Vanadium nitrogenase is a key

enzyme Enzymes () are proteins that act as biological catalysts by accelerating chemical reactions. The molecules upon which enzymes may act are called substrates, and the enzyme converts the substrates into different molecules known as products. A ...

for

nitrogen fixation Nitrogen fixation is a chemical process by which molecular nitrogen (), with a strong triple covalent bond, in the air is converted into ammonia () or related nitrogenous compounds, typically in soil or aquatic systems but also in industry. Atmo ...

found in nitrogen-fixing

bacteria Bacteria (; singular: bacterium) are ubiquitous, mostly free-living organisms often consisting of one biological cell. They constitute a large domain of prokaryotic microorganisms. Typically a few micrometres in length, bacteria were among ...

, and is used as an alternative to molybdenum

nitrogenase Nitrogenases are enzymes () that are produced by certain bacteria, such as cyanobacteria (blue-green bacteria) and rhizobacteria. These enzymes are responsible for the Organic redox reaction, reduction of nitrogen (N2) to ammonia (NH3). Nitrog ...

when

molybdenum Molybdenum is a chemical element with the symbol Mo and atomic number 42 which is located in period 5 and group 6. The name is from Neo-Latin ''molybdaenum'', which is based on Ancient Greek ', meaning lead, since its ores were confused with lea ...

is unavailable. Vanadium nitrogenases are an important biological use of

vanadium Vanadium is a chemical element with the symbol V and atomic number 23. It is a hard, silvery-grey, malleable transition metal. The elemental metal is rarely found in nature, but once isolated artificially, the formation of an oxide layer ( pas ...

, which is uncommonly used by life. An important component of the

nitrogen cycle The nitrogen cycle is the biogeochemical cycle by which nitrogen is converted into multiple chemical forms as it circulates among atmospheric, terrestrial, and marine ecosystems. The conversion of nitrogen can be carried out through both biologi ...

, vanadium nitrogenase converts

nitrogen Nitrogen is the chemical element with the symbol N and atomic number 7. Nitrogen is a nonmetal and the lightest member of group 15 of the periodic table, often called the pnictogens. It is a common element in the universe, estimated at se ...

gas to ammonia, thereby making otherwise inaccessible nitrogen available to plants. Unlike molybdenum nitrogenase, vanadium nitrogenase can also reduce

carbon monoxide Carbon monoxide (chemical formula CO) is a colorless, poisonous, odorless, tasteless, flammable gas that is slightly less dense than air. Carbon monoxide consists of one carbon atom and one oxygen atom connected by a triple bond. It is the simple ...

ethylene Ethylene (IUPAC name: ethene) is a hydrocarbon which has the formula or . It is a colourless, flammable gas with a faint "sweet and musky" odour when pure. It is the simplest alkene (a hydrocarbon with carbon-carbon double bonds). Ethylene i ...

ethane Ethane ( , ) is an organic chemical compound with chemical formula . At standard temperature and pressure, ethane is a colorless, odorless gas. Like many hydrocarbons, ethane is isolated on an industrial scale from natural gas and as a petr ...

and

propane Propane () is a three-carbon alkane with the molecular formula . It is a gas at standard temperature and pressure, but compressible to a transportable liquid. A by-product of natural gas processing and petroleum refining, it is commonly used a ...

but both enzymes can reduce

proton A proton is a stable subatomic particle, symbol , H+, or 1H+ with a positive electric charge of +1 ''e'' elementary charge. Its mass is slightly less than that of a neutron and 1,836 times the mass of an electron (the proton–electron mass ...

s to hydrogen gas and

acetylene Acetylene (systematic name: ethyne) is the chemical compound with the formula and structure . It is a hydrocarbon and the simplest alkyne. This colorless gas is widely used as a fuel and a chemical building block. It is unstable in its pure ...

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Biological functions

Vanadium nitrogenases are found in members of the bacterial genus ''

Azotobacter ''Azotobacter'' is a genus of usually motile, oval or spherical bacteria that form thick-walled cysts (and also has hard crust) and may produce large quantities of capsular slime. They are aerobic, free-living soil microbes that play an importan ...

'' as well as the species ''

Rhodopseudomonas palustris ''Rhodopseudomonas palustris'' is a rod-shaped, Gram-negative purple nonsulfur bacterium, notable for its ability to switch between four different modes of metabolism. ''R. palustris'' is found extensively in nature, and has been isolated from ...

'' and ''

Anabaena variabilis ''Anabaena variabilis'' is a species of filamentous cyanobacterium. This species of the genus ''Anabaena'' and the domain Eubacteria is capable of photosynthesis. This species is heterotrophic, meaning that it may grow without light in the presen ...

''. Most of the functions of vanadium nitrogenase match those of the more common molybdenum

s and serve as an alternative pathway for

deficient conditions. Like molybdenum nitrogenase,

dihydrogen Hydrogen is the chemical element with the symbol H and atomic number 1. Hydrogen is the lightest element. At standard conditions hydrogen is a gas of diatomic molecules having the formula . It is colorless, odorless, tasteless, non-toxic, and ...

functions as a

competitive inhibitor Competitive inhibition is interruption of a chemical pathway owing to one chemical substance inhibiting the effect of another by competing with it for binding or bonding. Any metabolic or chemical messenger system can potentially be affected b ...

and

functions as a non-competitive inhibitor of nitrogen fixation. Vanadium nitrogenase has an α₂β₂Ύ₂ subunit structure while molybdenum nitrogenase has an α₂β₂ structure. Though the structural genes encoding vanadium nitrogenase show only about 15% conservation with molybdenum nitrogenases, the two nitrogenases share the same type of iron-sulphur redox centers. At room temperature, vanadium nitrogenase is less efficient at fixing nitrogen than molybdenum nitrogenases because it converts more H⁺ to H₂ as a side reaction. However, at low temperatures vanadium nitrogenases have been found to be more active than the molybdenum type, and at temperatures as low as 5 °C its nitrogen-fixing activity is 10 times higher than that of molybdenum nitrogenase. Like molybdenum nitrogenase, vanadium nitrogenase is easily

oxidized Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or a ...

and is thus only active under

anaerobic Anaerobic means "living, active, occurring, or existing in the absence of free oxygen", as opposed to aerobic which means "living, active, or occurring only in the presence of oxygen." Anaerobic may also refer to: * Anaerobic adhesive, a bonding a ...

conditions. Various bacteria employ complex protection mechanisms to avoid

oxygen Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as wel ...

. The overall stoichiometry of nitrogen fixation catalyzed by vanadium nitrogenase can be summarized as follows: :N₂ + 12e⁻ + 14H⁺ + 24MgATP → 2NH₄⁺ + 3H₂ + 24MgADP + 24HPO₄²⁻ The crystal structure of ''A. vinelandii'' vanadium nitrogenase was resolved in 2017 (). Compared to Mo nitrogenase, V nitrogenase replaces one sulfide in the active site with a bridging ligand.

Carbon monoxide reduction

Research at the

University of California Irvine The University of California, Irvine (UCI or UC Irvine) is a public land-grant research university in Irvine, California. One of the ten campuses of the University of California system, UCI offers 87 undergraduate degrees and 129 graduate and pr ...

showed the ability of vanadium nitrogenase to convert

into trace amounts of

, and

in the absence of nitrogen through the reduction of carbon monoxide by

dithionite The dithionite is the oxyanion with the formula 2O4sup>2−. It is commonly encountered as the salt sodium dithionite. For historical reasons, it is sometimes called hydrosulfite, but it contains no hydrogen and is not a sulfite. The diani ...

and ATP hydrolysis . The process of forming these

hydrocarbons In organic chemistry, a hydrocarbon is an organic compound consisting entirely of hydrogen and carbon. Hydrocarbons are examples of group 14 hydrides. Hydrocarbons are generally colourless and hydrophobic, and their odors are usually weak or ex ...

is carried out through

and

electron The electron ( or ) is a subatomic particle with a negative one elementary electric charge. Electrons belong to the first generation of the lepton particle family, and are generally thought to be elementary particles because they have no kn ...

transfer in which short carbon chains are formed and may ultimately allow the production of hydrocarbon fuel from CO at an industrial scale.

References

{{DEFAULTSORT:Vanadium Nitrogenase Nitrogen cycle Organometallic chemistry Biofuels