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Table 3 Natural and synthetic biological carbon fixation cycles and pathways. References [145,146,147,148,149,150,151,152,153,154,155,156,157,158,159] were used to compile this table

From: Electrical energy storage with engineered biological systems

Cycle or Pathway

Substrate(s)

Product

ATP requirements

NAD(P)H

Number of substrate molecules

Number of each product

ATPs per substrate molecules

Key enzyme(s)

Specific activity of key enzyme(s) (μmol/min/mg protein)

Note

Reference

Naturally Evolved, Operates Under Aerobic Conditions

 Calvin cycle (CBB) or Reductive pentose phosphate pathway

CO2

Glyceraldehyde-3-phosphate (C3H7O6P)

9

6

3

1

3

A. RuBisCO (EC 4.1.1.39) (e.g. Gossypium hirsutum)

A. 0.01

The dominant autotrophic pathway, which loss of fixed carbon and thus photosynthetic energy by photorespiration.

Bar-even et al. [145], Dietz et al. [146], Claassens et al. [149]

Pyruvate (C3H3O3-)

7

5

2.3

 3-hydroxypropionate bicycle (3HP)

Bicarbonate (HCO3-)

Pyruvate (C3H3O3-)

5

6

3

1

1.6

A. Malonyl-CoA reductase (EC 1.2.1.75) (e.g. Chloroflexus aurantiacus, 55°C, pH 7.8)

A. 10

This pathway occurs only in photosynthetic organisms in non-sulfur bacteria of the Chloroflexaceae family.

Herter et al. [147], Zarzycki et al. [148], Claassens et al. [149]

B. Propionyl-CoA synthase (EC 6.2.1.17) (e.g. Chloroflexus aurantiacus, 55°C, pH 7.8)

B. 2.5

C. Acetyl-CoA carboxylase (EC 6.4.1.2) (e.g. Chloroflexus aurantiacus, 55°C, pH 7.8)

C. 0.015

 3-hydroxypropionate-4-hydroxybutyrate cycle (3HP-4HB)

Bicarbonate (HCO3-)

Acetyl-CoA (C2H3O-CoA)

4

6

2

1

2

A. Acetyl-CoA carboxylase (EC 6.4.1.2) (e.g. Chloroflexus aurantiacus, 55°C, pH 7.8)

A. 0.015

This pathway has been found in hyperthermophilic microorganisms.

Claassens et al. [149], Berg et al. [150]

Pyruvate (C3H3O3-)

5

5

2.5

B. Propionyl-CoA carboxylase (EC 6.4.1.3) (e.g. Metallosphaera sedula, 65°C, pH 7.5)

B. 3.3

Naturally Evolved, Operates Under Anaerobic Conditions

 Reductive Tricarboxylic Acid cycle (rTCA) or Arnon–Buchanan cycle

CO2

Acetyl-CoA (C2H3O-CoA)

2

4

2

1

1

A. Isocitrate dehydrogenase (ICDH) (EC 1.1.1.41) (e.g. Ostreococcus ‘lucimarinus’, 25°C, pH 7.5)

A. 3.8

This pathway is reversible and limited to microorganisms that are difficult to manipulate and engineer.

Claassens et al. [149], Alissandratos et al. [151]

Pyruvate (C3H3O3-)

2

3

1

B. 2-oxoglutarate synthase (EC 1.2.7.3) (r.g. Thauera aromatica, 30°C, pH 7.8)

B. 4.8

 Reductive acetyl-coenzyme A (acetyl-CoA) or Wood-Ljungdahl pathway (WL)

CO2

Acetyl-CoA (C2H3O-CoA)

1

4

2

1

0.5

A. CO dehydrogenase/acetyl-CoA synthase (EC 1.2.7.4) (e.g. Archaeoglobus fulgidus, 65°C, pH 7.5 )

A. 5.2

This reversible pathway is the most energetically favorable autotrophic carbon fixation pathway, but deactivates under ambient CO2 concentration.

Bar-even et al. [145], Claassens et al. [149], Liao et al. [152], Berg et al. [153], Fast et al. [154]

Pyruvate (C3H3O3-)

1

2

0.5

 dicarboxylate/4-hydroxybutyrate cycle (Di-4HB)

Bicarbonate (HCO3-) + CO2

Acetyl-CoA (C2H3O-CoA)

3

1

1 + 1

1

1.5

A. Pyruvate synthase (EC 1.2.7.1) (e.g. Archaeoglobus fulgidus, 65°C, pH 7.5 )

A. 0.7

The microorganisms with this pathway may require an electron acceptor such as elemental sulfur for anaerobic respiration.

Huber et al. [155]

Pyruvate (C3H3O3-)

5

3

2.5

B. 4-hydroxybutanoyl-CoA dehydratase (EC 4.2.1.120) (Clostridium aminobutyricum, 25°C, pH 9)

B. 12.5

 Reversed oxidative Tricarboxylic Acid cycle (roTCA)

CO2

Acetyl-CoA (C2H3O-CoA)

1

N.D

2

1

0.5

A. Reverse oxidative malate dehydrogenase (roMDH) (EC 1.1.1.37) (e.g. Thermoplasma acidophilum)

A. 180

This pathway has been found in two thermophilic bacteria, Desulfurella acetivorans and Thermosulfidibacter.

Mall et al. [156], Nunoura et al. [157]

B. Reverse oxidative citrate synthase (roCS) (EC 2.3.3.16) (e.g. Thermoplasma acidophilum)

B. 0.172

 Reductive hexulosephosphate (RHP) pathway

CO2

Glyceraldehyde-3-phosphate (C3H7O6P)

3

2

1

1

3

A. RuBisCO (EC 4.1.1.39) (e.g. Cupriavidus necator)

A. 1.56

The RHP pathway and the Calvin–Benson cycle only differ in a few steps, namely from F6P to Ru5P, without the release of carbon, but whether the RHP pathway allows for autotrophy remains unknown.

Kono et al. [158]

B. Phosphoribulokinase (PRK) (EC 2.7.1.19) (e.g. Cupriavidus necator)

B. 7.59

Synthetic, Operates Under Aerobic Conditions

 Malonyl-CoA oxaloacetate glyoxylate (MOG)

Bicarbonate (HCO3-)

Glyceraldehyde-3-phosphate (C3H7O6P)

8

6

1

1

8

A. PEP carboxylase (EC 4.1.1.31) (e.g. Escherichia coli)

A. 30

MOG pathway has not been established as functional CO2 fixation pathway yet.

Bar-even et al. [145]

Pyruvate (C3H3O3-)

6

5

6

 Crotonyl–coenzyme A (CoA)/ethylmalonyl-CoA/hydroxybutyryl-CoA (CETCH 5.4)

CO2

Glyoxylate (C2HO3-)

1

4

2

1

0.5

A. Engineered enzymes: succinyl-CoA reductase, methylmalonyl-CoA mutase, ethylmalonyl-CoA mutase, 4-hydroxybutyryl-CoA synthetase

A. 0.05 (total cycle activity)

The 13 core reactions catalyzed by 17 enzymes for the continuous fixation of CO2 in vitro.

Schwander et al. [159]

 HydrOxyPropionyl-CoA/ ACrylyl-CoA (HOPAC)

CO2

Glyoxylate (C2HO3-)

2

3

2

1

1

A. Theoretical network for 12 reactions have been defined, but specific enzyme for each reaction has not been defined.

A. Not measured.

Network reaction for CO2 fixation which has not been synthesized yet.

Schwander et al. [159]

 Crotonyl-CoA/ HYdroxyethylmalonyl-CoA/ MEthylmalonyl-CoA (CHYME)

CO2

Acetaldehyde (C2H4O)

3

6

2

1

1.5

A. Theoretical network for 15 reactions have been defined, but specific enzyme for each reaction has not been defined.

A. Not measured.

Network reaction for CO2 fixation which has not been synthesized yet.

Schwander et al. [159]