Hydrazide Mimics for Protein Lysine Acylation To Assess Nucleosome Dynamics and Deubiquitinase Action

J Am Chem Soc. 2018 Aug 1;140(30):9478-9485. doi: 10.1021/jacs.8b03572. Epub 2018 Jul 24.

Abstract

A range of acyl-lysine (acyl-Lys) modifications on histones and other proteins have been mapped over the past decade but for most, their functional and structural significance remains poorly characterized. One limitation in the study of acyl-Lys containing proteins is the challenge of producing them or their mimics in site-specifically modified forms. We describe a cysteine alkylation-based method to install hydrazide mimics of acyl-Lys post-translational modifications (PTMs) on proteins. We have applied this method to install mimics of acetyl-Lys, 2-hydroxyisobutyryl-Lys, and ubiquityl-Lys that could be recognized selectively by relevant acyl-Lys modification antibodies. The acyl-Lys modified histone H3 proteins were reconstituted into nucleosomes to study nucleosome dynamics and stability as a function of modification type and site. We also installed a ubiquityl-Lys mimic in histone H2B and generated a diubiquitin analog, both of which could be cleaved by deubiquitinating enzymes. Nucleosomes containing the H2B ubiquityl-Lys mimic were used to study the SAGA deubiquitinating module's molecular recognition. These results suggest that acyl-Lys mimics offer a relatively simple and promising strategy to study the role of acyl-Lys modifications in the function, structure, and regulation of proteins and protein complexes.

Publication types

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

MeSH terms

  • Alkylation
  • Animals
  • Antibodies / immunology
  • Biomimetics / methods
  • Cysteine / chemistry
  • Cysteine Endopeptidases / chemistry
  • Deubiquitinating Enzymes
  • Endopeptidases / chemistry
  • Escherichia coli / genetics
  • Histones / chemical synthesis
  • Histones / chemistry*
  • Histones / immunology
  • Histones / isolation & purification
  • Humans
  • Hydrazines / chemical synthesis
  • Hydrazines / chemistry*
  • Nuclear Proteins / chemistry
  • Nuclear Proteins / genetics
  • Nucleosomes / chemistry
  • Saccharomyces cerevisiae / enzymology
  • Saccharomyces cerevisiae Proteins / chemistry
  • Saccharomyces cerevisiae Proteins / genetics
  • Ubiquitin / chemical synthesis
  • Ubiquitin / chemistry*
  • Ubiquitin / immunology
  • Ubiquitin / isolation & purification
  • Ubiquitin Thiolesterase / chemistry
  • Ubiquitin Thiolesterase / genetics
  • Xenopus laevis

Substances

  • Antibodies
  • Histones
  • Hydrazines
  • Nuclear Proteins
  • Nucleosomes
  • Saccharomyces cerevisiae Proteins
  • Ubiquitin
  • Endopeptidases
  • Deubiquitinating Enzymes
  • OTUB1 protein, human
  • UBP10 protein, S cerevisiae
  • Ubiquitin Thiolesterase
  • Cysteine Endopeptidases
  • UBP8 protein, S cerevisiae
  • Cysteine