A dinuclear silver(I)-mediated base pair in DNA formed from 1,N6-ethenoadenine and thymine

Mandal S, Hebenbrock M, Müller J

Research article (journal) | Peer reviewed

Abstract

The artificial nucleobase 1,N 6-ethenoadenine (εA) is shown to form a dinuclear Ag(I)-mediated base pair with a complementary thymine (T) residue in double-helical DNA. The stabilizing effect brought about by the formation of such a metal-mediated base pair amounts to 5-6°C. It does not depend on the orientation of the base pair within the duplex, i.e. the εA-Ag(I)2-T base pair confers the same stability as the T-Ag(I)2-εA base pair. Circular dichroism studies and temperature-dependent UV spectroscopy were applied to establish the formation of this Ag(I)-mediated base pair. Based on DFT calculations, a base pair configuration is proposed in which one Ag(I) ion is coordinated by εA-N6 and T-O4, whereas the other Ag(I) ion forms coordinate bonds to εA-N7 and T-N3. The computations indicate a short intramolecular Ag⋯Ag contact of 2.87Å, suggesting that argentophilic interactions may be involved.

Details about the publication

Journal: Inorganica Chimica Acta

Volume: 472

Page range: 229-233

Status: Published

Release year: 2018 (31/05/2017)

Language in which the publication is written: English

DOI: 10.1016/j.ica.2017.05.072

Link to the full text: https://www.scopus.com/inward/record.uri?partnerID=HzOxMe3b&scp=85020304593&origin=inward

Keywords: Bioinorganic chemistry; Metal-mediated base pair; Nucleic acids; Silver

Authors from the University of Münster

Hebenbrock, Marian	Professorship of Inorganic Chemistry (Prof. Müller)
Mandal, Soham	Professorship of Inorganic Chemistry (Prof. Müller)
Müller, Jens	Professorship of Inorganic Chemistry (Prof. Müller)

Projects the publication originates from

CRC 858 B09 - Influence of consecutive metal-mediated base pairs in DNA double helices on charge transfer through DNA and other cooperative effects in metal… (SFB 858)

Duration: 01/01/2010 - 31/12/2017 | 2nd Funding period

Funded by: DFG - Collaborative Research Centre

Type of project: Subproject in DFG-joint project hosted at University of Münster

Doctorates the publication originates from

Metal-Mediated Base Pairs with Ethenoadenine, a Versatile Nucleobase Surrogate
Candidate: Mandal, Soham | Supervisors: Müller, Jens
Period of time: 08/10/2012 - 16/08/2016
Doctoral examination procedure finished at: Doctoral examination procedure at University of Münster