5'-(E)-Vinylphosphonate: A Stable Phosphate Mimic Can Improve the RNAi Activity of siRNA-GalNAc Conjugates

Chembiochem. 2016 Jun 2;17(11):985-9. doi: 10.1002/cbic.201600130. Epub 2016 Apr 28.

Abstract

Small interfering RNA (siRNA)-mediated silencing requires siRNA loading into the RNA-induced silencing complex (RISC). Presence of 5'-phosphate (5'-P) is reported to be critical for efficient RISC loading of the antisense strand (AS) by anchoring it to the mid-domain of the Argonaute2 (Ago2) protein. Phosphorylation of exogenous duplex siRNAs is thought to be accomplished by cytosolic Clp1 kinase. However, although extensive chemical modifications are essential for siRNA-GalNAc conjugate activity, they can significantly impair Clp1 kinase activity. Here, we further elucidated the effect of 5'-P on the activity of siRNA-GalNAc conjugates. Our results demonstrate that a subset of sequences benefit from the presence of exogenous 5'-P. For those that do, incorporation of 5'-(E)-vinylphosphonate (5'-VP), a metabolically stable phosphate mimic, results in up to 20-fold improved in vitro potency and up to a threefold benefit in in vivo activity by promoting Ago2 loading and enhancing metabolic stability.

Keywords: Clp1 kinase; RISC loading; oligonucleotides; phosphate mimic; siRNA.

MeSH terms

  • Acetylgalactosamine / chemistry*
  • Animals
  • Apolipoproteins B / antagonists & inhibitors
  • Apolipoproteins B / genetics
  • Apolipoproteins B / metabolism
  • Argonaute Proteins / antagonists & inhibitors
  • Argonaute Proteins / genetics
  • Argonaute Proteins / metabolism
  • Cells, Cultured
  • Factor IX / antagonists & inhibitors
  • Factor IX / genetics
  • Factor IX / metabolism
  • Hepatocytes / cytology
  • Hepatocytes / drug effects
  • Hepatocytes / metabolism
  • Humans
  • Lipoproteins, LDL / blood
  • Mice
  • Mice, Inbred C57BL
  • Organophosphonates / chemistry*
  • Organophosphonates / pharmacology
  • RNA Interference*
  • RNA, Small Interfering / chemistry*
  • RNA, Small Interfering / metabolism
  • RNA-Binding Proteins
  • RNA-Induced Silencing Complex / chemistry
  • RNA-Induced Silencing Complex / metabolism
  • Transcription Factors / metabolism
  • Vinyl Compounds / chemistry*
  • Vinyl Compounds / pharmacology

Substances

  • Apolipoproteins B
  • Argonaute Proteins
  • Hexim1 protein, mouse
  • Lipoproteins, LDL
  • Organophosphonates
  • RNA, Small Interfering
  • RNA-Binding Proteins
  • RNA-Induced Silencing Complex
  • Transcription Factors
  • Vinyl Compounds
  • vinylphosphonic acid
  • Factor IX
  • Acetylgalactosamine