In Situ Cyclization of Proteins (INCYPRO): Cross-Link Derivatization Modulates Protein Stability

J Org Chem. 2020 Feb 7;85(3):1476-1483. doi: 10.1021/acs.joc.9b02490. Epub 2019 Dec 16.

Abstract

Protein macrocyclization represents a very efficient strategy to increase the stability of protein tertiary structures. Here, we describe a panel of novel C3-symmetric tris-electrophilic agents and their use for the cyclization of proteins. These electrophiles are reacted with a protein domain harboring three solvent-exposed cysteine residues, resulting in the in situ cyclization of the protein (INCYPRO). We observe a clear dependency of cross-linking rates on the electrophilicity. All nine obtained cross-linked protein versions show considerably increased thermal stability (up to 29 °C increased melting temperature) when compared to that of the linear precursor. Most interestingly, the degree of stabilization correlates with the hydrophilicity of the cross-link. These results will support the development of novel cross-linked proteins and enable a more rational design process.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Cross-Linking Reagents
  • Cyclization
  • Protein Stability
  • Proteins*
  • Temperature

Substances

  • Cross-Linking Reagents
  • Proteins