Mechanistic analysis of a suicide inactivator of histone demethylase LSD1

Biochemistry. 2007 Jun 12;46(23):6892-902. doi: 10.1021/bi700414b. Epub 2007 May 19.

Abstract

Lysine-specific demethylase 1 (LSD1) is a transcriptional repressor and a flavin-dependent amine oxidase that is responsible for the removal of methyl from lysine 4 of histone H3. In this study, we characterize the mechanism and scope of LSD1 inhibition by a propargylamine-derivatized histone H3 substrate (1). Unlike aziridinyl and cyclopropylamine-derivatized histone H3 peptide substrate analogues, compound 1 appears to covalently modify and irreversibly inactivate LSD1 with high potency. Accompanying this inactivation is a spectroscopic change, which shifts the absorbance maximum to 392 nm. Spectral changes associated with the 1-LSD1 complex and reactivity to decreased pH and sodium borohydride treatment were suggestive of a structure involving a flavin-linked inhibitor conjugate between N5 of the flavin and the terminal carbon of the inhibitor. Using a 13C-labeled inhibitor, NMR analysis of the 1-flavin conjugate was consistent with this structural assignment. Kinetic analysis of the spectroscopic shift induced by 1 showed that the flavin adduct formed in a reaction with kinetic constants similar to those of the LSD1 inactivation process. Taken together, these data support a mechanism of LSD1 inactivation by 1 involving amine oxidation followed by Michael addition to the propargylic imine. We further examined the potential for a biotinylated analogue of 1 (1-Btn) to be used as a tool in affinity pulldown experiments. Using 1-Btn, it was feasible to selectively pull down spiked and endogenous LSD1 from HeLa cell nuclear extracts, setting the stage for activity-based demethylase proteomics.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't

MeSH terms

  • Amino Acid Sequence
  • Biotinylation
  • Enzyme Inhibitors / chemistry
  • Enzyme Inhibitors / pharmacology*
  • Flavins / pharmacology
  • Glutathione / metabolism
  • HeLa Cells
  • Histone Demethylases
  • Humans
  • Kinetics
  • Magnetic Resonance Spectroscopy
  • Molecular Sequence Data
  • Oxidation-Reduction
  • Oxidoreductases, N-Demethylating / antagonists & inhibitors*
  • Oxidoreductases, N-Demethylating / chemistry*
  • Oxidoreductases, N-Demethylating / isolation & purification
  • Spectrophotometry

Substances

  • Enzyme Inhibitors
  • Flavins
  • Histone Demethylases
  • KDM1A protein, human
  • Oxidoreductases, N-Demethylating
  • Glutathione