A Dinuclear Mercury(II)-Mediated Base Pair in DNA

Soham Mandal; Marian Hebenbrock; Jens Müller

doi:10.1002/anie.201608354

A Dinuclear Mercury(II)-Mediated Base Pair in DNA

Angew Chem Int Ed Engl. 2016 Dec 12;55(50):15520-15523. doi: 10.1002/anie.201608354. Epub 2016 Nov 15.

Authors

Soham Mandal^{1

2}, Marian Hebenbrock¹, Jens Müller^{1

2}

Affiliations

¹ Institut für Anorganische und Analytische Chemie, Westfälische Wilhelms-Universität Münster, Corrensstrasse 28/30, 48149, Münster, Germany.
² NRW Graduate School of Chemistry, Westfälische Wilhelms-Universität Münster, Corrensstrasse 28/30, 48149, Münster, Germany.

PMID: 27862734
DOI: 10.1002/anie.201608354

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 Hg^II and thereby partially compensates the charge accumulation due to the two closely spaced divalent metal ions, yields the dinuclear T-Hg^II₂ -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.

Keywords: bioinorganic chemistry; ethenoadenine; mercury; metal bioconjugates; metal-mediated base pair.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Adenine / analogs & derivatives*
Base Pairing*
Cations, Divalent / chemistry
DNA / chemistry*
Mercury / chemistry*
Models, Molecular
Nucleic Acid Conformation
Oligonucleotides / chemistry
Protons
Temperature
Thymine / chemistry*

Substances

Cations, Divalent
Oligonucleotides
Protons
DNA
Mercury
Adenine
Thymine