title: A Dinuclear Mercury(II)-Mediated Base Pair in DNA.
abstract: The first dinuclear metal-mediated base pair containing divalent metal ions has been prepared. A combination of the neutral bis(monodentate) purine derivative 1,N6-ethenoadenine (ϵA), which preferentially binds two metal ions with a parallel alignment of the N-M bonds, and the canonical nucleobase thymine (T), which readily deprotonates in the presence of HgIIand thereby partially compensates the charge accumulation due to the two closely spaced divalent metal ions, yields the dinuclear T-HgII2-ϵA base pair. This metal-mediated base pair stabilizes the DNA oligonucleotide duplex as shown by an increase of 8 °C in its melting temperature. Formation of the base pair was demonstrated by temperature-dependent UV spectroscopy as well as by titration experiments monitored by UV and CD spectroscopy.
authors.affiliation: Institut für Anorganische und Analytische Chemie, Westfälische Wilhelms-Universität Münster, Corrensstrasse 28/30, 48149, Münster, Germany.|NRW Graduate School of Chemistry, Westfälische Wilhelms-Universität Münster, Corrensstrasse 28/30, 48149, Münster, Germany.
authors.forename: Soham
authors.initials: S
authors.lastname: Mandal
authors.affiliation: Institut für Anorganische und Analytische Chemie, Westfälische Wilhelms-Universität Münster, Corrensstrasse 28/30, 48149, Münster, Germany.
authors.forename: Marian
authors.initials: M
authors.lastname: Hebenbrock
authors.affiliation: Institut für Anorganische und Analytische Chemie, Westfälische Wilhelms-Universität Münster, Corrensstrasse 28/30, 48149, Münster, Germany.|NRW Graduate School of Chemistry, Westfälische Wilhelms-Universität Münster, Corrensstrasse 28/30, 48149, Münster, Germany.
authors.forename: Jens
authors.identifier: 0000-0003-4713-0606
authors.initials: J
authors.lastname: Müller
mesh_terms: D000225:Adenine / Q000031:analogs & derivatives*; D020029:Base Pairing; D002413:Cations, Divalent / Q000737:chemistry; D004247:DNA / Q000737:chemistry*; D008628:Mercury / Q000737:chemistry*; D008958:Models, Molecular; D009690:Nucleic Acid Conformation; D009841:Oligonucleotides / Q000737:chemistry; D011522:Protons; D013696:Temperature; D013941:Thymine / Q000737:chemistry*
chemical_list: D002413:Cations, Divalent; D009841:Oligonucleotides; D011522:Protons; D004247:DNA; D008628:Mercury; D000225:Adenine; D013941:Thymine
keywords: bioinorganic chemistry; ethenoadenine; mercury; metal bioconjugates; metal-mediated base pair