Sequence specificity of alkylation for a series of nitrogen mustard-containing analogues of distamycin of increasing binding site size: evidence for increased cytotoxicity with enhanced sequence specificity

Biochemistry. 1995 Oct 10;34(40):13034-41. doi: 10.1021/bi00040a014.

Abstract

The covalent sequence specificity of a series of nitrogen mustard-containing analogues of distamycin was determined using modified sequencing techniques. The analogues tether benzoic acid mustard (BAM) and possess either one, two, or three pyrrole-amide units. Previous characterization of the biological profile of the series revealed an increase in cytotoxicity for each corresponding increase in the number of pyrrole units, while showing poor cross-link formation in isolated and cellular DNA. Examination of the sequence specificity revealed that BAM produced guanine-N7 lesions in similar manner to other conventional nitrogen mustards. The monopyrrole BAM conjugate also produced guanine-N7 alkylation in a similar pattern to BAM. However, alkylation of adenines was also seen that was found to be minor groove adenine-N3 lesions. The dipyrrole and tripyrrole conjugates did not produce detectable guanine-N7 alkylation but only alkylated in AT tracts. In addition, the tripyrrole conjugate preferentially alkylated only a subset of those sites alkylated by the monopyrrole and dipyrrole conjugates. Two sites, 5'-TTTTGG and 5'-TTTTGA, confirmed as guanine-N3 and adenine-N3 lesions, respectively, were strongly alkylated by the tripyrrole conjugate in preference to other similar sites including three occurrences of 5'-TTTTAA. Footprinting studies comparing distamycin and the tripyrrole conjugate showed identical non-covalent recognition of AT-rich sites. Hence, the drug that possessed the most enhanced sequence specificity for alkylation was also the most cytotoxic of this series.

Publication types

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

MeSH terms

  • Antineoplastic Agents, Alkylating / chemistry*
  • Base Sequence
  • Benzoates / chemistry
  • Benzoic Acid
  • DNA / biosynthesis
  • DNA / chemistry*
  • DNA Adducts / chemistry
  • DNA Damage
  • DNA Primers / chemistry
  • Distamycins / chemistry*
  • Mechlorethamine / chemistry*
  • Molecular Sequence Data
  • Nitrogen Mustard Compounds / chemistry*
  • Structure-Activity Relationship

Substances

  • Antineoplastic Agents, Alkylating
  • Benzoates
  • DNA Adducts
  • DNA Primers
  • Distamycins
  • Nitrogen Mustard Compounds
  • Mechlorethamine
  • tallimustine
  • Benzoic Acid
  • DNA