Replica of a fishy enzyme: structure-function analogue of trimethylamine-N-oxide reductase

Inorg Chem. 2013 May 6;52(9):5316-27. doi: 10.1021/ic4002576. Epub 2013 Apr 17.

Abstract

Three new complexes, [Mo(IV)O(mnt)(SS)](2-) (SS = dimethylethylenedicarboxylate (DMED), toluenedithiolate (tdt), benzenedithiolate (bdt); mnt = maleonitriledithiolate), each possessing two different dithiolene ligands, are synthesized as model of trimethylamine-N-oxide reductase. The asymmetric dithiolene ligands present in these complexes simulate the two different (P and Q) pterin coordinations in the family of DMSO reductase. These complexes reduce trimethylamine-N-oxide ((CH3)3N(+)-O(-) or TMANO), the biological substrate of trimethylamine-N-oxide reductase, to trimethylamine ((CH3)3N), responsible for the fishy smell of dead aquatic animals. The reaction kinetics of trimethylamine-N-oxide reduction by these complexes follow the Michaelis-Menten saturation kinetics. These experimental findings have been rationalized by DFT, TD-DFT level of calculations.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Benzene Derivatives / chemistry
  • Carboxylic Acids / chemistry
  • Coordination Complexes / chemistry*
  • Crystallography, X-Ray
  • Cytochrome P-450 Enzyme System / chemistry*
  • Ethylenes / chemistry
  • Methylamines / chemistry*
  • Models, Molecular
  • Molybdenum / chemistry*
  • Oxidation-Reduction
  • Oxygen / chemistry
  • Quantum Theory
  • Shewanella / enzymology*
  • Sulfhydryl Compounds / chemistry
  • Toluene / analogs & derivatives

Substances

  • Benzene Derivatives
  • Carboxylic Acids
  • Coordination Complexes
  • Ethylenes
  • Methylamines
  • Sulfhydryl Compounds
  • maleinitriledithiolate
  • Toluene
  • Molybdenum
  • Cytochrome P-450 Enzyme System
  • tertiary amine N-oxide reductase
  • trimethyloxamine
  • Oxygen