Nitrogen fixation is the process by which nitrogen is taken from its natural, relatively inert molecular form (N2) in the atmosphere and converted into nitrogen compounds (such as, notably, ammonia, nitrate and nitrogen dioxide) useful for other chemical processes.
Nitrogen fixation is performed naturally by a number of different prokaryotes, including bacteria, actinobacteria, and certain types of anaerobic bacteria. Microorganisms that fix nitrogen are called diazotrophs. Some higher plants, and some animals (termites), have formed associations with diazotrophs.
Biological nitrogen fixation was discovered by the Dutch microbiologist Martinus Beijerinck.
Biological nitrogen fixation
- N2 + 8H+ + 8e− + 16 ATP → 2NH3 + H2 + 16ADP + 16 Pi
Although ammonia (NH3) is the direct product of this reaction, it is quickly protonated into ammonium (NH4+). In free-living diazotrophs, the nitrogenase-generated ammonium is assimilated into glutamate through the glutamine synthetase/glutamate synthase pathway.
In most bacteria, the nitrogenase enzymes are very susceptible to destruction by oxygen (and many bacteria cease production of the enzyme in the presence of oxygen). Low oxygen tension is achieved by different bacteria by: living in anaerobic conditions, respiring to draw down oxygen levels, or binding the oxygen with a protein (e.g. leghaemoglobin). The great majority of legumes have this association, but a few genera (e.g., Styphnolobium) do not.
Non-leguminous nitrogen-fixing plants
Although by far the majority of nitrogen-fixing plants are in the legume family Fabaceae, there are a few non-leguminous plants that can also fix nitrogen. These plants, referred to as actinorhizal plants, consist of 22 genera of woody shrubs or trees scattered in 8 plant families. The ability to fix nitrogen is not universally present in these families. For instance, of 122 genera in the Rosaceae, only 4 genera are capable of fixing nitrogen.
Microorganisms that fix nitrogen
Nitrogen Fixation by Cyanobacteria
Cyanobacteria inhabit nearly all illuminated environments on Earth and play key roles in the carbon and nitrogen cycle of the biosphere. Generally, cyanobacteria are able to utilize a variety of inorganic and organic sources of combined nitrogen, like nitrate, nitrite, ammonium, urea or some amino acids. Several cyanobacterial strains are also capable of diazotrophic growth. Genome sequencing has provided a large amount of information on the genetic basis of nitrogen metabolism and its control in different cyanobacteria. Comparative genomics, together with functional studies, has led to a significant advance in this field over the past years. 2-oxoglutarate has turned out to be the central signalling molecule reflecting the carbon/nitrogen balance of cyanobacteria. Central players of nitrogen control are the global transcriptional factor NtcA, which controls the expression of many genes involved in nitrogen metabolism, as well as the PII signalling protein, which fine-tunes cellular activities in response to changing C/N conditions. These two proteins are sensors of the cellular 2-oxoglutarate level and have been conserved in all cyanobacteria. In contrast, the adaptation to nitrogen starvation involves heterogeneous responses in different strains.
Chemical nitrogen fixation
Nitrogen can also be artificially fixed for use in fertilizer, explosives, or in other products. The most popular method is by the Haber process. This artificial fertilizer production has achieved such scale that it is now the largest source of fixed nitrogen in the Earth's ecosystem.
The Haber process requires high pressures and very high temperatures and active research is committed to the development of catalyst systems that convert nitrogen to ammonia at ambient temperatures. Many compounds can react with atmospheric nitrogen under ambient conditions (eg lithium makes lithium nitride if left exposed), but the products of such reactions are not easily converted into biologically accessible nitrogen sources. After the first dinitrogen complex was discovered in 1965 based on ammonia coordinated to ruthenium ([Ru(NH3)5(N2)]2+), research in chemical fixation focused on transition metal complexes. However, progress has been slow; dinitrogen is a poor ligand and the N-N triple bond is very strong.
The first example of homolytic cleavage of dinitrogen under mild conditions was published in 1995. Two equivalents of a molybdenum complex reacted with one equivalent of dinitrogen, creating a triple bonded MoN complex. The first catalytic system converting nitrogen to ammonia at room temperature and 1 atmosphere was discovered in 2003 and is based on another molybdenum catalyst, a proton source and a strong reducing agent. Unfortunately, the catalytic reduction only undergoes a few turnovers before the catalyst dies.
- Postgate, J (1998). Nitrogen Fixation, 3rd Edition. Cambridge University Press, Cambridge UK.
- Smil, V (2000). Cycles of Life. Scientific American Library.
- Herrero A and Flores E (editor). (2008). The Cyanobacteria: Molecular Biology, Genomics and Evolution (1st ed. ed.). Caister Academic Press. ISBN 978-1-904455-15-8 .
- Chem. Commun. 1965, pp. 621-622
- C. E. Laplaza and C. C. Cummins, Science, 1995, 268, pp 861
- Synthesis and Reactions of Molybdenum Triamidoamine Complexes Containing Hexaisopropylterphenyl Substituents Dmitry V. Yandulov, Richard R. Schrock, Arnold L. Rheingold, Christopher Ceccarelli, and William M. Davis Inorg. Chem.; 2003; 42(3) pp 796 - 813; (Article) doi:10.1021/ic020505l
- Catalytic Reduction of Dinitrogen to Ammonia at a Single Molybdenum Center Dmitry V. Yandulov and Richard R. Schrock Science 4 July 2003: Vol. 301. no. 5629, pp. 76 - 78 doi:10.1126/science.1085326
- The catalyst is based on molybdenum(V) chloride and tris(2-aminoethyl)amine substituted with three very bulky hexa-isopropylterphenyl (HIPT) groups. Nitrogen adds end-on to the molybdenum atom and the bulky HIPT substituents prevent the formation of the stable and nonreactive Mo-N=N-Mo dimer, and the nitrogen is reduced in an isolated pocket. The proton donor is a pyridinium cation which is accompanied by a tetraborate counter ion. The reducing agent is the chromium metallocene CrCp2* where Cp* stands for the pentamethylcyclopentadiene ligand.
- George Washington Carver
- Nitrogen cycle
- Nitrogen deficiency
- Birkeland-Eyde process