Discovery of Selective Cyclic d-Sulfopeptide Ligands of the Chemokine CCL22 via Mirror-Image mRNA Display with Genetic Reprogramming

J Am Chem Soc. 2024 Dec 18;146(50):34253-34259. doi: 10.1021/jacs.4c12057. Epub 2024 Dec 4.

Abstract

Chemokines are small proteins involved in recruiting leukocytes to sites of inflammation via interactions with specific cell surface receptors. CCL22 is a chemokine known to play a critical role in inflammatory diseases such as atopic dermatitis and asthma; inhibition of this chemokine therefore represents an attractive therapeutic strategy. Herein, we describe the discovery of cyclic d-sulfopeptide inhibitors of CCL22 identified through mirror-image mRNA display with genetic reprogramming. Chemical synthesis of mirror-image d-CCL22 enabled screening of a cyclic peptide library comprised of all l-amino acids, with reprogramming of l-sulfotyrosine to mimic the presence of this post-translational modification on native chemokine receptors. Enriched macrocyclic peptides were prepared in their mirror-image d-form and assessed for binding against native l-CCL22. The most potent ligand, a plasma-stable d-cyclic peptide bearing four d-sulfotyrosine residues, exhibited nanomolar affinity for CCL22, high selectivity over other chemokines, and nanomolar inhibition of CCL22 signaling through CCR4. This work highlights the vast potential of mirror-image mRNA display technology for discovering proteolytically stable d-peptide inhibitors of protein-protein interactions relevant across a range of therapeutic indications.

MeSH terms

  • Chemokine CCL22* / metabolism
  • Drug Discovery
  • Humans
  • Ligands
  • Peptides, Cyclic* / chemical synthesis
  • Peptides, Cyclic* / chemistry
  • Peptides, Cyclic* / pharmacology
  • RNA, Messenger* / genetics
  • RNA, Messenger* / metabolism

Substances

  • Peptides, Cyclic
  • Ligands
  • RNA, Messenger
  • Chemokine CCL22
  • CCL22 protein, human