title: Sequence-Dependent Duplex Stabilization upon Formation of a Metal-Mediated Base Pair.
abstract: An artificial nucleoside surrogate with 1H-imidazo[4,5-f][1,10]phenanthroline (P) acting as an aglycone has been introduced into DNA oligonucleotide duplexes. This nucleoside surrogate can act as a bidentate ligand, and so is useful in the context of metal-mediated base pairs. Several duplexes involving a hetero base pair with an imidazole nucleoside have been investigated. The stability of DNA duplexes incorporating the respective Ag(I) -mediated base pairs strongly depends on the sequence context. Quantum mechanical/molecular mechanical (QM/MM) calculations have been performed in order to gain insight into the factors determining this sequence dependence. The results indicated that, in addition to the stabilizing effect that results from the formation of coordinative bonds, destabilizing effects may occur when the artificial base pair does not fit optimally into the surrounding B-DNA duplex.
authors.affiliation: Westfälische Wilhelms-Universität Münster, Institut für Anorganische und Analytische Chemie, Corrensstrasse 28/30, 48149 Münster (Germany).|Current address: University of Iceland, Science Institute, Dunhagi 3, 107 Reykjavík (Iceland).
authors.forename: Philipp
authors.initials: P
authors.lastname: Scharf
authors.affiliation: Westfälische Wilhelms-Universität Münster, Institut für Anorganische und Analytische Chemie, Corrensstrasse 28/30, 48149 Münster (Germany).|Westfälische Wilhelms-Universität Münster, Graduate School of Chemistry, Corrensstrasse 28/30, 48149 Münster (Germany).
authors.forename: Biswarup
authors.initials: B
authors.lastname: Jash
authors.affiliation: Westfälische Wilhelms-Universität Münster, Organisch-Chemisches Institut and Center for Multiscale Theory and Computation, Corrensstrasse 40, 48149 Münster (Germany).
authors.forename: Jissy A
authors.initials: JA
authors.lastname: Kuriappan
authors.affiliation: Westfälische Wilhelms-Universität Münster, Organisch-Chemisches Institut and Center for Multiscale Theory and Computation, Corrensstrasse 40, 48149 Münster (Germany).
authors.forename: Mark P
authors.initials: MP
authors.lastname: Waller
authors.affiliation: Westfälische Wilhelms-Universität Münster, Institut für Anorganische und Analytische Chemie, Corrensstrasse 28/30, 48149 Münster (Germany). mueller.j@uni-muenster.de.|Westfälische Wilhelms-Universität Münster, Graduate School of Chemistry, Corrensstrasse 28/30, 48149 Münster (Germany). mueller.j@uni-muenster.de.
authors.forename: Jens
authors.initials: J
authors.lastname: Müller
mesh_terms: D020029:Base Pairing; D002942:Circular Dichroism; D059371:DNA, B-Form / Q000737:chemistry*; D007093:Imidazoles / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D009841:Oligonucleotides / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D010618:Phenanthrolines / Q000737:chemistry*; D012834:Silver / Q000737:chemistry*
chemical_list: C000608462:1H-imidazo(4,5-f)(1,10)phenanthroline; D059371:DNA, B-Form; D007093:Imidazoles; D008024:Ligands; D009841:Oligonucleotides; D009942:Organometallic Compounds; D010618:Phenanthrolines; D012834:Silver; C029899:imidazole
keywords: DNA; bioinorganic chemistry; phenanthroline; quantum mechanics/molecular mechanics; silver