Anaerobic degradation of n-hexane in a denitrifying bacterium: further degradation of the initial intermediate (1-methylpentyl)succinate via C-skeleton rearrangement

Arch Microbiol. 2002 Mar;177(3):235-43. doi: 10.1007/s00203-001-0381-3. Epub 2001 Dec 14.


The anaerobic degradation pathway of the saturated hydrocarbon n-hexane in a denitrifying strain (HxN1) was examined by gas chromatography-mass spectrometry of derivatized extracts from cultures grown with unlabeled and deuterated substrate; several authentic standard compounds were included for comparison. The study was focused on possible reaction steps that follow the initial formation of (1-methylpentyl)succinate from n-hexane and fumarate. 4-Methyloctanoic, 4-methyloct-2-enoic, 2-methylhexanoic, 2-methylhex-2-enoic and 3-hydroxy-2-methylhexanoic acids (in addition to a few other methyl-branched acids) were detected in n-hexane-grown but not in n-hexanoate-grown cultures. Labeling indicated preservation of the original carbon chain of n-hexane in these acids. Tracing of the deuterium label of 3- d1-(1-methylpentyl)succinate in tentative subsequent products indicated a deuterium/carboxyl carbon exchange in the succinate moiety. This suggests that the metabolism of (1-methylpentyl)succinate employs reactions analogous to those in the established conversion of succinyl-CoA via methylmalonyl-CoA to propionyl-CoA. Accordingly, a pathway is proposed in which (1-methylpentyl)succinate is converted to the CoA-thioester, rearranged to (2-methylhexyl)malonyl-CoA and decarboxylated (perhaps by a transcarboxylase) to 4-methyloctanoyl-CoA. The other identified fatty acids match with a further degradation of 4-methyloctanoyl-CoA via rounds of conventional beta-oxidation. Such a pathway would also allow regeneration of fumarate (for n-hexane activation) from propionyl-CoA formed as intermediate and hence present a cyclic process.

Publication types

  • Comparative Study
  • Research Support, Non-U.S. Gov't

MeSH terms

  • Alkanes / analysis
  • Alkanes / metabolism*
  • Anaerobiosis
  • Bacteria / growth & development
  • Bacteria / metabolism*
  • Caproates / metabolism
  • Culture Media
  • Deuterium
  • Fumarates / metabolism
  • Gas Chromatography-Mass Spectrometry
  • Hexanes / chemistry
  • Hexanes / metabolism*
  • Nitrates / metabolism
  • Oxidation-Reduction
  • Succinates / analysis
  • Succinates / metabolism*


  • (1-methylpentyl)succinate
  • Alkanes
  • Caproates
  • Culture Media
  • Fumarates
  • Hexanes
  • Nitrates
  • Succinates
  • hexanoic acid
  • n-hexane
  • fumaric acid
  • Deuterium