Abstract
Hydrocarbons represent “energy-rich” growth substrates for aerobic microorganisms and in principle allow high growth yields. In contrast, the energy gain with hydrocarbons in many anaerobic microorganisms is very low. The maximum gain of energy per mol of hydrocarbon degraded in the catabolism is predicted from calculated ΔG values. Some anaerobic degradation reactions of hydrocarbons with very low-energy gain as well as anaerobic activation reactions of hydrocarbons deserve particular attention from a bioenergetic point of view.
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Notes
- 1.
A fermentable hydrocarbon is, for instance, the unsaturated acetylene. Also some other unsaturated hydrocarbons are, at least theoretically, fermentable.
- 2.
H, 1.008; C, 12.011.
- 3.
Heat change of reaction under constant pressure.
- 4.
\( \mathrm{T}=298.15\ \mathrm{K}\ \left(25{}^{\circ}\mathrm{C}\right) \); standard activity of solutes, \( a=1 \); standard (partial) pressure of gases \( =101 \) kPa (standard fugacity \( =1 \)).
- 5.
ΔG Standard values at temperatures other than 298.15 K can be calculated via the integrated “Delta-version” of the Gibbs-Helmholtz equation \( {\left(\frac{\partial }{\partial T}\frac{\Delta \mathrm{G}}{T}\right)}_p=\frac{\Delta H}{T^2}. \) Assuming that temperature dependence of ΔH within the range of physiologically relevant temperatures is negligible, the free energy change at temperatures other than 298.15 K (but at standard activities) is
$$ \Delta {G}_T^{Standard}=\frac{T}{298.15}\Delta {G}^{{}^{\circ}}\kern0.66em +\kern0.66em \left(1-\frac{T}{298.15}\right)\Delta {H}^{{}^{\circ}} $$The same result is obtained from \( \Delta G=\Delta H- T\Delta S \) S by assuming that ΔH and ΔS are essentially constant within the range of physiologically relevant temperatures.
- 6.
The apparent correctness of the old unit atm is due to the fact that it is numerically equivalent with standard fugacity \( =1 \). Activities and fugacities are by definition without units, and the formally correct approximated substitution would \( {a}_{\mathrm{A}}=\frac{{\left[\mathrm{A}\right]}_{Actual}}{{\left[\mathrm{A}\right]}_{Standard}} \), etc. Here, the use of the modern unit Pa or kPa for [A], etc. is coherent.
- 7.
The extremely low hypothetical equilibrium concentrations of these species can be calculated.
- 8.
Linearity in the series of the higher alkanes may be a “pre-assumption” and basis for calculation of ΔG ° f or ΔH ° f values of compounds in homologous series via incremental additions. In the numerous sources of thermodynamic data, the original basis underlying such data is often difficult to trace back.
- 9.
Also, the highly ordered (“improbable”) structure of the long-chain alkane contributes to thermodynamic instability.
- 10.
A prominent example is nitrogenase: Despite the long evolution of nitrogen fixation, an enzyme type has not evolved that catalyzes the thermodynamically feasible N2 reduction with H2 or energetically equivalent electron donors without an investment of energy.
- 11.
- 12.
The Haldane equation describes the connection between the equilibrium concentrations of the reactants and products and their kinetic constants k cat and K m . The equilibrium constant is also thermodynamically given by the concentrations at \( \Delta G = 0 \). In case of the reaction \( \mathrm{S}\to \mathrm{P} \), the connection is \( {\left(\frac{\left[\mathrm{P}\right]}{\left[\mathrm{S}\right]}\right)}_{\mathrm{e}\mathrm{q}}=\frac{k_{cat}^{\mathrm{S}}/{K}_m^{\mathrm{S}}}{k_{cat}^{\mathrm{P}}/{K}_m^{\mathrm{P}}}={\mathrm{e}}^{-\Delta {G}^{{}^{\circ}}/(RT)}. \)
- 13.
The q ATP is conceptually related to the \( \mathrm{P}/2{\mathrm{e}}^{-} \) ratio in aerobic and anaerobic respiration which indicates the number of ATP molecules formed per electron pair transported in the respiratory chain (in aerobes also P/O ratio). However, the q ATP also includes ATP from substrate level phosphorylation.
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Widdel, F., Musat, F. (2016). Energetic and Other Quantitative Aspects of Microbial Hydrocarbon Utilization: An Introduction. In: Rojo, F. (eds) Aerobic Utilization of Hydrocarbons, Oils and Lipids. Handbook of Hydrocarbon and Lipid Microbiology . Springer, Cham. https://doi.org/10.1007/978-3-319-39782-5_2-1
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