A Dinuclear Mercury(II)‐Mediated Base Pair in DNA. Issue 50 (15th November 2016)

• Record Type: Journal Article
• Authors: Mandal, Soham; Hebenbrock, Marian; Müller, Jens
• Is Part Of: Angewandte Chemie international edition. Volume 55:Issue 50(2016)
• Page Start: 15520
• Page End: 15523
• Publication Date: 2016-11-15
• Subjects: bioinorganic chemistry -- ethenoadenine -- metal bioconjugates -- metal-mediated base pair -- mercury; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201608354
• Languages: English
• ISSNs: 1433-7851

Abstract

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, N 6 ‐ethenoadenine ( ϵ A), 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 II 2 ‐ ϵ A 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. Abstract : Two's company : The first dinuclear metal‐mediated base pair bearing divalent metal ions was formed by combining thymine with an appropriately chosen artificial nucleobase, which through two separate monodentate coordination sites allows the binding of two Hg II ions in close proximity to each other.