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In
chemistry Chemistry is the science, scientific study of the properties and behavior of matter. It is a natural science that covers the Chemical element, elements that make up matter to the chemical compound, compounds made of atoms, molecules and ions ...
, a superoxide is a
compound Compound may refer to: Architecture and built environments * Compound (enclosure), a cluster of buildings having a shared purpose, usually inside a fence or wall ** Compound (fortification), a version of the above fortified with defensive struct ...
that contains the superoxide
ion An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by conve ...
, which has the chemical formula . The systematic name of the anion is dioxide(1−). The reactive oxygen ion superoxide is particularly important as the product of the one-electron reduction of
dioxygen There are several known allotropes of oxygen. The most familiar is molecular oxygen (O2), present at significant levels in Earth's atmosphere and also known as dioxygen or triplet oxygen. Another is the highly reactive ozone (O3). Others are: *A ...
, which occurs widely in nature. Molecular oxygen (dioxygen) is a
diradical In chemistry, a diradical is a molecular species with two electrons occupying molecular orbitals (MOs) which are degenerate. The term "diradical" is mainly used to describe organic compounds, where most diradicals are extremely reactive and in ...
containing two
unpaired electron In chemistry, an unpaired electron is an electron that occupies an orbital of an atom singly, rather than as part of an electron pair. Each atomic orbital of an atom (specified by the three quantum numbers n, l and m) has a capacity to contain ...
s, and superoxide results from the addition of an electron which fills one of the two
degenerate Degeneracy, degenerate, or degeneration may refer to: Arts and entertainment * Degenerate (album), ''Degenerate'' (album), a 2010 album by the British band Trigger the Bloodshed * Degenerate art, a term adopted in the 1920s by the Nazi Party i ...
molecular orbital In chemistry, a molecular orbital is a mathematical function describing the location and wave-like behavior of an electron in a molecule. This function can be used to calculate chemical and physical properties such as the probability of finding ...
s, leaving a charged ionic species with a single unpaired electron and a net negative charge of −1. Both dioxygen and the superoxide anion are
free radicals In chemistry, a radical, also known as a free radical, is an atom, molecule, or ion that has at least one unpaired valence electron. With some exceptions, these unpaired electrons make radicals highly chemically reactive. Many radicals spont ...
that exhibit
paramagnetism Paramagnetism is a form of magnetism whereby some materials are weakly attracted by an externally applied magnetic field, and form internal, induced magnetic fields in the direction of the applied magnetic field. In contrast with this behavior, ...
. Superoxide was historically also known as "hyperoxide".


Salts

Superoxide forms salts with
alkali metal The alkali metals consist of the chemical elements lithium (Li), sodium (Na), potassium (K),The symbols Na and K for sodium and potassium are derived from their Latin names, ''natrium'' and ''kalium''; these are still the origins of the names ...
s and
alkaline earth metal The alkaline earth metals are six chemical elements in group 2 of the periodic table. They are beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and radium (Ra).. The elements have very similar properties: they are al ...
s. The salts
caesium superoxide Caesium superoxide is the superoxide of caesium. It is an orange solid. Preparation Burning caesium in excess oxygen will produce caesium superoxide. : Properties Caesium superoxide's crystal structure is same as calcium carbide. It contains ...
(),
rubidium superoxide Rubidium superoxide or Rubidium hyperoxide is a compound with the formula . In terms of oxidation states, the negatively charged superoxide and positively charged rubidium give it a structural formula of (Rb+)(O2−). Chemistry It can be created ...
(),
potassium superoxide Potassium superoxide is an inorganic compound with the formula KO2. It is a yellow paramagnetic solid that decomposes in moist air. It is a rare example of a stable salt of the superoxide anion. It is used as a scrubber, dehumidifier, and gen ...
(), and
sodium superoxide Sodium superoxide is the inorganic compound with the formula Na O2. This yellow-orange solid is a salt of the superoxide anion. It is an intermediate in the oxidation of sodium by oxygen. Preparation NaO2 is prepared by treating sodium peroxide ...
() are prepared by the reaction of with the respective alkali metal. The alkali salts of are orange-yellow in color and quite stable, if they are kept dry. Upon dissolution of these salts in water, however, the dissolved undergoes
disproportionation In chemistry, disproportionation, sometimes called dismutation, is a redox reaction in which one compound of intermediate oxidation state converts to two compounds, one of higher and one of lower oxidation states. More generally, the term can b ...
(dismutation) extremely rapidly (in a pH-dependent manner): :2 O2- + H2O -> 3/2 O2 + 2 OH- This reaction (with moisture and carbon dioxide in exhaled air) is the basis of the use of
potassium superoxide Potassium superoxide is an inorganic compound with the formula KO2. It is a yellow paramagnetic solid that decomposes in moist air. It is a rare example of a stable salt of the superoxide anion. It is used as a scrubber, dehumidifier, and gen ...
as an oxygen source in
chemical oxygen generator A chemical oxygen generator is a device that releases oxygen via a chemical reaction. The oxygen source is usually an inorganic superoxide, chlorate, or perchlorate; ozonides are a promising group of oxygen sources. The generators are usually igni ...
s, such as those used on the
Space Shuttle The Space Shuttle is a retired, partially reusable low Earth orbital spacecraft system operated from 1981 to 2011 by the U.S. National Aeronautics and Space Administration (NASA) as part of the Space Shuttle program. Its official program na ...
and on
submarine A submarine (or sub) is a watercraft capable of independent operation underwater. It differs from a submersible, which has more limited underwater capability. The term is also sometimes used historically or colloquially to refer to remotely op ...
s. Superoxides are also used in
firefighter A firefighter is a first responder and rescuer extensively trained in firefighting, primarily to extinguish hazardous fires that threaten life, property, and the environment as well as to rescue people and in some cases or jurisdictions also ...
s'
oxygen tank An oxygen tank is an oxygen storage vessel, which is either held under pressure in gas cylinders, or as liquid oxygen in a cryogenic storage tank. Uses Oxygen tanks are used to store gas for: * medical breathing at medical facilities and at home ...
s to provide a readily available source of oxygen. In this process, acts as a Brønsted base, initially forming the
hydroperoxyl The hydroperoxyl radical, also known as the hydrogen superoxide, is the protonated form of superoxide with the chemical formula HO2. This species plays an important role in the atmosphere and as a reactive oxygen species in cell biology. Struc ...
radical (). The superoxide anion, , and its protonated form, hydroperoxyl, are in equilibrium in an
aqueous solution An aqueous solution is a solution in which the solvent is water. It is mostly shown in chemical equations by appending (aq) to the relevant chemical formula. For example, a solution of table salt, or sodium chloride (NaCl), in water would be re ...
: :O2- + H2O <=> HO2 + OH- Given that the hydroperoxyl radical has a p''K''a of around 4.8, superoxide predominantly exists in the anionic form at neutral pH. Potassium superoxide is soluble in
dimethyl sulfoxide Dimethyl sulfoxide (DMSO) is an organosulfur compound with the formula ( CH3)2. This colorless liquid is the sulfoxide most widely used commercially. It is an important polar aprotic solvent that dissolves both polar and nonpolar compounds a ...
(facilitated by
crown ethers In organic chemistry, crown ethers are cyclic chemical compounds that consist of a Ring (chemistry), ring containing several ether groups (). The most common crown ethers are cyclic oligomers of ethylene oxide, the repeating unit being ethyleneo ...
) and is stable as long as protons are not available. Superoxide can also be generated in
aprotic A polar aprotic solvent is a solvent that lacks an acidic proton and is polar. Such solvents lack hydroxyl and amine groups. In contrast to protic solvents, these solvents do not serve as proton donors in hydrogen bonding In chemistry, a hydro ...
solvents by
cyclic voltammetry Cyclic voltammetry (CV) is a type of potentiodynamic electrochemical measurement. In a cyclic voltammetry experiment, the working electrode potential is ramped linearly versus time. Unlike in linear sweep voltammetry, after the set potential is re ...
. Superoxide salts also decompose in the solid state, but this process requires heating: :2 NaO2 -> Na2O2 + O2


Biology

Superoxide and hydroperoxyl () are often discussed interchangeably, although superoxide predominates at physiological pHs. Both superoxide and hydroperoxyl are classified as
reactive oxygen species In chemistry, reactive oxygen species (ROS) are highly reactive chemicals formed from diatomic oxygen (). Examples of ROS include peroxides, superoxide, hydroxyl radical, singlet oxygen, and alpha-oxygen. The reduction of molecular oxygen () p ...
. It is generated by the
immune system The immune system is a network of biological processes that protects an organism from diseases. It detects and responds to a wide variety of pathogens, from viruses to parasitic worms, as well as cancer cells and objects such as wood splinte ...
to kill invading
microorganism A microorganism, or microbe,, ''mikros'', "small") and ''organism'' from the el, ὀργανισμός, ''organismós'', "organism"). It is usually written as a single word but is sometimes hyphenated (''micro-organism''), especially in olde ...
s. In
phagocyte Phagocytes are cells that protect the body by ingesting harmful foreign particles, bacteria, and dead or dying cells. Their name comes from the Greek ', "to eat" or "devour", and "-cyte", the suffix in biology denoting "cell", from the Greek ...
s, superoxide is produced in large quantities by the
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 ...
NADPH oxidase NADPH oxidase (nicotinamide adenine dinucleotide phosphate oxidase) is a membrane-bound enzyme complex that faces the extracellular space. It can be found in the plasma membrane as well as in the membranes of phagosomes used by neutrophil white ...
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 (CGD), also known as Bridges–Good syndrome, chronic granulomatous disorder, and Quie syndrome, is a diverse group of hereditary diseases in which certain cells of the immune system have difficulty forming the reacti ...
, characterized by extreme susceptibility to infection, especially
catalase Catalase is a common enzyme found in nearly all living organisms exposed to oxygen (such as bacteria, plants, and animals) which catalyzes the decomposition of hydrogen peroxide to water and oxygen. It is a very important enzyme in protecting t ...
-
positive Positive is a property of positivity and may refer to: Mathematics and science * Positive formula, a logical formula not containing negation * Positive number, a number that is greater than 0 * Plus sign, the sign "+" used to indicate a posit ...
organisms. In turn, micro-organisms genetically engineered to lack the superoxide-scavenging enzyme
superoxide dismutase Superoxide dismutase (SOD, ) is an enzyme that alternately catalyzes the dismutation (or partitioning) of the superoxide () radical into ordinary molecular oxygen (O2) and hydrogen peroxide (). Superoxide is produced as a by-product of oxygen me ...
(SOD) lose
virulence Virulence is a pathogen's or microorganism's ability to cause damage to a host. In most, especially in animal systems, virulence refers to the degree of damage caused by a microbe to its host. The pathogenicity of an organism—its ability to ca ...
. Superoxide is also deleterious when produced as a byproduct of
mitochondria A mitochondrion (; ) is an organelle found in the Cell (biology), cells of most Eukaryotes, such as animals, plants and Fungus, fungi. Mitochondria have a double lipid bilayer, membrane structure and use aerobic respiration to generate adenosi ...
l
respiration Respiration may refer to: Biology * Cellular respiration, the process in which nutrients are converted into useful energy in a cell ** Anaerobic respiration, cellular respiration without oxygen ** Maintenance respiration, the amount of cellul ...
(most notably by
Complex I Respiratory complex I, (also known as NADH:ubiquinone oxidoreductase, Type I NADH dehydrogenase and mitochondrial complex I) is the first large protein complex of the Electron transport chain, respiratory chains of many organisms from bacteria to ...
and
Complex III Complex commonly refers to: * Complexity, the behaviour of a system whose components interact in multiple ways so possible interactions are difficult to describe ** Complex system, a system composed of many components which may interact with each ...
), as well as several other enzymes, for example
xanthine oxidase Xanthine oxidase (XO, sometimes XAO) is a form of xanthine oxidoreductase, a type of enzyme that generates reactive oxygen species. These enzymes catalyze the oxidation of hypoxanthine to xanthine and can further catalyze the oxidation of xanthin ...
, which can catalyze the transfer of electrons directly to molecular oxygen under strongly reducing conditions. Because superoxide is toxic at high concentrations, nearly all organisms living in the presence of oxygen express SOD. SOD efficiently catalyzes the
disproportionation In chemistry, disproportionation, sometimes called dismutation, is a redox reaction in which one compound of intermediate oxidation state converts to two compounds, one of higher and one of lower oxidation states. More generally, the term can b ...
of superoxide: :2 HO2 -> O2 + H2O2 Other proteins that can be both oxidized and reduced by superoxide (such as
hemoglobin Hemoglobin (haemoglobin BrE) (from the Greek word αἷμα, ''haîma'' 'blood' + Latin ''globus'' 'ball, sphere' + ''-in'') (), abbreviated Hb or Hgb, is the iron-containing oxygen-transport metalloprotein present in red blood cells (erythrocyte ...
) have weak SOD-like activity. Genetic inactivation ("
knockout A knockout (abbreviated to KO or K.O.) is a fight-ending, winning criterion in several full-contact combat sports, such as boxing, kickboxing, muay thai, mixed martial arts, karate, some forms of taekwondo and other sports involving striking, a ...
") of SOD produces deleterious
phenotype In genetics, the phenotype () is the set of observable characteristics or traits of an organism. The term covers the organism's morphology or physical form and structure, its developmental processes, its biochemical and physiological proper ...
s in organisms ranging from bacteria to mice and have provided important clues as to the mechanisms of toxicity of superoxide in vivo.
Yeast Yeasts are eukaryotic, single-celled microorganisms classified as members of the fungus kingdom. The first yeast originated hundreds of millions of years ago, and at least 1,500 species are currently recognized. They are estimated to constitut ...
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 Liver cancer (also known as hepatic cancer, primary hepatic cancer, or primary hepatic malignancy) is cancer that starts in the liver. Liver cancer can be primary (starts in liver) or secondary (meaning cancer which has spread from elsewhere to th ...
,
muscle atrophy Muscle atrophy is the loss of skeletal muscle mass. It can be caused by immobility, aging, malnutrition, medications, or a wide range of injuries or diseases that impact the musculoskeletal or nervous system. Muscle atrophy leads to muscle weakness ...
,
cataracts A cataract is a cloudy area in the lens of the eye that leads to a decrease in vision. Cataracts often develop slowly and can affect one or both eyes. Symptoms may include faded colors, blurry or double vision, halos around light, trouble w ...
, 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 In physics, radiation is the emission or transmission of energy in the form of waves or particles through space or through a material medium. This includes: * ''electromagnetic radiation'', such as radio waves, microwaves, infrared, visi ...
poisoning and hyperoxic injury), and perhaps also to
aging Ageing ( BE) or aging ( AE) is the process of becoming older. The term refers mainly to humans, many other animals, and fungi, whereas for example, bacteria, perennial plants and some simple animals are potentially biologically immortal. In ...
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 organism A model organism (often shortened to model) is a non-human species that is extensively studied to understand particular biological phenomena, with the expectation that discoveries made in the model organism will provide insight into the workin ...
s (yeast, the fruit fly Drosophila, and mice), genetically
knocking out A knockout (abbreviated to KO or K.O.) is a fight-ending, winning criterion in several full-contact combat sports, such as boxing, kickboxing, muay thai, mixed martial arts, karate, some forms of taekwondo and other sports involving striking ...
CuZnSOD shortens lifespan and accelerates certain features of aging: (
cataracts A cataract is a cloudy area in the lens of the eye that leads to a decrease in vision. Cataracts often develop slowly and can affect one or both eyes. Symptoms may include faded colors, blurry or double vision, halos around light, trouble w ...
,
muscle atrophy Muscle atrophy is the loss of skeletal muscle mass. It can be caused by immobility, aging, malnutrition, medications, or a wide range of injuries or diseases that impact the musculoskeletal or nervous system. Muscle atrophy leads to muscle weakness ...
,
macular degeneration Macular degeneration, also known as age-related macular degeneration (AMD or ARMD), is a medical condition which may result in blurred or no vision in the center of the visual field. Early on there are often no symptoms. Over time, however, som ...
, and
thymic involution Thymic involution is the shrinking (involution) of the thymus with age, resulting in changes in the architecture of the thymus and a decrease in tissue mass. Thymus involution is one of the major characteristics of vertebrate immunology, and occ ...
). But the converse, increasing the levels of CuZnSOD, does not seem to consistently increase lifespan (except perhaps in ''
Drosophila ''Drosophila'' () is a genus of flies, belonging to the family Drosophilidae, whose members are often called "small fruit flies" or (less frequently) pomace flies, vinegar flies, or wine flies, a reference to the characteristic of many species ...
''). The most widely accepted view is that oxidative damage (resulting from multiple causes, including superoxide) is but one of several factors limiting lifespan. The binding of by reduced ()
heme Heme, or haem (pronounced / hi:m/ ), is a precursor to hemoglobin, which is necessary to bind oxygen in the bloodstream. Heme is biosynthesized in both the bone marrow and the liver. In biochemical terms, heme is a coordination complex "consisti ...
proteins involves formation of Fe(III) superoxide complex.


Assay in biological systems

The assay of superoxide generated in biological systems is a difficult task because of its high reactivity and short half-life. One approach that has been used in quantitative assays converts superoxide to
hydrogen peroxide Hydrogen peroxide is a chemical compound with the formula . In its pure form, it is a very pale blue liquid that is slightly more viscous than water. It is used as an oxidizer, bleaching agent, and antiseptic, usually as a dilute solution (3% ...
, which is relatively stable. Hydrogen peroxide is then assayed by a fluorimetric method. As a free radical, superoxide has a strong EPR signal, and it is possible to detect superoxide directly using this method when it is abundant enough. For practical purposes, this can be achieved only in vitro under non-physiological conditions, such as high pH (which slows the spontaneous dismutation) with the enzyme
xanthine oxidase Xanthine oxidase (XO, sometimes XAO) is a form of xanthine oxidoreductase, a type of enzyme that generates reactive oxygen species. These enzymes catalyze the oxidation of hypoxanthine to xanthine and can further catalyze the oxidation of xanthin ...
. Researchers have developed a series of tool compounds termed " spin traps" that can react with superoxide, forming a meta-stable radical (
half-life Half-life (symbol ) is the time required for a quantity (of substance) to reduce to half of its initial value. The term is commonly used in nuclear physics to describe how quickly unstable atoms undergo radioactive decay or how long stable ato ...
1–15 minutes), which can be more readily detected by EPR. Superoxide spin-trapping was initially carried out with DMPO, but phosphorus derivatives with improved half-lives, such as DEPPMPO and DIPPMPO, have become more widely used.


Bonding and structure

Superoxides are compounds in which the
oxidation number In chemistry, the oxidation state, or oxidation number, is the hypothetical charge of an atom if all of its bonds to different atoms were fully ionic. It describes the degree of oxidation (loss of electrons) of an atom in a chemical compound. Co ...
of oxygen is −. Whereas molecular oxygen (dioxygen) is a
diradical In chemistry, a diradical is a molecular species with two electrons occupying molecular orbitals (MOs) which are degenerate. The term "diradical" is mainly used to describe organic compounds, where most diradicals are extremely reactive and in ...
containing two
unpaired electron In chemistry, an unpaired electron is an electron that occupies an orbital of an atom singly, rather than as part of an electron pair. Each atomic orbital of an atom (specified by the three quantum numbers n, l and m) has a capacity to contain ...
s, the addition of a second electron fills one of its two
degenerate Degeneracy, degenerate, or degeneration may refer to: Arts and entertainment * Degenerate (album), ''Degenerate'' (album), a 2010 album by the British band Trigger the Bloodshed * Degenerate art, a term adopted in the 1920s by the Nazi Party i ...
molecular orbital In chemistry, a molecular orbital is a mathematical function describing the location and wave-like behavior of an electron in a molecule. This function can be used to calculate chemical and physical properties such as the probability of finding ...
s, leaving a charged ionic species with single unpaired electron and a net negative charge of −1. Both dioxygen and the superoxide anion are
free radicals In chemistry, a radical, also known as a free radical, is an atom, molecule, or ion that has at least one unpaired valence electron. With some exceptions, these unpaired electrons make radicals highly chemically reactive. Many radicals spont ...
that exhibit
paramagnetism Paramagnetism is a form of magnetism whereby some materials are weakly attracted by an externally applied magnetic field, and form internal, induced magnetic fields in the direction of the applied magnetic field. In contrast with this behavior, ...
. The derivatives of dioxygen have characteristic O–O distances that correlate with the order of the O–O bond.


See also

*
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 ...
, O2 *
Ozonide Ozonide is the polyatomic anion . Cyclic organic compounds formed by the addition of ozone () to an alkene are also called ozonides. Ionic ozonides Inorganic ozonides are dark red salts. The anion has the bent shape of the ozone molecule. Inor ...
, *
Peroxide In chemistry, peroxides are a group of compounds with the structure , where R = any element. The group in a peroxide is called the peroxide group or peroxo group. The nomenclature is somewhat variable. The most common peroxide is hydrogen p ...
, *
Oxide An oxide () is a chemical compound that contains at least one oxygen atom and one other element in its chemical formula. "Oxide" itself is the dianion of oxygen, an O2– (molecular) ion. with oxygen in the oxidation state of −2. Most of the E ...
, O2− *
Dioxygenyl The dioxygenyl ion, , is a rarely-encountered oxycation in which both oxygen atoms have a formal oxidation state of . It is formally derived from oxygen by the removal of an electron: :O2 → + e− The energy change for this process is call ...
, *
Antimycin A Antimycin A (more exactly Antimycin A1b) is a secondary metabolite produced by ''Streptomyces'' bacteria and a member of a group of related compounds called antimycins. Antimycin A is classified as an List of extremely hazardous substances, extr ...
– used in fishery management, this compound produces large quantities of this free radical. *
Paraquat Paraquat (trivial name; ), or ''N'',''N''′-dimethyl-4,4′-bipyridinium dichloride (systematic name), also known as methyl viologen, is an organic compound with the chemical formula C6H7N)2l2. It is classified as a viologen, a family of redox ...
– used as a herbicide, this compound produces large quantities of this free radical. *
Xanthine oxidase Xanthine oxidase (XO, sometimes XAO) is a form of xanthine oxidoreductase, a type of enzyme that generates reactive oxygen species. These enzymes catalyze the oxidation of hypoxanthine to xanthine and can further catalyze the oxidation of xanthin ...
– This form of the enzyme xanthine dehydrogenase produces large amounts of superoxide.


References

{{oxygen compounds Anions Oxygen compounds Oxyanions Immune system Free radicals Reactive oxygen species