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

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Aerobic Utilization of Hydrocarbons, Oils, and Lipids

Part of the book series: Handbook of Hydrocarbon and Lipid Microbiology ((HHLM))

Abstract

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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Notes

  1. 1.

    Chemical generation of singlet dioxygen is difficult to achieve. An example is the oxidation of hydrogen peroxide with hypochlorous acid \( \left({\mathrm{H}}_2{\mathrm{O}}_2+\mathrm{HClO}\to {\mathrm{H}}_2\mathrm{O}\ {+}^1{\Delta}_g\;{\mathrm{O}}_2+{\mathrm{Cl}}^{-}+{\mathrm{H}}^{+}\right) \).

  2. 2.

    Another redox potential often indicated, \( {E}^{{}^{\circ}}=-0.16\ \mathrm{V} \), is based on standard activity (concentration) of aqueous O2 (dissolved in H2O) dissolved. Despite the relatively negative standard redox potential, the low \( {{\mathrm{O}}_2}^{\bullet -} \) concentration that is in equilibrium with O2 can nevertheless be relevant with respect to reactivity. Also, the equilibrium concentration of \( {{\mathrm{O}}_2}^{\bullet -} \) (that is formed by a one-electron step) does not decrease as dramatically (factor 10 per 0.0592 V, according to Nernst equation) with increasing redox potential as that of species formed by a two electron step (factor 100 per 0.0592 V). The reduction around \( \mathrm{pH}=7 \) does not involve a proton, because superoxide is deprotonated \( \left({{\mathrm{O}}_2}^{\bullet -}/{{\mathrm{HO}}_2}^{\bullet },{\mathrm{pK}}_{\mathrm{a}}=4.6\right) \).

  3. 3.

    Hence, the formal oxidation state of the carbon changes by \( +\mathrm{II} \). Assignment of formal oxidation states to the involved C–atoms before and after oxygenation may thus be used to check consistency of the formulated activation reaction. Examples: In terminal alkane oxygenation, the methyl group \( \left(-{\mathrm{CH}}_3,-\mathrm{III}\right) \) is converted to a hydroxymethyl group \( \left(-{\mathrm{CH}}_2\mathrm{OH},-\mathrm{I}\right) \). In an aromatic hydrocarbon, the (formally localized) “vinylen” \( \left(- \mathrm{CH}=\mathrm{CH} - , 2\times -\mathrm{I}=-\mathrm{I}\mathrm{I}\right) \) can be dioxygenated yielding a hydrodiol \( \left(-\mathrm{CHOH}-\mathrm{CHOH}-,2\times 0=0\right) \) and a non-aromatic ring, or can be monooxygenated yielding an “enol” \( \left(-\mathrm{CH}=\mathrm{COH}-,-\mathrm{I}+\mathrm{I}=0\right) \) with maintenance of the aromatic ring. However, because the two electrons for O2 reduction are derived from an intermediate of hydrocarbon degradation, oxygenation totally consumes 4 electrons from the hydrocarbon substrate (Fig. 2)

  4. 4.

    Named after the National Institute of Health where this hydrogen shift was first detected (Guroff et al. 1967).

  5. 5.

    Abbreviation AMO must not be confused with the same one sometimes used for alkene monooxygenase.

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Authors and Affiliations

  1. Max Planck Institute for Marine Microbiology, Bremen, Germany

    F. Widdel

  2. UFZ – Helmholtz Centre for Environmental Research, Leipzig, Germany

    F. Musat

Authors
  1. F. Widdel
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  2. F. Musat
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Correspondence to F. Widdel .

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Editors and Affiliations

  1. Centro Nacional de Biotecnología, CSIC, Madrid, Spain

    Fernando Rojo

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Widdel, F., Musat, F. (2019). Diversity and Common Principles in Enzymatic Activation of Hydrocarbons: An Introduction. In: Rojo, F. (eds) Aerobic Utilization of Hydrocarbons, Oils, and Lipids. Handbook of Hydrocarbon and Lipid Microbiology . Springer, Cham. https://doi.org/10.1007/978-3-319-50418-6_50

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