Methanogenesis
Methanogenesis, the biological production of methane, is
a fascinating process carried out by a group of strictly
anaerobic Archaea called methanogens. This process
involves a unique series of biochemical reactions that
employ novel coenzymes, making it a captivating subject
for study.
Methanogenesis is the biological production of methane
•It is carried out by a unique group of Archaea
known as methanogens.
•Only occurs in strictly anaerobic (oxygen-free)
environments.
Key Players – The
Methanogens
•Strictly anaerobic Archaea.
•Found in environments like wetlands, animal guts, and landfills.
•Phylogenetic diversity and evolutionary significance
Examples:-. Methanobacterium, Methanococcus
Steps in Anaerobic
Environments
•Hydrolysis: Complex organic polymers (e.g., carbohydrates, lipids, proteins) are
broken down into simpler monomers like glucose, amino acids, and fatty acids
•Acidogenesis: Monomers are fermented by microbes into short-chain fatty acids
(e.g., acetate), alcohols, hydrogen and carbon dioxide
Acetogenesis: Fatty acids and alcohols are converted into acetate, hydrogen, and
carbon dioxide
Methanogenesis: Methanogens use acetate or CO₂ + H₂ to produce methane.
The Pathway Overview
•Input: CO₂, H₂ (or alternatives like formate, CO, alcohols).
•Output: Methane (CH₄).
•Intermediate steps involve carbon moving from oxidation
state +4 (CO₂) to -4 (CH₄).
Coenzymes in Action
•C1 Carriers: Methanofuran, Methanopterin, Coenzyme M (CoM), Coenzyme F430
•Electron Donors: Coenzyme F420, Coenzyme B (CoB).
•Specialized coenzymes make methanogenesis unique.
C1 Carriers in Methanogenesis
1 Methanofuran 2 Methanopterin
This coenzyme is essential Resembling folic acid,
for the first step of methanopterin plays a
methanogenesis, role analogous to
containing a five- tetrahydrofolate, carrying
membered furan ring and the C1 unit in the
an amino nitrogen atom intermediate steps of CO2
that binds CO2. reduction to CH4.
3 Coenzyme M (CoM) 4 Coenzyme F430
A small molecule required A nickel (Ni2+)-containing
for the terminal step of tetrapyrrole coenzyme needed
methanogenesis, the for the terminal step of
conversion of a methyl methanogenesis as part of the
group (CH3) to CH4. methyl reductase enzyme
complex.
Redox Coenzymes in Methanogenesis
Coenzyme F420 Coenzyme B (CoB)
A flavin derivative, F420 acts as the electron Also known as 7-mercaptoheptanoylthreonine
donor in several steps of CO2 reduction. Its phosphate, CoB is required for the terminal step
oxidized form absorbs light at 420 nm and of methanogenesis catalyzed by the methyl
fluoresces blue-green, aiding in methanogen reductase enzyme complex. Its structure
identification. resembles pantothenic acid, a component of
acetyl-CoA.
Methanogenesis from CO2
1 Step 1: CO2 Activation
CO2 is activated by a methanofuran-containing enzyme and reduced
to the formyl level. The immediate electron donor is ferredoxin, a
strong reductant.
2
Step 2: Formyl Group Transfer and Reduction
The formyl group is transferred to methanopterin and subsequently
dehydrated and reduced in two steps to the methylene and methyl levels.
Reduced F420 acts as the electron donor.
3
Step 3: Methyl Group Transfer
The methyl group is transferred from methanopterin to CoM by methyl
transferase, a highly exergonic reaction linked to Na+ pumping across
4 the membrane.
Step 4: Methane Formation
Methyl-CoM is reduced to methane by methyl reductase, requiring F430 and CoB.
Coenzyme F430 removes the CH3 group, forming a Ni2+–CH3 complex, which is
5 reduced by CoB, generating CH4 and a disulfide complex of CoM and CoB.
Step 5: Coenzyme Regeneration
Free CoM and CoB are regenerated by the reduction of CoM-S—S-CoB with H2.
Summary
CO₂ Activation:
1. CO₂ is turned into a formyl group using ferredoxin for
electrons.
Formyl to Methyl:
2. The formyl group becomes a methyl group with help from
[Link]:
Energy
3. The methyl group moves to Coenzyme M (CoM), releasing
energy to pump sodium (Na⁺).
Methane Formation:
4. The methyl group is turned into methane (CH₄) by an
enzyme, forming a bond between CoM and CoB.
Reset:
5. H₂ breaks the CoM-CoB bond, resetting the cycle.
This is how CO₂ becomes methane while storing energy!
Methanogenesis from
Methylated Compounds
Methanogens can also form CH4 from methylated compounds like
methanol and acetate. Methanol is catabolized by donating
methyl groups to a corrinoid protein, forming CH3–corrinoid. This
complex then transfers the methyl group to CoM, yielding CH3–
CoM, from which methane is formed in the same way as in the
terminal step of CO2 reduction.
Methanogenesis from Acetate
Acetate Breakdown: Acetate (CH₃COO⁻) is split into two parts:
•The methyl group (CH₃-) becomes methane (CH₄).
•The carboxyl group (-COO⁻) becomes carbon dioxide (CO₂).
When acetate is the substrate for methanogenesis, it is first activated to acetyl-CoA, which interacts with CO
dehydrogenase. The methyl group of acetate is then transferred to the corrinoid enzyme to yield CH3–
corrinoid, and from there it goes through the CoM-mediated terminal step of methanogenesis.
Simultaneously, the CO group is oxidized to yield CO2.
Energy Conservation in
Methanogenesis
Energy conservation in methanogenesis occurs at the expense of
a proton or sodium motive force, depending on the substrate
used. When methanogenesis is supported by CO2 + H2, ATP is
produced from the sodium motive force generated during methyl
transfer from MP to CoM. This energized state of the membrane
then drives the synthesis of ATP.
Energy Conservation in
Acetate- and Methanol-
Grown Cells
In acetate- and methanol-grown cells, energy conservation is
linked to the terminal step in methanogenesis, the methyl
reductase step. The interaction of CoB with CH3–CoM and
methyl reductase forms CH4 and a heterodisulfide, CoM-S—S-
CoB. The latter is reduced by F420 to regenerate CoM-SH and
CoB-SH. This reduction, carried out by heterodisulfide
reductase, is exergonic and is coupled to the pumping of H+
across the membrane.
