Nitrite bacterial oxidation

Denitrification involves the sequential formation of nitrite, nitric oxide, and nitrous oxide. Two aspects of nitric oxide have attracted attention (a) chemical oxidation of biogenic nitric oxide to Nq, in the context of increased ozone formation (Stohl et al. 1996) and (b) the physiological role in mammalian systems (Feldman et al. 1993 Stuehr et al. 2004), in parasitic infections (James 1995), and in the inhibition of bacterial respiration (Nagata et al. 1998). Nitric oxide may be produced microbiologically in widely different reactions such as... 

Betlach, M. R., and Tiedje, J. M. (1981). Kinetic explanation for accumulation of nitrite, nitric oxide, and nitrous oxide during bacterial denitrification. Appl. Environ. Microbiol. 

A question occurs as to why the bacterial enzyme has such a complicated structure, because hydroxylamine is oxidized to nitrite by the catalysis of ferric ion under aerobic conditions. In the nonenzymatic reaction, molecular oxygen is incorporated into nitrite formed by the oxidation of hydroxylamine, while the oxygen atom of water is incorporated into nitrite formed by the enzymatic oxidation of hydroxylamine (see below) (Yamanaka and Sakano, 1980 Andersson and Hooper, 1983). The mechanism in the bacterial oxidation of hydroxylamine will have been devised to reserve efficiently the energy of the reaction for the biosynthesis of adenosine triphosphate (ATP). 

In the enzymatic oxidation of hydroxylamine catalyzed by hydroxylamine oxidoreductase, the electron acceptor for the oxidoreductase, cytochrome c-554, should be kept in the oxidized form as much as possible to accept electrons rapidly from hydroxylamine and NOH. For this purpose, sufficient air should be supplied for the bacteria to oxidize ammonia efficiently. If the air supply is not enough to oxidize hydroxylamine to nitrite, nitrous oxide (N20) occurs during the bacterial oxidation of ammonia (Poth, 1986 Anderson et al., 1993). Probably... 

Most nitrites are soluble in water and mildly toxic. Despite their toxicity, nitrites are used in the processing of meat products because they retard bacterial growth and form a pink complex with hemoglobin that inhibits the oxidation of blood (a reaction that would otherwise turn the meat brown). Nitrites are responsible for the pink color of ham, sausages, and other cured meat. 

An D, DT Gibson, JC Spain (1994) Oxidative release of nitrite from 2-nitrotoluene by a three component enzyme system from Pseudomonas sp strain JS42. J Bacterial 176 7462-7467. 

Sigman et al. [134] have described a bacterial method for measuring the isotopic composition of seawater nitrate at the natural-abundance level. The method is based on the analysis of nitrous oxide gas (N2O) produced quantitatively from nitrate by denitrifying bacteria. The classical denitrification pathway consists of the stepwise reduction of nitrate (NOp to nitrite (N02), nitric oxide (NO), nitrous oxide (N2O), and dinitrogen (N2) ... 

The NO/NO+ and NO/NO- self-exchange rates are quite slow (42). Therefore, the kinetics of nitric oxide electron transfer reactions are strongly affected by transition metal complexes, particularly by those that are labile and redox active which can serve to promote these reactions. Although iron is the most important metal target for nitric oxide in mammalian biology, other metal centers might also react with NO. For example, both cobalt (in the form of cobalamin) (43,44) and copper (in the form of different types of copper proteins) (45) have been identified as potential NO targets. In addition, a substantial fraction of the bacterial nitrite reductases (which catalyze reduction of NO2 to NO) are copper enzymes (46). The interactions of NO with such metal centers continue to be rich for further exploration. 

Since HA is unstable in vivo , and is known to rapidly associate with the heme part of heme proteins , and possibly also with a variety of biological oxidants, such as the superoxide anion that is produced by many mammalian cells, it is difficult to demonstrate its accumulation in vivo. Already in 1932 Lindsey and Rhines discussed some analytical difficulties in the detection of HA, since when added externally, it disappeared rapidly from bacterial cultures this led to the conclusion that even if it is produced as an intermediate, its consumption is too fast to allow the accumulation of sufficient quantities for analytical demonstration. Compelling indirect evidence for the presence of HA as an intermediate in the enzymatically catalyzed reduction of nitrite (N02 ) to NH3 was provided by Einsle and colleagues , who characterized the crystal structure of the complex obtained by soaking cytochrome c-nitrite reductase with NH20H. ... 

Nitrite reductases and nitrous oxide reductases are relatively newly found copper-containing proteins involved in bacterial denitrification. N2O reductase may bear a relationship to cytochrome oxidase and, indeed, parallels it somewhat in function, being the terminal electron acceptor in its pathway. 

Nitric oxide and iron nitrosyl complexes have been observed in the reduction of nitrite by bacterial nitrite reductases, which contain iron chlorin or iron isobac-terichlorin [151]. A specific nitric oxide reductase also exists to convert NO to nitrous oxide [9]. Iron complexes of chlorins, isobacteriochlorins, and porphyrins, as well as ruthenium and osmium polypyridines, and cobalt and nickel... 

Ye, R. W., Arunakumari, A., Averill, B. A., and Tiedje, J. M. (1992a). Mutants of Pseudomonas fluorescens deficient in dissimilatory nitrite reduction are also altered in nitric oxide reduction.). Bacterial. 174, 2560-2564-Ye, R. W., Averill, B. A., and Tiedje, J. M. (1992b). Characterization of Tn5 mutants deficient in dissimilatory nitrite reduction in Pseudomonas sp. strain G-179, which contains a copper nitrite reductase.). Bacteriol. 174, 6653-6658. 

Bacterial assimilatory nitrate reductases have similar properties.86/86a In addition, many bacteria, including E. coli, are able to use nitrate ions as an oxidant for nitrate respiration under anaerobic conditions (Chapter 18). Tire dissimilatory nitrate reductases involved also contain molybdenum as well as Fe-S centers.85 Tire E. coli enzyme receives electrons from reduced quinones in the plasma membrane, passing them through cytochrome b, Fe-S centers, and molybdopterin to nitrate. The three-subunit aPy enzyme contains cytochrome b in one subunit, an Fe3S4 center as well as three Fe4S4 clusters in another, and the molybdenum cofactor in the third.87 Nitrate reduction to nitrite is also on the pathway of denitrification, which can lead to release of nitrogen as NO, NzO, and N2 by the action of dissimi-latory nitrite reductases. These enzymes873 have been discussed in Chapters 16 and 18. 

Biodegradation. The biological mineralization of fixed nitrogen is well studied ammonia is oxidized to nitrite, and nitrite to nitrate, by autotrophic bacteria, and nitrate is reduced to nitrogen by anaerobic bacteria. On the other hand, ammonia and nitrate are essential nutrients for plant and bacterial growth, so one option is to use these organisms to take up and use the contaminants. 

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