Superoxide
Encyclopedia
Redox
Redox reactions describe all chemical reactions in which atoms have their oxidation state changed....
of dioxygen O2, which occurs widely in nature. With one unpaired electron
Electron
The electron is a subatomic particle with a negative elementary electric charge. It has no known components or substructure; in other words, it is generally thought to be an elementary particle. An electron has a mass that is approximately 1/1836 that of the proton...
, the superoxide ion
Ion
An ion is an atom or molecule in which the total number of electrons is not equal to the total number of protons, giving it a net positive or negative electrical charge. The name was given by physicist Michael Faraday for the substances that allow a current to pass between electrodes in a...
is a free radical, and, like dioxygen, it is paramagnetic.
Properties
Superoxides are compounds in which the oxidation numberOxidation number
In coordination chemistry, the oxidation number of a central atom in a coordination compound is the charge that it would have if all the ligands were removed along with the electron pairs that were shared with the central atom. Oxidation numbers are often confused with oxidation states.The...
of oxygen is −½ and the valence
Valence (chemistry)
In chemistry, valence, also known as valency or valence number, is a measure of the number of bonds formed by an atom of a given element. "Valence" can be defined as the number of valence bonds...
½. The O-O bond distance in O2− is 1.33 Å
Ångström
The angstrom or ångström, is a unit of length equal to 1/10,000,000,000 of a meter . Its symbol is the Swedish letter Å....
, vs. 1.21 Å in O2 and 1.49 Å in O22−.
The salts CsO2, RbO2, KO2
Potassium superoxide
Potassium superoxide is the chemical compound with the formula KO2. This rare salt of the superoxide ion is produced by burning molten potassium in pure oxygen...
, and NaO2
Sodium superoxide
Sodium superoxide is the inorganic compound with the formula NaO2. This yellow-orange solid is a salt of the superoxide anion. It is an intermediate in the oxidation of sodium by oxygen....
are prepared by the direct reaction of O2 with the respective alkali metal. The overall trend corresponds to a reduction in the bond order from 2 (O2), to 1.5 (O2−), to 1 (O22−).
The alkali salts of O2− are orange-yellow in color and quite stable, provided they are kept dry. Upon dissolution of these salts in water, however, the dissolved O2− undergoes disproportionation
Disproportionation
Disproportionation, also known as dismutation is used to describe a specific type of redox reaction in which a species is simultaneously reduced and oxidized so as to form two different products....
(dismutation) extremely rapidly:
- 2 O2− + 2 H2O → O2 + H2O2 + 2 OH−
In this process O2− acts as a Brønsted base
Acid-base reaction theories
An acid–base reaction is a chemical reaction that occurs between an acid and a base. Several concepts that provide alternative definitions for the reaction mechanisms involved and their application in solving related problems exist...
, initially forming the radical HO2·. But the pKa
PKA
PKA, pKa, or other similar variations may stand for:* pKa, the symbol for the acid dissociation constant at logarithmic scale* Protein kinase A, a class of cAMP-dependent enzymes* Pi Kappa Alpha, the North-American social fraternity...
of its conjugate acid
Conjugate acid
Within the Brønsted–Lowry acid-base theory , a conjugate acid is the acid member, HX, of a pair of two compounds that transform into each other by gain or loss of a proton. A conjugate acid can also be seen as the chemical substance that releases, or donates, a proton in the forward chemical...
, hydrogen superoxide (HO2·, also known as "hydroperoxyl
Hydroperoxyl
The hydroperoxyl radical, also known as the perhydroxyl radical, is the protonated form of superoxide with the chemical formula HO2.-Reactivity:The superoxide anion, O2−, and the hydroperoxyl radical are in equilibrium in aqueous solution:...
" or "perhydroxy radical"), is 4.88 so that at neutral pH
PH
In chemistry, pH is a measure of the acidity or basicity of an aqueous solution. Pure water is said to be neutral, with a pH close to 7.0 at . Solutions with a pH less than 7 are said to be acidic and solutions with a pH greater than 7 are basic or alkaline...
7 the vast majority of superoxide is in the anionic form, O2−.
Salts also decompose in the solid state, but this process requires heating:
- 2 NaO2 → Na2O2 + O2
This reaction is the basis of the use of potassium superoxide as an oxygen source in chemical oxygen generator
Chemical oxygen generator
A chemical oxygen generator is a device releasing oxygen created by a chemical reaction. The oxygen source is usually an inorganic superoxide, chlorate, or perchlorate. A promising group of oxygen sources are ozonides. The generators are usually ignited mechanically, by a firing pin, and the...
s, such as those used on the space shuttle
Space Shuttle
The Space Shuttle was a manned orbital rocket and spacecraft system operated by NASA on 135 missions from 1981 to 2011. The system combined rocket launch, orbital spacecraft, and re-entry spaceplane with modular add-ons...
and on submarine
Submarine
A submarine is a watercraft capable of independent operation below the surface of the water. It differs from a submersible, which has more limited underwater capability...
s. Superoxides are also used in firefighter
Firefighter
Firefighters are rescuers extensively trained primarily to put out hazardous fires that threaten civilian populations and property, to rescue people from car incidents, collapsed and burning buildings and other such situations...
s' oxygen tank
Oxygen tank
An oxygen tank is a storage vessel for oxygen, which is either held under pressure in gas cylinders or as liquid oxygen in a cryogenic storage tank.Oxygen tanks are used to store gas for:* industrial processes including the manufacture of steel and monel...
s in order to provide a readily available source of oxygen.
Biology
Superoxide is biologically quite toxic and is deployed by the immune systemImmune system
An immune system is a system of biological structures and processes within an organism that protects against disease by identifying and killing pathogens and tumor cells. It detects a wide variety of agents, from viruses to parasitic worms, and needs to distinguish them from the organism's own...
to kill invading microorganism
Microorganism
A microorganism or microbe is a microscopic organism that comprises either a single cell , cell clusters, or no cell at all...
s. In phagocyte
Phagocyte
Phagocytes are the white blood cells that protect the body by ingesting harmful foreign particles, bacteria, and dead or dying cells. Their name comes from the Greek phagein, "to eat" or "devour", and "-cyte", the suffix in biology denoting "cell", from the Greek kutos, "hollow vessel". They are...
s, superoxide is produced in large quantities by the enzyme
Enzyme
Enzymes are proteins that catalyze chemical reactions. In enzymatic reactions, the molecules at the beginning of the process, called substrates, are converted into different molecules, called products. Almost all chemical reactions in a biological cell need enzymes in order to occur at rates...
NADPH oxidase
NADPH oxidase
The NADPH oxidase is a membrane-bound enzyme complex. It can be found in the plasma membrane as well as in the membrane of phagosome.-Subunits:It is made up of six subunits...
for use in oxygen-dependent killing mechanisms of invading pathogens. Mutations in the gene coding for the NADPH oxidase cause an immunodeficiency syndrome called chronic granulomatous disease
Chronic granulomatous disease
Chronic granulomatous disease is a diverse group of hereditary diseases in which certain cells of the immune system have difficulty forming the reactive oxygen compounds used to kill certain ingested pathogens...
, characterized by extreme susceptibility to infection, especially catalase positive organisms. In turn, micro-organisms genetically engineered to lack superoxide dismutase
Superoxide dismutase
Superoxide dismutases are a class of enzymes that catalyze the dismutation of superoxide into oxygen and hydrogen peroxide. As such, they are an important antioxidant defense in nearly all cells exposed to oxygen...
(SOD), lose virulence
Virulence
Virulence is by MeSH definition the degree of pathogenicity within a group or species of parasites as indicated by case fatality rates and/or the ability of the organism to invade the tissues of the host. The pathogenicity of an organism - its ability to cause disease - is determined by its...
. Superoxide is also deleteriously produced as a byproduct of mitochondrial respiration
Cellular respiration
Cellular respiration is the set of the metabolic reactions and processes that take place in the cells of organisms to convert biochemical energy from nutrients into adenosine triphosphate , and then release waste products. The reactions involved in respiration are catabolic reactions that involve...
(most notably by Complex I and Complex III), as well as several other enzymes, for example xanthine oxidase
Xanthine oxidase
Xanthine oxidase Xanthine oxidase Xanthine oxidase (XO (sometimes 'XAO'), a form of xanthine oxidoreductase that generates reactive oxygen species. Is an enzyme that catalyzes the oxidation of hypoxanthine to xanthine and can further catalyze the oxidation of xanthine to uric acid...
.
Because superoxide is toxic, nearly all organisms living in the presence of oxygen contain isoforms of the superoxide scavenging enzyme, superoxide dismutase
Superoxide dismutase
Superoxide dismutases are a class of enzymes that catalyze the dismutation of superoxide into oxygen and hydrogen peroxide. As such, they are an important antioxidant defense in nearly all cells exposed to oxygen...
, or SOD. SOD is an extremely efficient enzyme; it catalyzes the neutralization of superoxide nearly as fast as the two can diffuse together spontaneously in solution. Other proteins, which can be both oxidized and reduced by superoxide, have weak SOD-like activity (e.g. hemoglobin). Genetic inactivation ("knockout") of SOD produces deleterious phenotype
Phenotype
A phenotype is an organism's observable characteristics or traits: such as its morphology, development, biochemical or physiological properties, behavior, and products of behavior...
s in organisms ranging from bacteria to mice and have provided important clues as to the mechanisms of toxicity of superoxide in vivo.
Yeast lacking both mitochondrial and cytosolic SOD grow very poorly in air, but quite well under anaerobic conditions. Absence of cytosolic SOD causes a dramatic increase in mutagenesis and genomic instability.
Mice lacking mitochondrial SOD (MnSOD) die around 21 days after birth due to neurodegeneration, cardiomyopathy and lactic acidosis. Mice lacking cytosolic SOD (CuZnSOD) are viable but suffer from multiple pathologies, including reduced lifespan, liver cancer
Hepatocellular carcinoma
Hepatocellular carcinoma is the most common type of liver cancer. Most cases of HCC are secondary to either a viral hepatitide infection or cirrhosis .Compared to other cancers, HCC is quite a rare tumor in the United States...
, muscle atrophy
Muscle atrophy
Muscle atrophy, or disuse atrophy, is defined as a decrease in the mass of the muscle; it can be a partial or complete wasting away of muscle. When a muscle atrophies, this leads to muscle weakness, since the ability to exert force is related to mass...
, cataracts, thymic involution, haemolytic anemia and a very rapid age-dependent decline in female fertility.
Superoxide may contribute to the pathogenesis of many diseases (the evidence is particularly strong for radiation
Radiation
In physics, radiation is a process in which energetic particles or energetic waves travel through a medium or space. There are two distinct types of radiation; ionizing and non-ionizing...
poisoning and hyperoxic
Hyperoxia
Hyperoxia is excess oxygen or higher than normal partial pressure of oxygen.In medicine, it refers to excess oxygen in the lungs or other body tissues, which can be caused by breathing air or oxygen at pressures greater than normal atmospheric pressure...
injury), and perhaps also to aging via the oxidative damage that it inflicts on cells. While the action of superoxide in the pathogenesis of some conditions is strong, for instance, mice and rats overexpressing CuZnSOD or MnSOD are more resistant to strokes and heart attacks, the role of superoxide in aging must be regarded as unproven for now. In model organisms (yeast, the fruit fly Drosophila and mice), genetically knocking out
Gene knockout
A gene knockout is a genetic technique in which one of an organism's genes is made inoperative . Also known as knockout organisms or simply knockouts, they are used in learning about a gene that has been sequenced, but which has an unknown or incompletely known function...
CuZnSOD shortens lifespan and accelerates certain features of aging (cataracts, muscle atrophy
Muscle atrophy
Muscle atrophy, or disuse atrophy, is defined as a decrease in the mass of the muscle; it can be a partial or complete wasting away of muscle. When a muscle atrophies, this leads to muscle weakness, since the ability to exert force is related to mass...
, macular degeneration
Macular degeneration
Age-related macular degeneration is a medical condition which usually affects older adults and results in a loss of vision in the center of the visual field because of damage to the retina. It occurs in “dry” and “wet” forms. It is a major cause of blindness and visual impairment in older adults...
, thymic involution
Thymic involution
One of the major characteristics of vertebrate immunology is thymic involution, the shrinking of the thymus with age, resulting in changes in the architecture of the thymus and a decrease in tissue mass...
), but the converse, increasing the levels of CuZnSOD, does not seem (except perhaps in Drosophila
Drosophila
Drosophila is a genus of small flies, belonging to the family Drosophilidae, whose members are often called "fruit flies" or more appropriately pomace flies, vinegar flies, or wine flies, a reference to the characteristic of many species to linger around overripe or rotting fruit...
), to consistently increase lifespan. The most widely accepted view is that oxidative damage (derived amongst other factors, from superoxide) is but one of several factors limiting lifespan.
See also
- OzonideOzonideOzonide is an unstable, reactive polyatomic anion O3−, derived from ozone, or an organic compound similar to organic peroxide formed by a reaction of ozone with an unsaturated compound.-Inorganic ozonides:...
, O3− - PeroxidePeroxideA peroxide is a compound containing an oxygen–oxygen single bond or the peroxide anion .The O−O group is called the peroxide group or peroxo group. In contrast to oxide ions, the oxygen atoms in the peroxide ion have an oxidation state of −1.The simplest stable peroxide is hydrogen peroxide...
, O22− - OxideOxideAn oxide is a chemical compound that contains at least one oxygen atom in its chemical formula. Metal oxides typically contain an anion of oxygen in the oxidation state of −2....
, O2− - DioxygenylDioxygenylThe dioxygenyl ion, O2+, is a rarely encountered oxycation in which both oxygen atoms have a formal oxidation state of +½. It is formally derived from oxygen by the removal of an electron:...
, O2+ - Antimycin AAntimycin AAntimycins are a group of secondary metabolites produced by Streptomyces bacteria.-Uses:It is the active ingredient in Fintrol, a chemical piscicide used in fisheries management and in the catfish industry.-Mechanism of action:...
- used in fishery management, this compound produces large quantities of this free radical. - ParaquatParaquatParaquat is the trade name for N,N′-dimethyl-4,4′-bipyridinium dichloride, one of the most widely used herbicides in the world. Paraquat, a viologen, is quick-acting and non-selective, killing green plant tissue on contact. It is also toxic to human beings and animals...
- used as an herbicide, this compound produces large quantities of this free radical.