6-Substituted purines containing thienyl or furyl substituents as artificial nucleobases for metal-mediated base pairing

Dalton Trans. 2013 Dec 7;42(45):16080-9. doi: 10.1039/c3dt51691a. Epub 2013 Aug 28.

Abstract

The artificial nucleobases 6-(2'-thienyl)-purine (6TP) and 6-(2'-furyl)-purine (6FP) have been investigated in terms of their applicability in metal-mediated base pairs. In principle, these nucleobases should be capable of providing an S,N- and O,N-coordination environment, respectively. Two metal complexes have been synthesized and structurally characterized, using the N9-methylated derivatives of 6TP and 6FP as model nucleobases. The silver(I) complex [Ag(9-Me6TP)(CH3CN)(NO3)]n is of polymeric nature. The thienyl substituent is not involved in metal binding. In contrast, the dinuclear copper(II) complex [Cu(9-Me6FP)Cl2(OH2)]2 clearly shows that the furyl substituent can participate in the coordination of the metal ion. Oligonucleotide double helices comprising a 6TP:6TP or a 6FP:6FP mispair are slightly stabilized in the presence of silver(I). However, a distinction between the formation of a metal-mediated base pair and an unspecific binding event cannot be finally made. Based on these studies, it is proposed that the formation of Hoogsteen-type metal-mediated base pairs should be the more promising alternative compared with the originally anticipated Watson-Crick-type metal-mediated base pairs.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Base Pairing
  • Coordination Complexes / chemistry*
  • Copper / chemistry*
  • Metals / chemistry
  • Models, Molecular
  • Purines / chemistry*
  • Silver / chemistry*

Substances

  • Coordination Complexes
  • Metals
  • Purines
  • Silver
  • Copper
  • purine