In chemistry, a superoxide is a compound that contains the superoxide ion, 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 , which occurs widely in nature. Molecular oxygen (dioxygen) is a diradical containing two unpaired electrons, and superoxide results from the addition of an electron which fills one of the two degenerate molecular orbitals, 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 that exhibit paramagnetism. Superoxide was historically also known as "hyperoxide".
Salts
Superoxide forms salts with alkali metals and alkaline earth metals. The salts caesium superoxide (), rubidium superoxide (), potassium superoxide (), and sodium superoxide () 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 (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 as an oxygen source in chemical oxygen generators, such as those used on the Space Shuttle and on submarines. Superoxides are also used in firefighters' oxygen tanks to provide a readily available source of oxygen. In this process, acts as a Brønsted base, initially forming the hydroperoxyl radical ().
The superoxide anion, , and its protonated form, hydroperoxyl, are in equilibrium in an aqueous solution: O2- + H2O <=> HO2 + OH-
Given that the hydroperoxyl radical has a pKa of around 4.8, superoxide predominantly exists in the anionic form at neutral pH.
Potassium superoxide is soluble in dimethyl sulfoxide (facilitated by crown ethers) and is stable as long as protons are not available. Superoxide can also be generated in aprotic solvents by cyclic voltammetry.
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. It is generated by the immune system to kill invading microorganisms. In phagocytes, superoxide is produced in large quantities by the enzyme NADPH oxidase 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, characterized by extreme susceptibility to infection, especially catalase-positive organisms. In turn, micro-organisms genetically engineered to lack the superoxide-scavenging enzyme superoxide dismutase (SOD) lose virulence. Superoxide is also deleterious when produced as a byproduct of mitochondrial respiration (most notably by Complex I and Complex III), as well as several other enzymes, for example xanthine oxidase, 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 of superoxide: 2 HO2 -> O2 + H2O2 Other proteins that can be both oxidized and reduced by superoxide (such as hemoglobin) have weak SOD-like activity. Genetic inactivation ("knockout") of SOD produces deleterious phenotypes 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, muscle atrophy, cataracts, thymic involution, haemolytic anemia, and a very rapid age-dependent decline in female fertility.