Catalytic detoxification of nerve agent and pesticide organophosphates by butyrylcholinesterase assisted with non-pyridinium oximes

Biochem J. 2013 Feb 15;450(1):231-42. doi: 10.1042/BJ20121612.

Abstract

In the present paper we show a comprehensive in vitro, ex vivo and in vivo study on hydrolytic detoxification of nerve agent and pesticide OPs (organophosphates) catalysed by purified hBChE (human butyrylcholinesterase) in combination with novel non-pyridinium oxime reactivators. We identified TAB2OH (2-trimethylammonio-6-hydroxybenzaldehyde oxime) as an efficient reactivator of OP-hBChE conjugates formed by the nerve agents VX and cyclosarin, and the pesticide paraoxon. It was also functional in reactivation of sarin- and tabun-inhibited hBChE. A 3-5-fold enhancement of in vitro reactivation of VX-, cyclosarin- and paraoxon-inhibited hBChE was observed when compared with the commonly used N-methylpyridinium aldoxime reactivator, 2PAM (2-pyridinealdoxime methiodide). Kinetic analysis showed that the enhancement resulted from improved molecular recognition of corresponding OP-hBChE conjugates by TAB2OH. The unique features of TAB2OH stem from an exocyclic quaternary nitrogen and a hydroxy group, both ortho to an oxime group on a benzene ring. pH-dependences reveal participation of the hydroxy group (pKa=7.6) forming an additional ionizing nucleophile to potentiate the oxime (pKa=10) at physiological pH. The TAB2OH protective indices in therapy of sarin- and paraoxon-exposed mice were enhanced by 30-60% when they were treated with a combination of TAB2OH and sub-stoichiometric hBChE. The results of the present study establish that oxime-assisted catalysis is feasible for OP bioscavenging.

Publication types

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

MeSH terms

  • Animals
  • Butyrylcholinesterase / metabolism*
  • Catalysis
  • Chemical Warfare Agents / metabolism*
  • Chemical Warfare Agents / toxicity
  • Female
  • Humans
  • Hydrogen-Ion Concentration
  • Inactivation, Metabolic
  • Kinetics
  • Mice
  • Mice, Inbred Strains
  • Organophosphates / metabolism*
  • Organophosphates / toxicity
  • Oximes / chemistry*
  • Oximes / metabolism
  • Paraoxon / metabolism*
  • Paraoxon / toxicity
  • Sarin / metabolism*
  • Sarin / toxicity

Substances

  • Chemical Warfare Agents
  • Organophosphates
  • Oximes
  • Sarin
  • Butyrylcholinesterase
  • Paraoxon