dA(R)s and dC(R)s) bearing bipyridine or terpyridine ligands attached through an octadiyne linker were prepared by single-step aqueous-phase Sonogashira cross-coupling of 7-iodo-7-deaza-2'-deoxyadenosine and 5-iodo-2'-deoxycytidine with the corresponding bipyridine- or terpyridine-octadiynes and were triphosphorylated to the corresponding nucleoside triphosphates (dA(R)TPs and dC(R)TPs). The modified dN(R)TPs were successfully incorporated into the oligonucleotides by primer extension experiment (PEX) using different DNA polymerases and the PEX products were used for post-synthetic complexation with divalent metal cations. The complexation of these DNAs containing flexibly-tethered ligands was compared with the previously reported ones bearing rigid acetylene-linked ligands suggesting the possible formation of both inter- and intra-strand complexes with Ni(2+) or Fe(2+).
authors.affiliation: Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Gilead & IOCB Research Center, Flemingovo nam. 2, CZ-16610 Prague 6, Czech Republic.
authors.forename: Lubica
authors.initials: L
authors.lastname: Kalachova
authors.forename: Radek
authors.initials: R
authors.lastname: Pohl
authors.forename: Lucie
authors.initials: L
authors.lastname: Bednárová
authors.forename: Jindřich
authors.initials: J
authors.lastname: Fanfrlík
authors.forename: Michal
authors.initials: M
authors.lastname: Hocek
mesh_terms: D000480:Alkynes / Q000737:chemistry*; D002412:Cations / Q000737:chemistry; D004247:DNA / Q000737:chemistry*; D008024:Ligands; D015394:Molecular Structure; D009705:Nucleosides / Q000138:chemical synthesis* / Q000737:chemistry; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D011122:Polyphosphates / Q000138:chemical synthesis* / Q000737:chemistry; D011725:Pyridines / Q000737:chemistry*; D028561:Transition Elements / Q000737:chemistry*
chemical_list: D000480:Alkynes; D002412:Cations; D008024:Ligands; D009705:Nucleosides; D009942:Organometallic Compounds; D011122:Polyphosphates; D011725:Pyridines; D028561:Transition Elements; D004247:DNA; C005692:triphosphoric acid