Potent and Prolonged Innate Immune Activation by Enzyme-Responsive Imidazoquinoline TLR7/8 Agonist Prodrug Vesicles

J Am Chem Soc. 2020 Jul 15;142(28):12133-12139. doi: 10.1021/jacs.0c01928. Epub 2020 Jun 30.

Abstract

Synthetic immune-stimulatory drugs such as agonists of the Toll-like receptors (TLR) 7/8 are potent activators of antigen-presenting cells (APCs), however, they also induce severe side effects due to leakage from the site of injection into systemic circulation. Here, we report on the design and synthesis of an amphiphilic polymer-prodrug conjugate of an imidazoquinoline TLR7/8 agonist that in aqueous medium forms vesicular structures of 200 nm. The conjugate contains an endosomal enzyme-responsive linker enabling degradation of the vesicles and release of the TLR7/8 agonist in native form after endocytosis, which results in high in vitro TLR agonist activity. In a mouse model, locally administered vesicles provoke significantly more potent and long-lasting immune stimulation in terms of interferon expression at the injection site and in draining lymphoid tissue compared to a nonamphiphilic control and the native TLR agonist. Moreover, the vesicles induce robust activation of dendritic cells in the draining lymph node in vivo.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Animals
  • Imidazoles / chemistry
  • Imidazoles / metabolism
  • Imidazoles / pharmacology*
  • Immunity, Innate / drug effects
  • Immunity, Innate / immunology
  • Membrane Glycoproteins / agonists*
  • Membrane Glycoproteins / immunology
  • Mice
  • Molecular Structure
  • Particle Size
  • Polyethylene Glycols / chemistry
  • Polyethylene Glycols / metabolism
  • Polyethylene Glycols / pharmacology
  • Prodrugs / chemistry
  • Prodrugs / metabolism
  • Prodrugs / pharmacology*
  • Quinolines / chemistry
  • Quinolines / metabolism
  • Quinolines / pharmacology*
  • Surface Properties
  • Toll-Like Receptor 7 / agonists*
  • Toll-Like Receptor 7 / immunology
  • Toll-Like Receptor 8 / agonists*
  • Toll-Like Receptor 8 / immunology
  • beta-Galactosidase / chemistry
  • beta-Galactosidase / immunology*
  • beta-Galactosidase / metabolism

Substances

  • Imidazoles
  • Membrane Glycoproteins
  • Prodrugs
  • Quinolines
  • TLR8 protein, mouse
  • Tlr7 protein, mouse
  • Toll-Like Receptor 7
  • Toll-Like Receptor 8
  • Polyethylene Glycols
  • beta-Galactosidase