Diversity and Common Principles in Enzymatic Activation of Hydrocarbons: An Introduction

  • F. WiddelEmail author
  • F. Musat
Reference work entry
Part of the Handbook of Hydrocarbon and Lipid Microbiology book series (HHLM)


Hydrocarbons are apolar compounds devoid of functional groups and therefore exhibit (with some exceptions) low chemical reactivity at room temperature. Utilization of hydrocarbons by microorganisms as growth substrates is initiated by the introduction of a functional group. An astounding diversity of activation reactions has evolved in microorganisms, notably in bacteria. Saturated hydrocarbons are activated by initial C–H-bond cleavage, while unsaturated (including aromatic) hydrocarbons are activated by an addition of a co-reactant to form an initial σ-bonded adduct. There is a principal difference between co-reactants and activation reactions in (1) aerobic and (2) anaerobic microorganisms. (1) Aerobic microorganisms always make use of molecular oxygen as a co-substrate so as to introduce one or two oxygen atoms by means of oxygenases. These enzymes usually contain metals (iron, copper). A common principle is the reduction of metal-bound O2 to the peroxide level; this converts into a metal-bound oxygen atom that performs the primary attack on the hydrocarbon. (2) Mechanisms in anaerobic activation of hydrocarbons are principally different. The anaerobic oxidation of methane is associated with a redox reaction of a nickel cofactor that is also involved in methanogenesis. The apparently most widely employed anaerobic activation mechanism of non-methane alkanes and alkyl-substituted aromatic hydrocarbons is a C–H-bond cleavage by a protein-hosted radical followed by addition of the radical product to fumarate; this results in a substituted succinate. A few alkyl-substituted aromatic hydrocarbons may be anaerobically hydroxylated (with the HO-group originating from H2O) at the side chain. In addition, there may be yet unknown mechanisms in anaerobic hydrocarbon activation.


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Authors and Affiliations

  1. 1.Max Planck Institute for Marine MicrobiologyBremenGermany
  2. 2.UFZ – Helmholtz Centre for Environmental ResearchLeipzigGermany

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