Design and synthesis of heterocyclic cations for specific DNA recognition: from AT-rich to mixed-base-pair DNA sequences

J Org Chem. 2014 Feb 7;79(3):852-66. doi: 10.1021/jo402599s. Epub 2014 Jan 21.

Abstract

The compounds synthesized in this research were designed with the goal of establishing a new paradigm for mixed-base-pair DNA sequence-specific recognition. The design scheme starts with a cell-permeable heterocyclic cation that binds to AT base pair sites in the DNA minor groove. Modifications were introduced in the original compound to include an H-bond accepting group to specifically recognize the G-NH that projects into the minor groove. Therefore, a series of heterocyclic cations substituted with an azabenzimidazole ring has been designed and synthesized for mixed-base-pair DNA recognition. The most successful compound, 12a, had an azabenzimidazole to recognize G and additional modifications for general minor groove interactions. It binds to the DNA site -AAAGTTT- more strongly than the -AAATTT- site without GC and indicates the design success. Structural modifications of 12a generally weakened binding. The interactions of the new compound with a variety of DNA sequences with and without GC base pairs were evaluated by thermal melting analysis, circular dichroism, fluorescence emission spectroscopy, surface plasmon resonance, and molecular modeling.

Publication types

  • Research Support, N.I.H., Extramural

MeSH terms

  • Base Pairing
  • Base Sequence
  • Binding Sites
  • Cations / chemistry*
  • Circular Dichroism
  • DNA / chemical synthesis*
  • DNA / chemistry*
  • Dimerization
  • Heterocyclic Compounds / chemical synthesis*
  • Heterocyclic Compounds / chemistry*
  • Molecular Structure
  • Spectrometry, Fluorescence
  • Surface Plasmon Resonance / methods

Substances

  • Cations
  • Heterocyclic Compounds
  • DNA