Effects of the A.T/T.A degeneracy of pyrrole--imidazole polyamide recognition in the minor groove of DNA

Biochemistry. 1996 Sep 24;35(38):12532-7. doi: 10.1021/bi960744i.

Abstract

Pairing rules have been developed to predict the sequence specificity of minor groove binding polyamides containing pyrrole (Py) and imidazole (Im) amino acids. An Im/Py pair distinguishes G.C from C.G and both of these from A.T/T.A base pairs. A Py/Py pair appears not to distinguish A.T from T.A base pairs. To test the extent of this degeneracy, the affinity and binding orientation of the hairpin polyamide ImPyPy-gamma-PyPyPy-beta-Dp were measured for eight possible five base pair 5'-TG(A,T)(3)-3' match sites. Affinity cleavage experiments using a polyamide with an EDTA.Fe(II) moiety at the carboxy terminus, ImPyPy-gamma-PyPyPy-beta-Dp-EDTA.Fe(II), are consistent with formation of an oriented 1:1 hairpin polyamide complex at all eight 5'-TG(A,T)(3)-3' binding sites [20 mM HEPES, 200 mM NaCl, 50 mg/ml glycogen, pH 7.0, 22 degrees C, 5 mM DTT, 1 mM Fe(II)]. Quantitative DNase I footprint titration experiments reveal that ImPyPy-gamma-PyPyPy-beta-Dp binds all eight 5'-TG(A,T)(3)-3' target sites with only a 12-fold difference in the equilibrium association constants between the strongest site, 5'-TGTTT-3' (Ka = 2.1 x 10(8) M-1), and the weakest site, 5'-TGAAT-3' (Ka = 1.8 x 10(7) M-1) (10 mM Tris.HCl, 10 mM KCl, 10 mM MgCl2, 5 mM CaCl2, pH 7.0, 22 degrees C). This relatively small range indicates that the Py/Py pair is approximately degenerate for recognition of A,T base pairs, affording generality with regard to targeting sequences of mixed A.T/T.A composition.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, P.H.S.

MeSH terms

  • Base Composition
  • Base Sequence
  • Binding Sites
  • DNA / chemistry*
  • DNA / metabolism*
  • DNA Footprinting
  • Deoxyribonuclease I / metabolism
  • Edetic Acid / metabolism
  • Electrophoresis, Polyacrylamide Gel
  • Imidazoles / metabolism
  • Iron Compounds / chemistry
  • Iron Compounds / metabolism
  • Models, Molecular
  • Molecular Sequence Data
  • Nucleic Acid Conformation*
  • Nylons / chemistry
  • Nylons / metabolism*
  • Oligodeoxyribonucleotides / chemical synthesis
  • Oligodeoxyribonucleotides / metabolism
  • Pyrroles / metabolism

Substances

  • Imidazoles
  • Iron Compounds
  • Nylons
  • Oligodeoxyribonucleotides
  • Pyrroles
  • DNA
  • Edetic Acid
  • Deoxyribonuclease I