Supercharging Prions via Amyloid-Selective Lysine Acetylation

Angew Chem Int Ed Engl. 2021 Jun 25;60(27):15069-15079. doi: 10.1002/anie.202103548. Epub 2021 May 26.

Abstract

Repulsive electrostatic forces between prion-like proteins are a barrier against aggregation. In neuropharmacology, however, a prion's net charge (Z) is not a targeted parameter. Compounds that selectively boost prion Z remain unreported. Here, we synthesized compounds that amplified the negative charge of misfolded superoxide dismutase-1 (SOD1) by acetylating lysine-NH3+ in amyloid-SOD1, without acetylating native-SOD1. Compounds resembled a "ball and chain" mace: a rigid amyloid-binding "handle" (benzothiazole, stilbene, or styrylpyridine); an aryl ester "ball"; and a triethylene glycol chain connecting ball to handle. At stoichiometric excess, compounds acetylated up to 9 of 11 lysine per misfolded subunit (ΔZfibril =-8100 per 103 subunits). Acetylated amyloid-SOD1 seeded aggregation more slowly than unacetylated amyloid-SOD1 in vitro and organotypic spinal cord (these effects were partially due to compound binding). Compounds exhibited reactivity with other amyloid and non-amyloid proteins (e.g., fibrillar α-synuclein was peracetylated; serum albumin was partially acetylated; carbonic anhydrase was largely unacetylated).

Keywords: acetylation; amyotrophic lateral sclerosis; neurodegeneration; protein aggregation; superoxide dismutase.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Acetylation
  • Amyloid / chemistry
  • Amyloid / metabolism*
  • Humans
  • Lysine / chemistry
  • Lysine / metabolism*
  • Molecular Structure
  • Prions / chemistry
  • Prions / metabolism*
  • Superoxide Dismutase-1 / chemistry
  • Superoxide Dismutase-1 / metabolism*

Substances

  • Amyloid
  • Prions
  • SOD1 protein, human
  • Superoxide Dismutase-1
  • Lysine