γ-Secretase Cleaves Bifunctional Fatty Acid-Conjugated Small Molecules with Amide Bonds in Mammalian Cells

ACS Chem Biol. 2024 Dec 20;19(12):2438-2450. doi: 10.1021/acschembio.4c00432. Epub 2024 Nov 20.

Abstract

Connecting two small molecules, such as ligands, fluorophores, or lipids, together via a linker with amide bonds is a widely used strategy to generate synthetic bifunctional molecules for various biological and biomedical applications. Such bifunctional molecules have been used in live-cell experiments under the assumption that they should be stable in cells. However, we recently found that a membrane-targeting bifunctional molecule, composed of a lipopeptide and the small-molecule ligand trimethoprim, referred to as mgcTMP, underwent amide-bond cleavage in mammalian cells. In this work, we first identified γ-secretase as the major protease degrading mgcTMP in cells. We next investigated the intracellular degradation of several different types of amide-linked bifunctional compounds and found that N-terminally fatty acid-conjugated small molecules are susceptible to γ-secretase-mediated amide-bond cleavage. In contrast, amide-linked bifunctional molecules composed of two small molecules, such as ligands and hydrophobic groups, which lack lipid modification, did not undergo intracellular degradation. These findings highlight a previously overlooked consideration for the development and application of lipid-based bifunctional molecules in chemical biology research.

MeSH terms

  • Amides* / chemistry
  • Amides* / metabolism
  • Amyloid Precursor Protein Secretases* / chemistry
  • Amyloid Precursor Protein Secretases* / metabolism
  • Animals
  • Fatty Acids* / chemistry
  • Fatty Acids* / metabolism
  • HEK293 Cells
  • Humans
  • Ligands
  • Small Molecule Libraries / chemistry
  • Small Molecule Libraries / pharmacology

Substances

  • Amyloid Precursor Protein Secretases
  • Amides
  • Fatty Acids
  • Small Molecule Libraries
  • Ligands