Site-Specific Histidine Aza-Michael Addition in Proteins Enabled by a Ferritin-Based Metalloenzyme

J Am Chem Soc. 2024 Dec 11;146(49):33309-33315. doi: 10.1021/jacs.4c14446. Epub 2024 Nov 5.

Abstract

Histidine modifications of proteins are broadly based on chemical methods triggering N-substitution reactions such as aza-Michael addition at histidine's moderately nucleophilic imidazole side chain. While recent studies have demonstrated chemoselective, histidine-specific modifications by further exploiting imidazole's electrophilic reactivity to overcome interference from the more nucleophilic lysine and cysteine, achieving site-specific histidine modifications remains a major challenge due to the absence of spatial control over chemical processes. Herein, through X-ray crystallography and cryo-electron microscopy structural studies, we describe the rational design of a nature-inspired, noncanonical amino-acid-incorporated, human ferritin-based metalloenzyme that is capable of introducing site-specific post-translational modifications (PTMs) to histidine in peptides and proteins. Specifically, chemoenzymatic aza-Michael additions on single histidine residues were carried out on eight protein substrates ranging from 10 to 607 amino acids including the insulin peptide hormone. By introducing an insulin-targeting peptide into our metalloenzyme, we further directed modifications to be carried out site-specifically on insulin's B-chain histidine 5. The success of this biocatalysis platform outlines a novel approach in introducing residue- and, moreover, site-specific post-translational modifications to peptides and proteins, which may further enable reactions to be carried out in vivo.

MeSH terms

  • Aza Compounds / chemistry
  • Crystallography, X-Ray
  • Ferritins* / chemistry
  • Ferritins* / metabolism
  • Histidine* / chemistry
  • Humans
  • Metalloproteins* / chemistry
  • Metalloproteins* / metabolism
  • Models, Molecular
  • Protein Processing, Post-Translational

Substances

  • Histidine
  • Ferritins
  • Metalloproteins
  • Aza Compounds