Design of a New Fluorescent Oligonucleotide-Based Assay for a Highly Specific Real-Time Detection of Apurinic/Apyrimidinic Site Cleavage by Tyrosyl-DNA Phosphodiesterase 1

Bioconjug Chem. 2015 Oct 21;26(10):2046-53. doi: 10.1021/acs.bioconjchem.5b00451. Epub 2015 Sep 10.

Abstract

Tyrosyl-DNA phosphodiesterase 1 (Tdp1) promotes catalytic scission of a phosphodiester bond between the 3'-end of DNA and the hydroxyl group of a tyrosine residue, as well as cleaving off a variety of other 3'-terminal phosphate-linked DNA substituents. We have shown recently that Tdp1 can initiate an apurinic/apyrimidinic (AP) site repair pathway that is independent from the one mediated by AP endonuclease 1 (APE1). Until recently, there was no method available of tracking the AP-site cleaving activity of Tdp1 by real-time fluorescence assay. In the present study we demonstrate a highly specific real-time detection of the AP-site cleaving activity of Tdp1 which allows one to distinguish it from the activity of APE1 by using a short hairpin oligonucleotide with a 1,12-dodecanediol loop, a 5'-fluorophore, and a 3'-quencher. Specific phosphodiesterase activity of Tdp1, which is usually able to remove quencher from the 3'-end of DNA, was suppressed in our approach by introducing a noncleavable phosphate group mimic between the 3'-end and the quencher. As a nondigestible 3'-phosphate analogue, we have used a new uncharged tetramethyl phosphoryl guanidine (Tmg) group, which is resistant to 3'-phosphodiesterase cleavage.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Apurinic Acid / metabolism*
  • Biological Assay / methods*
  • DNA-(Apurinic or Apyrimidinic Site) Lyase / metabolism
  • Fluorescent Dyes / chemistry
  • Kinetics
  • Microscopy, Fluorescence
  • Mutation
  • Oligonucleotides / chemistry*
  • Oligonucleotides / metabolism
  • Phosphoric Diester Hydrolases / analysis
  • Phosphoric Diester Hydrolases / genetics
  • Phosphoric Diester Hydrolases / metabolism*
  • Polynucleotides / metabolism*
  • Substrate Specificity

Substances

  • Fluorescent Dyes
  • Oligonucleotides
  • Polynucleotides
  • apyrimidinic acid
  • Apurinic Acid
  • Phosphoric Diester Hydrolases
  • TDP1 protein, human
  • APEX1 protein, human
  • DNA-(Apurinic or Apyrimidinic Site) Lyase